Document 44vNeZ0jG4G0ZvOE6xjjp5qVR

Mr. A. B. Cftiwis UCC Clefins Division 28th floor - N. Y. Mr. J. M. Bilderback January 16, 1967 Aerosol Booklet Dear Mr. Chiwis; Enclosed is a revision of the aerosol booklet that was put together about a year ago. The Appendix, which made tip nearly half of die previous work, has been removed; the introduction has been redone and some Silicones formulations have been added. Assorted other corrections and changes have been made throughout die text. On Page 11 mention is made of methylene iodide as an Inhibitor. The purpose here is to provide public disclosure of methyleneYas an inhibitor so as to preclude anyone else patenting it. It would be appreciated if you would review the booklet and, if you think it could be used to advantage, please send it on to Mr. Klderfaack for his review and comments also. Very truly yours RJ Scott/eao Enclosure BLAND/UCC 358 J AEROSOL HANDBOOK (Hex) UCON Aerosol Chemicals BLAND/UCC 359 XERO COPY c.Jf T? mtfttiitMirniVifl t VfJril-tyj-rWflftfrffiiirfri ^liWttftllW : i - >*> .igtlV.H i-f .............. ., r~\ vy X#Ot copy f \ TABLE OF CONTENTS I. INTRODUCTION A, What is an Aerosol? B, Types of Aerosol Systems C. Propellants D. Containers E, Valves F. Filling II. PROPELLANTS A. Fluorocarbons B. Hydrocarbons C. Dimethyl Ether and Vinyl Chloride D. Specialty Blends 1. UCON Fragrance Propellant 2. UCON Vinyl Chloride Blend 3. UCON Propellant A 4. UCON Paint Propellant E. Azeotropes F. Compressed Gases III. WATER-BASED SYSTEMS IV. FORMULATIONS A. Adhesive B. Dust Mop Spray C. Foam for Pharmaceuticals ysrr*~' ` *r Page 1 4 6 7 8 9 11 11 13 16 18 :i8 18 18 18 22 23 27; 28 32 33 34 BLAND/UCC 360 [| xCOwPoYl J&Mt, >- --J^-=--. 1 D. Flowering Fertilizer E. Furniture Polish F. Hair Spray G. Hand Cleaner and Ink Stain Remover H. Paint Brush Conditioner and Preservative I. Personal Deodorant J. (Jfuick-Breaking Foam K. Spray Starch L. Touch-Up Floor Polish M. Wax for Wood Floors N. Window Cleaner V. THE AEROSOL LABORATORY VI. PRELIMINARY DESIGN OF AN AEROSOL FILLING LINE VII. STORAGE AND HANDLING VIII. BIBLIOGRAPHY IX. GENERAL APPENDIX A. Dimethyl Ether/Fluoroearbon Aerosol Propellant Blend B. Vinyl Chloride/Fluorocarbon Aerosol Propellant Blend C. Hydrocarbon/Fluorocarbon Aerosol Propellant Blend D. General Equations for Calculating the Composition of Aerosol Propellant Blends of Intermediate Pressures E. UCON Propellant 12/llr Vapor Pressure vs. Temperature F. UCON Propellant A and Vinyl Chloride Blend Vapor Pressure vs. Temperature ii Page 36 38 39 39 41 42 43 44 45 46 47 48 50 78 98 mv 1 ~~ ` BLANO/UCC 361 xr.ftoi {COPT ( ' rr G. UCON Propellant A and Vinyl Chloride Blend - Density vs. Temperature H. UCON Propellant 12/Propane 90/10 - Vapor Pressure vs. Temperature I. UCON Propellant 12/Propane 90/10 - Specific Gravity vs. Temperature J. UCON Propellant 12/Isobutane - Specific Gravity vs. Composition K. UCON Propane/Isobutane Blends - / Vapor Pressure vs. Composition L. UCON Hydrocarbon Propellants - Vapor Pressure vs. Temperature M. Azeotropic Aerosol Propellants N. A Basic System for Water-Based Products O. Equipment Suppliers ill Page BLAND/UCC 362 ,;a.- iv important Unton Carbide is a supplier of a complete line of propellants and chemicals to the aerosol industry. Fluorocarbons, hydrocarbons, vinyl chloride, dimethyl ether, specialty blends, compressed gases, alcohol, solvents, and other materials are available from this single source. Their use varies widely over a range of nineteen categories of aerosol products, as differentiated by the CSMA, Which propellant, solvent or other component is to be used in a given instance depends upon the product itself. This book does not cover the technology of all of the products involved in the nineteen categories, but basic technology is presented which can be helpful in aolving formulation and product development prob lems. In addition, the resources of Union Carbide are available to you for further assistance. BLAND/UCC 363 1 XF-0* ) copr ` u" * .1 ,'CKQERPO*:f I. INTRODUCTION A, What Is an Aerosol? Scientifically, an aerosol is a suspension of fine solid or liquid particles in air or gas. However, the term is now used for practically any product dispensed from a container by means of self-contained pres sure, e.g. hair sprays, starch, shave cream, etc. All aerosols have at least one common denominator - product is dispensed by means of a propellant acting as the force to drive the contents through the valve and out of the container. The propellant can be either a liquefied or a compressed gas, but the spray charac teristics of the product depend to a considerable extent on which is used. In the case of a liquefied gas there exists a kinetic equilibrium between liquid and vapor when the pressure in the container equals the vapor pressure of the liquid phase at any given temperature. In other words, molecules are constantly leaving the liquid in the form of vapor. The accumulated molecules of vapor exert a pressure within the container and the pressure continues to increase until the pressure in the container equals the vapor pressure-of the liquid at the given temperature. At that point, the number of molecules of propellant that leave the liquid phase is equalled by the number of molecules that are returned from the vapor phase to the liquid; hence, a state of equilibrium. When the contents are dispensed, there is an increase in head space, with a resulting momentary decrease in pressure. This lowered pressure . lessens the return of the molecules of propellant vapor to the liquid ssr^T 364bland/ucc f ; ropf phase until the pressure in the container again reaches the inherent vapor pressure. The transition takes place instantaneously, so that there is no measurable drop in pressure. Thus, with a liquified gas, the pressure inside the container remains constant as the product is used, and the spray characteristics are not significantly changed. If the propellant is dissolved in a product (commonly referred to as the "concentrate"), the same considerations apply, except that the vapor, pressure is usually lower than for pure propellant, in accordance with the basic laws of physical chemistry. In the case of compressed gases such as carbon dioxide or nitrous oxide, the situation is somewhat different, since there is no liquid phase of propellant to provide a reservoir of pressure. As the product is sprayed, the headspace inside the container increases, and the pres sure decreases. At best, this is only partially offset from vaporization of the small quantity of gas dissolved in the concentrate, so that the pressure inside the container gradually drops as the product is used. Products pressurized with compressed gases usually have coarse sprays which become more so with use, and these propellants are generally used where spray characteristics are not critical (e.g., engine starters, windshield de-icers, etc.). Compressed gases have a unique advantage, however, in that their pressure does not change with temperature as much as that of the liquefied gases. For example, a container pressurized with carbon dioxide to 70 psig at 70F. will have a pressure of approximately 65 psig at 32F,, whereas propellant 12, with a vapor pressure of 70 psig at 70F., exerts only 30 psig at 32F., and exerts no pressure at BLAND/UCC  Ml r IT r n jffjl I "gr^lfnfn'|!Sl|] irr>fiilMll I'i III Yir.i'Atr*n iHiiMrii n ife. SfL. 3 all below its boiling point C-22P.). Thus, compressed gases can be used for products at low temperatures where;lique.fied gases could not function. '1 jxRO| { COPYj 366bland/ucc f; XCOEPRYol' --uii ii^ j iii'ii ftlf'nffifau.pint .& j~*ii i~ ifffi AplfgfrjSjfclj* 4 B. Types of Aerosol Systems Aerosols can be classified into two-phase and three-phase systems. The term "two-phase" refers to propellant vapor in equilibrium with a single-phase liquid solution of propellant and concentrate; it is commonly applied to liquefied gases, but can also include compressed gases. A three-phase system consists of propellant vapor in equilibrium with two liquid phases. A pressurized emulsion, for example, consists of a vapor phase and two liquid phases, one dispersed in the other. The propellant itself can form the nonaqueous phase of the emulsion, or it may be dis solved in the material constituting the nonaqueous phase. (All of the common propellants, with the exception of dimethyl ether, are virtually insoluble in water.) To obtain a fine spray, it is usually necessary to use a two-phase system with a high propellant content. With such an arrangement, the mechanical atomization produced by the valve as the liquid phase passes through it is augmented by instantaneous evaporation of the propellant. The atomized droplets literally explode into smaller droplets, which form a fine spray. This fineness of spray allows a rapid and wide disper sion of product mist which tends to remain suspended in the air, in accordance with the definition of a true aerosol. Not all two-phase systems produce fine sprays, however, because low propellant content, the use of compressed gases, or large valve orifices can result in sprays of varying coarseness and wetness. Three-phase systems usually produce coarse sprays, because the only atomization provided is that contributed mechanically by the valve. i^-s^r v . ! ijtij. , i.Mfii'li&illii ftlafc. 5 The spray can be made finer by incorporation of a "vapor tap" (a small orifice in the valve body which allows vapor from the headspace to be mixed with the liquid stream as it flows through the passageways of the valve), or by devising a water-in-propellant emulsion, which is a means for drawing propellant into the spray. These methods produce a finer spray than could be obtained without them, but the degree of fineness is seldom near that obtainable from a two-phase system. Products such as starches, furniture polishes, or window cleaners often utilizethree-phase systems with coarse Cor "residual") sprays since the objec tive is simply to deposit the product on the surface where it is to be used. It might be noted at this point that vapor tap valves cannot be used with compressed gases because the vapor tap would permit loss of gas and, since there is no reservoir to replace that removed, the pressure will drop rapidly. BLAND/UCC 368 6 C. Propellants The halocarbons, such as trichloromonofluoromethane and dichlorodifluoromethane, are the most widely employed propellants because of their low toxicity and complete nonflammability, but hydrocarbons Cfor example propane and Isobutane) are also used, either alone or in combination with the halocarlTons. The advantages of hydrocarbons are their comparatively low cost, resistance to hydrolysis, and low specific gravity. However, safety measures are required in the handling of hydrocarbon propellants, because they are flammable. Compressed gases are limited to COj, N^O, and Both CO^ and NjO are soluble in many materials. However, since CO^ is an acid anhydride, it is not aften used with aqueous products. N2 exhibits very little solubility and has only limited application. I I BLAND/UCC 369 D. Containers Container choice involves such considerations as product type, corrosion factors, consumer appeal, and cost. Metal cans are generally used for products that exceed 25 psig internal pressure. Two types of metal containers are available: the extruded or seamless type, which has as ICC limit of 70 psig, and the rolled or solder-seam type, which is limited to 40 psig. Tin plate and aluminum are the metals most commonly used. In recent years, glass containers have come into prominence, particularly for cosmetic and pharmaceutical products. Glass aerosol containers are available in both uncoated and plastic-coated types. The uncoated is suitable for internal pressures up to 15 psig, and the coated for pressures up to 25 psig. More recently, all-plastic containers molded or extruded from several types of plastic have been made available for aerosol use. XERO ^ COPY BLAND/UCC 370 !r\ XCEORP' OYii I K i^'ii'iii itoiiiirf1lttrT^ii?^MiViilflhMi'$(-ii-uli II1 II iff M`i^r *--- li.i ftwTAiJi. 8 E. Valves: Aerosol valve mechanisms are many and varied, and several hundred patents have been issued on them. The reason for such diversity is the fact that aerosol valves do much more than perform a simple on-and-off function. They must also atomize and produce a uniform spray. Although there are many variations in valve design, the basic segments are the same: an entrance orifice into the valve, an expansion chamber, and an exit orifice covered by a gasket to perform the on-and-off function. A diptube extending to the bottom of the can is attached to the entrance -orifice (unless the container is to be used in an inverted position, and an actuator button is attached to the exit stem. The size of the exit orifice of the valve and actuator largely determine the degree of /'"'v atomization. Metering valves, which deliver an equal volume at each actuation, are often used with products such as pharmaceuticals and perfumes where continuous discharge is unnecessary or undesirable. Most metering valves are based on the "aerosol-within-an-aerosol" concept, where a quantity of propellant-concentrate solution is isolated in a valve chamber, and its own vapor pressure is then used to eject it. This means that two-phase, liquefied gas systems must be used, since a com pressed gas or a three-phase system (except for emulsions) would not carry propellant into the isolated chamber. Metering systems for the compressed gas or three-phase system are available in the form of rising ball check valves, which are placed in the diptube, but these are not widely used. KCTOl copr } i'XERO] ri?OPyJw BLAND/UCC 371 " p7 ' 9 F* Filling Aerosol containers can be pressurized in three ways: 1) Pressure filling by forcing the propellant through the valve after the container is sealed; 2) Cold filling by chilling the propellant and other compo nents below the,boiling point and pouring them into the container before it is sealed, and, 3) "Under-the-Cap" pressure filling, wherein the valve is lifted off the container, propellant is forced under it, and the valve is then crimped on. The third method is receiving increasing acceptance in the industry, gradually displacing the more expensive cold filling technique. The first method is the mo3t suitable when filling low concentrations of propellant. BLAND/UCC 372 10 There is a large amount of literature availble on aerosol technol- ogy. In addition to texts (1 ' 2) , trade publications such as "Aerosol Age" and "Soap and Chemical Specialties" regularly carry articles of both technical and marketing interest. Publications by suppliers to the industry are further sources of technical information. J rKERO copy i: to* BLAND/UCC 373 V ^ ITT I CXCORPOY*\ &T 11 II. PROPELLANTS A. Fluorocarbons The so-called fluorocarbons are halogenated derivatives of methane and ethane and are the principal propellants for the aerosol industry. The UCQN fluorocarbon propellants are inert, nonflammable, non-toxic, and can meet the pressure requirements of almost any product. They are chemically and thermally stable, although the stability varies somewhat among the members of the group. Their pertinent physical properties are given in Table I. BLAND/UCC 374 | ........S-i---..^y r.L--"-'fi '-----J .-me..r- .t~ ^ Tjs,-jgi .,S.-^X* *,u mi TABLE I Physical Properties of Ucon Fluorocarbon Propellants 12 Name Formula or Composition Ucon 11 cci3f Ucon 12 cci2f2 Ucon 22 chcif2 Ucon 113 cci2f-ccif2 Ucon 114 ccif2-ccif, {\ V^' Molecular Weight 137.4 120.9 86.5 Boiling Pt, at atmos. pressure F. 74.8 C. 23.8 -21,6 -29.8 -41.3 -40.8 Liquid Density-lb./gal. at 70F. <21C. ) 12,4 11.1 10.1 Liquid Density-lb./cu. ft. at 70F. (21C,) 92.7 82.7 75.5 at 130F. (55C. ) 87.6 74.4 66.4 Liquid Density-g./c.c. at 70f, (21C.) at 130F. (55C. ) 1.49 1.40 1.33 . 1.19 1.21 1.06 Solubility of Water in Ucon Propellant-% by wt. at 70f. (21C. ) at 32F. (0 C.) 0.009 0,0036 0.008 0.0024 .114 -- Vapor Pressure at 70F. (21C.>, psig. _ Explosive Limits-% by vol. in air 70.1 123.3 Upper Lower NonFlam mable NonFlam. mable NonFlam mable 187.4 117.6 47.1 13.2 98.3 93.2 1.58 1.50 0.009 0.0036 tmm.-- NonFlam mable 170.9 38.4 3.6 12.3 91.6 84.9 1.47 1.36 0.007 0.0026 12.9 NonFlam mable f CXCORPOY|I iXEROl ;COPY| ?s* W5 BLAND/UCC 375 I xr.poi ]COPY 7-- / iiftiiAwii, 13 B. Hydrocarbons UCON isobutane, UCON propane, and their blends are odorless, non- ^ corrosive saturated hydrocarbons. Comparatively nontoxic, they are "generally recognized as safe" by the United States Food and Drug Administration. Further, they are stable and entirely compatible with' fluorocarbon propellants, UCON hydrocarbons are extremely pure in com parison to refinery stocks, which contain sulfur compounds and varying amounts of unsaturated hydrocarbons, which possess strong, characteris tic odors, and which may react with other ingredients in an aerosol formulation. The physical properties of UCON hydrocarbon propellants are given in Table II. < BLAND/UCC 376 mr--i `liUhnfflfy- --- - TABLE II Physical Properties of Ucon Hydrocarbon Propellants m imj _ i^i UCON Isobutane UCON Isobutane is a colorless, easily liquefied gas. It is virtually insoluble in water, slightly soluble in alcohol, and quite soluble in ether. It is shipped as a colorless, liquefied gas under its own vapor pressure of 30.7 psig at 70P. UCON Propane UCON Propane is a gas at atmospheric pressure and normal temperatures and is colorless in both its gaseous and liquid phases. It is soluble In ether and alcohol, and virtually insoluble in water. Propane is shipped as a liquefied gas under its own vapor pressure of 110 psig at 70f. PHYSICAL PROPERTIES UCON Isobutane Formula Molecular Weight C4H10 58.120 Boiling Point at 14.696 psla 10.9F. Freezing Point at 14.696 psta -255.3F. ^ Specific Gravity, Liquid, at 60/60F. 0.5631 ^J Weight/Gal., Liquid, at 60F. 4.685 lb. Specific Gravity, Gas, (Air = 1) 2.066 Volume of Vapor/Lb., at 60F. and 14.696 psia 6.339 cu. ft. Volume of Vapor/Gal, Liquid, at 60F. and 14. 696 psia 29.70 cu, ft. Ratio, Gas Volume/Liquid Volume at 60F. and 14.696 psia 222.1 Critical Temperature 275.0F. Critical Pressure 529 psia Autoignition Temperature 1010F. Coefficient of Liquid Expansion at 60p. 0.0012 Solubility in Water in, at 70F. 0.0073% by wt. Solubility in Water at 70F. 0.0085% by wt. Surface Tension at 70F. 10.05 dynes/cm. Toxicity, U. L. rating system 5. UCON Propane C3H8 44.094 -43.7F. -305.8F. 0.5077 4.224 lb. 1.522 8.471 cu. ft 35.78 cu. ft 267.6 206.3F. 617 psia 874F. 0.0016 0.016% by wt. 0.007% by wt. 7.0 dynes/cm. 5. SB rrr^ bland/ucc 377 t xeROi j COPYr ------------------r  15 TABLE II (continued) UCON Blend (90-10) UCON Blend (90-10) is a combination consisting of 89.5 per cent isobutane and 10.5 per cent propane, by weight. This special blend complies with the Interstate Commerce Commission Regulations, Tariff No. 13, Article 73.302(a) (3), for regular metal containers, filled to a pressure not in excess of 55 psia at 70F. UCON Blend (90-10) is shipped as a liquefied gas under its own vapor pressure of 40 psig at 70F. UCON Blend (84-16) UCON Blend (84-16) is a combination consisting of 84.1 percent iso butane and 15.9 per cent propane by weight. This blend has a vapor pressure of 46 psig at 70F. PHYSICAL PROPERTIES UCON Blend (90-10) (84-16) Weight Per Cent, Isobutane 89.5 84.1 Weight Per Cent, Propane ' 10.5 15.9 Mol Per Cent, Isobutane 87 80 Mol Per Cent, Propane Liquid Volume Per Cent, Isobutane, at 70F. Liquid Volume Per Cent, Propane, at 70F. Specific Gravity, Liquid, at 60/60F. 13 88.5 11.5 0.557 20 82.7 17.3 0.554 XERO COPT *" ; bland/ucc 378 | XF.*Ol COPT 16 C. Dimethyl Ether and Vinyl Chloride Dimethyl ether and vinyl chloride are not used by themselves to any great extent, but they are used in mixtures as discussed below. Their physical properties are listed in Table III. XERO ^ COPY bland/ucc 379 XEBOfc af copr I - - |-[ |!| fiy wafe^j.-^r-attearWh'* 17 TABLE III Physical Properties of UCON Vinyl Chloride and UCON Dimethyl Ether Name UCON Vinyl Chloride Formula or Composition Molecular Weight CH^CHCl 62,5 Boiling Point at atmospheric pressure F. 7.0 C. -13.4 Liquid Density-lb./gal. at 70F. (21C. ) 7.6 * UCON Dimethyl Ether CH3--CH3 46.1 -11.0 -23.7 Liquid Density-lb./cu. ft. at 70F. (21C.) at 130F. (55C.) 56.9^* *; 41.2 Liquid Density-g./c.c. iit 70F. (21C. ) at 130F. (55C.) 0.9121* ' 0.661* Solubility of Water in UCON Propellant-% by wt. at 70F. (21C.) 0.09 at 32F. (0C.) Vapor Pressure at 70F. (21C.), psig. 35 60 Explosive Limits-% by vol. in air Upper 21,0 Lower 4.0 18.1 3.5 ----------------------------------------' At 20C, 380bland/ucc -UiiwJtoi lii ill itliigirth 18 '\ '-_y D, Specialty Blends Union Carbide pioneered the development of economical mixtures of fluorocarbons with lower-cost flammable gases, arriving at blends that' are still nonflammable and can be used without extensive safety systems . In filling plants and with no inherent hazard to consumers. The technology of propellant blends has been published^3'***and is repro duced in Appendices A, B, and C. The blends were designed on the basis of pressure so as to serve broad areas of application--a high-pressure mixture to substitute for propellant 12 in products such as paints, moderate-pressure blends for low-viscosity, alcohol-type products, and a low-pressure blend for glass bottle items such as perfumes and colognes. Based on techniques used by the Bureau of Mines^, four standard mixtures were devised, with the properties shown in Table IV. They can all be used with the same equipment as for fluorocarbons. BLAND/UCC 381 TABLE IV Physical Properties of UCON Specialty Blends Name UCON Fragrance Propellant UCON UCON UCON Vinyl Chlor- Propellant Paint Propellant ide Propellant A Formula or Composition Molecular Weight 82.3% UCON 114 9.2%UCON12 8,5%3utane 39%UCON 11 39%UCON 12 22% Vinyl- Chloride 45%UC0N 11 15% Dimethyl Ether 45%UC0N 12 75% UCON 12 10%Isobutane 10% UCON 11 ___ Boiling Point at atmospheric pressure F. -- C. -- -- -- ---- ---- Liquid Denaity-lb./gal. at 70F. (21C, ) ' 11.5 10.5 10.6 10.1 Liquid Density-lb./cu. ft. at 70F. (21C.) at 130F. (55C.) 86.1 78.6 Liquid Density-g./c.c. at 70F. (21C.) at 130F. (55C.) 1.38 -- 1.26 -- Solubility of Water in UCON Propellant-% by wt. at 70F. (21C.) at 32F. (0 c.) -- -- Vapor Pressure at 70F. (21C. ), psig. 20 36,5 Explosive Limits-% by vol. in air Upper Lower NonFlammable NonFlammable 79.2' 75.5 1.27"*' -- 1.21 ----- . ---- 38 62 NonFlammable NonFlammable '(*'At 77F, ,j 382bland/ucc '^y r^H.^'O.- iTHfl^' 20 1. UCON Fragrance Propellant is a substitute for propellant 12/114 10/90, often used for aerosol perfumes and colognes. Butane is used as the low-cost blending agent, and the resulting mixture is comparable in performance with the straight fluorocarbons. It is suitable for use with uncoated glass containers as well as other aerosol packages. 2. UCON Vinyl Chloride Blend is a moderate-pressure blend that can be substituted for propellant 12/11 50/50. It is competitive in perfor mance and economy with the fluorocarbons and is particularly suitable for insecticides, room deodorants, and other products utilizing moderate-pressure propellants. 3. UCON Propellant A is also a moderate-pressure blend that can be substituted for propellant 12/11 50/50. Repeated laboratory tests t and field experience have verified its adaptability to a variety of products, and it can be used in the same manner and with the same equipment as any of the UCON Fluorocarbon Propellants. 4. UCON Paint Propellant is a high-pressure mixture designed as a substi tute for propellant 12 and is so named because its principal application is in aerosol paints. It can generally be used, however, with any product that would use propellant 12. KEROl COPY | c XEROt ;coptI 383bland/ucc (jVCcORPofl1 ~~ L`-f *'lWVA-f.fh,n-im~-^-ifrfl,.,iii n 'mii^ iIikIi A'lli, 21 Occasionally a pressure is desired which falls in a different range from that of the standard blends. This is often the case when other ratios than 50/50 of propellant 12 and 11 are being used. It is possible to adjust the composition of a standard blend to duplicate the desired pressure, and the calculations are given In Appendix D. It should be noted that this usually involves a reduction in the concentration of the flammable componentj i. e., the concentration of the flammable component cannot be held constant k while the fluorocarbon ratios are varied at will. Charts showing vapor pressure and density versus temperature relation ships for selected blends are given in Appendix E, F, G, H, I, J, K, and L. See explanation in Reference 1 BLAND/UCC 384 --' g^*w'" r 7rr^ ,rfll,r' -**S*- 22 E, Azeotropes AH of the propellant blends discussed above exhibit fractionation when exposed to evaporative conditions. For this reasons, they contain less than the theoretically allowable concentration of the flammable com ponent to maintain safety In spite of fractionation. An a.zeotrope does not fractionate, however, and in the case of azeotropes of the fluoro carbons with other compounds there Is no "head and tall" requirement, assuming the mixture Itself to be nonflammable. A definitive study of azeotropes has been published and is reproduced in Appendix Only two azeotropes are listed which are deemed suitable for aerosol use,, both based on UCON propellant 114 and serving the same function. I, Binary Azeotrope Ethyl Chloride UCON Propellant 114 II, Ternary Azeotrope UCON Propellant 21 Ethyl Chloride UCON Propellant 114 83.7% Of the two, the binary mixture is the more economical and has advantages as a substitute for propellant 114, particularly in perfumes and colognes. r*>. ' : -j':T bund/ucc 385 { XCRO* J copy.' w ' M 23 F, Compressed Gases The comparatively low cost of the compressed gases makes them attractive as aerosol propellants. However, their limited solubility, and the fact that all aerosols pressurized with them experience a pressure drop as the product is dispensed, keep the compressed gases from being the solution to all propellant problems. In spite of these drawbacks, there are many aerosol applications for carbon dioxide, nitrous oxide, and nitrogen. A list of their physical properties is given in Table V, and solubility data is shown in Table VI. 386bland/ucc i4**lvt**-*>t` <. Sr1*- 7W 'l*^ TABLE V Physical Properties of Compressed Gas Propellants 24 Carbon Dioxide Nitrous Oxide Nitrogen Chemical Symbol co2 Molecular Weight 44.010 Specific Gravity (Air =1) 70F., l-ATM 1.5292 Density LB./CU. FT. 70F., l-ATM 0.1146 Specific Volume cu. ft./lb. 70F., l-ATM Normal Boiling Point, F. 8.729 Sublimation Temperature, F. -109.17 Latent Heat of Evaporation, BTTJ/lb. Critical Pressure, Atmospheres, Abs 72.292 Critical Pressure, lbs./sq.in., Abs 1071.7 Critical Temperature, F. Triple Point Temperature, F. +88.410 -69.884 Specific Heat, Constant Pressure, 70 F. 0.2016 Specific Heat, Constant Volume, 70 F. Color Odor Taste 0.1543 None None None n2o 44.016 1.532 0.1148 81711 -127.3 161.78 71.70 1053.7 -97.700 -131.456 0.2095 0.1609 None None Slight (Sweet) N2 28.016 0.9670 0.07247 13.80 -320.45 85., 67 33.49 492.2 -232.870 -346.027 0.2484 0.1774 None `None None rCXOEPYb 387bland/ucc T rr TABLE VI Solubility* of Compressed Gas Propellants in Various Solvents Water Acetone Acetic Acid Pyridine Methyl Alcohol Ethyl Alcohol Benzaldehyde Aniline Amyl Acetate Ethylene Bromide Isoamyl Alcohol Chloroform Cyelohexanol Glycerol Carbon Disulfide Nitrobenzene Benzene Xylene Toluene Amyl Alcohol Ethyl Acetate Xsobutyl Acetate Methyl Acetate Carbon Tetrachloride Petroleum Distillate? Ethylene Chloride Isobutyl Chloride Mineral Oil Heavy Naphtha Carbon Dioxide 0.82 6.3 4.7 3.6 3.8 2.6 2.8 1.3 4.1 2.1 1.8 3.4 -- 0.03 0.87 -- 2.40 2.15 1.80 2.30 -- -- 6.5 4.15 -- 3.23 2.84 -- Nitrous Oxide 0.6 5.3 4.5 3.4 3.2 2.8 3.0 1.4 4.9 2.7 2.4 5.2 0.23 1.20 -- ---------- -- -- -- -- -- -- 4.28 2.10 3.20 -- -- ---- Nitrogen 0.016 0.15 0.12 -- 0.14 0.14 0.03 0.15 -- -- 0.13 -- -- 0.06 0.06 0.12 0.12 0.12 0.12 0.17 0.17 0.18 . 0.148 0.109 -- -- 0.071 o.io ............ fCOprj > Wj-'1- *y*---------- ---------- JXEROl jcopyj 388bland/ucc J 5COPY | to.aS-wo^.-V**-..v, *^t,_ 4tfl 26 * Bunsen Coefficient: The solubility coefficient is defined as the number of ml. of gas, reduced to 0C. and 760 an of mercury, dissolved by one ml. of solvent at 1 atm and the designated temperature. The units of solubility are ml. gas (STP)/ATM-ml. liquid. To find the volume (standard conditions) of gas dissolved at any other pressure, the solubility coefficient is multiplied by the pressure in atmospheres. The reliability of measurements is estimated to be - 5% for a solubility coefficient of 1.0. m!cxoepyoIf E?n t BLAND/UCC 389 t xr.oi ... i copy* At nfrninMitoMfliw 27 III. water-based systems Water-based space sprays, in contrast to the residual-type products such as starches and polishes, are relatively new to the aerosol field, but they are receiving increasing attention. They consist of water-in-oil <w/o) emulsions with the propellant as the external phase. This arrange ment provides a finer spray than could be obtained by an oil-in-water (o/w) emulsion, and hydrolysis problems are minimized since water fotms the internal phase. An experimental program on water-based space sprays was carried out in the UCON Propellants Laboratory and the work has been (85 published . This discussion appears in Appendix N. The following formulations were found to produce relatively fine sprays and are suggested as starting points for developing aqueous space spray products: Concentration, % by weight Component I II Light Mineral Oil ("Isopar M," "Shell Sol 71," etc.) Elncol 14 Deionized Water UCON Propellant 12/Isobutane 30/70 UCON Propellant 12/Isobutane 25/75 10% 1% 44% 45% __ 5% 1% 46% -- 48% '\ 390bland/ucc 28 _> IV. FORMULATIONS Aerosol products are as varied as the chemical specialties Industry itself and, as a result, their formulation encompasses a wide range of materials and combinations. The type of system, components, valve, and . container to be used depend upon the product and what it must do. If a fine spray is desired, a two-phase system with a high propellant content would be the logical starting point, with a small exit orifice in the valve and possibly a mechanical breakup actuator. If a coarse, wet spray is preferable, the propellant content could be lowered or a three-phase system could be chosen, especially if water is present. If maintenance of pressure at low temperatures Is critical, as would be the case with an engine starting fluid, a compressed gas would be required. In the case of foams, the stability and stiffness of the foam will depend greatly on the J-'' propellant used and its concentration. These are examples of some of the factors that the aerosol chemist must deal with In formulating his products, (Figures 1 and 2),. and they can be pictured graphically by the following "trend curves"^ The curves do not represent experimental data but show the qualitative relation ships between formulating variables. tco74 BLAND/UCC 391 fxKJot iCOPY 'TTTf ]prr;T SC 10 X IO T O T H E CM. 3 5 9 - 1 4 K E U F F E L E S S C A C O . M A D tift U..A, 'xepo! COPY r\ Figure 2 /xERQt j COPY; T? F* XCPO' COPY j&- A , :' v iii f idO^l 5 idOO toaaxf i OM3Xj 31 As a general rule, the higher the pressure inside an aerosol container and the higher the propellant content, the finer will be the spray. There are 1imitations to the container pressure, however, and it is often neces sary to use mixtures of propellants to obtain the best results. IJCON propellant 12 has a pressure of 70 psig at 70F. (Table I), and if dilution with the concentrate does not lower the pressure below ICC limits, some of the propellant 12 will have to be replaced with a higher boiling material such as propellant 11 or 114. A common mixture in wide use Is propellant 12/11 50/50, although many other ratios can be utilized. If water is present in the formulation,propellant 114 should be used instead f 11,since the latter is susceptible to hydrolysis and may cause corrosion problems. Hydrocarbon propellants are also used with water-based products because they do not hydrolyze and the presence of water suppresses their flammability. When three-phase, water-based systems are used,the specific gravity of the propellant becomes important. Hydrocarbons, with their low density, float on top of the aqueous phase, which allows the use of a vapor tap valve to assist in providing breakup to the spray. High-density fluoro carbons, on the other hand, sink below the aqueous phase and their vapor must bubble up through it to provide pressure in the headspace. This causes erratic behavior of the spray, especially with vapor tap valves, and for this reason hydrocarbons are generally preferred for three-phase, water-based products. . A method for utilizing this system for space sprays was mentioned previously(8) , BLAND/UCC 394 ^ .... M- ` AdOOt tOd3X| ui. 32 Aerosol foams are emulsions,and the foam characteristics depend on a number of factors, including the type of emulsion itself, i.e., whether it is a water-in-oil Cw/o) or an oil-in-water (o/w) emulsion. Products such as furniture polishes, window cleaners and shave creams are usually o/w emulsions, with the propellant dissolved in the oil phase or itself forming the oil phase. They can be ejected as a foam by use of special foam valves, although the first two are usually applied as a coarse spray. In the case of shave-cream-type foams, the higher the propellant content the more stable and drier the foam will be. Conversely, low propellant contents usually produce wet, running foams. Other factors, of course, influence foam characteristics, and the presence of polymeric thickeners, for exmaple, will contribute greatly to stability. <8uick-breaking foams can be obtained by adding alcohol and defoamants. Presented below is a group of formulations representative of various types of products and propellant systems. They are suggested as starting points from which finished products can be developed. All have passed limited storage stability tests, but their suitability for the market ' should be verified. A large number of formulations are also on file in the UCON Propellants Laboratory and are available on request. A,* Adhesive The following formulation produces a coarse spray which is desirable for a pressure-sensitive adhesive. A finer spray can be obtained by reducing the resin content and increasing the methylene chloride. The sprayed coating should be allowed to dry for about 30 seconds before cementing the surfaces. BLAND/UCC 395 jy M- ilQAdbo3oXLj __________ ^1. jjAodo3aX<j iAdOOI fO&3Xj 33 Component Concentration. % "Vistanex" LMMH Polymer (Enjay Chemical Company)* 4,0 Methylene Chloride 46.0 UCON Propellant 12 50.0 Valve Orifices = ,080*' x .018" Actuator e .018" ` *The polymer can be modified by addition of other resins to obtain specific properties desired -- see literature avail able from Enjay Chemical Company. B. Dust Mop Spray The active component of a dust mop spray is usually a light mineral oil. The oil can either be packaged in an anhydrous system with a fluoro carbon, or incorporated into an aqueous emulsion and packaged with a hydrocarbon propellant, as shown by the following two formulations: I II Mineral Oil Oleic Acid Triethanolamine Deionized Hater UCON Propellant 12 UCON Isobutane 50% 40% -- 10% -- 3% -- 25% 50% -- 22% Mixing Procedure for Formulation II: Add oleic acid to mineral oil and triethanolamine.to water. Add the oil to the water slowly with stirring. Package in the usual manner. Valve Orifices .080" x >0l8 bland/ucc 39fi ~i -- |jjj' I? 0A&tiO3XD 34 C, Foam for Pharmaeeutteals r The use of aerosol foams as carriers for medicinal products has received increasing attention from pharmaceutical marketers. Convenience of application, sterility, and maintenance of biological activity are among the numerous advantages. Since aerosol foams are emulsions, however, the usual difficulties of gelling or phase separation are often encountered. Particularly troublesome are those products involving cationic materials, which require specific surfactants.to form stable emulsions. Listed below are two formulations that exhibit long-term stability with cationic pharmaceuticals. Both have been packaged with varying amounts of propellant to produce foams of different types, from a very wet to stiff and dry. The texture of the foams produced by the "Polawax" formula may be a little more -preferable than those of glycerol monostearate, but the ultimate choice will depend on the intended applications and compatibility with active ingredients. BLAND/UCC 397 AoadO'JOx fM| - .Jr -.,,i Jai ]IqAhdOsxO]` ~-im--" Part A Glycerol Monostearate "Polawax" Cetyl Alcohol Glycerine "Span" 80 Part B "Atlas" G-271 "Sorbo" Deionized Water I 2.5% -- 1.0% -- 0.5% II TM 2.5% -- 5.0% 0.5% 3.5% 5.0% 87.5% 3.5% -88,5% Mixing Procedure: Parts A and B are mixed> separately, heated 80-90C., and then combined with stirring until cool. I Package: Concentrate S 96% II 90% OCON Propellant 12/114 20/80 - 4% 10% 35 BLAND/UCC 398 'ioAadOaOxli ut joaaxj 36 D, Flowering Fertilizer It has been shown by radioactive tracer techniques that plant feeding through the foliage can be more effective than feeding through the root system(8) . The nutrients used for this purpose are so-called soluble fertilizers, i.e,, water-soluble salts containing the elements nitrogen, phosphorus, and potassium. A solution of these salts in an aerosol container offers convenience both from the standpoint of storage and elimination of mixing of the salts each time they are to be used. It is generally preferred to have separate fertilizers for flowering and nonflowering plants. The two formulations below evolved from tests conducted on a number of plant species that responded with increased lustre and vigor, rather than growth -- a desirable feature for indoor plants: BLAND/UCC 399 AeiOO I ,Ott3Xf A .. `Tiil. *dOO i"2if M* :aL 37 Flowering Plants*) (Should not be sprayed directly on blooms) Nonflowering Plants^) Ammonium Nitrate Potassium Nitrate 2.00 Parts a 1.00 Diammonium Phosphate = 0.75 Calcium Sulfate = 0.25 Ferrous Sulfate = 0.25 Ammonium Chloride = 0.25 Potassium Nitrate = 44.00 Ammonium Sulfate = 6.00 Urea = 10,00 Triple Superphosphate * 15.00 Calcium Carbonate * 0.04 C*)ory Mir Basis Mixing Procedure; Dry Powder Mix 0.5 gms.................0.25 gms. Sterile Water.........................................i liter Package: Concentrate UCON Propane/Isobutane 10/90 Valve Orifices Actuator 95% 5% .013" - 2 x .020" Mechanical Breakup BLAND/UCC 400 i idOO Od'JX , 38 E.T.f 1F"u1 r1 nit" u1 re P" oli"sh Furniture polishes generally consist of oil-in-water emulsions that remove both oil- and water-soluble soils and impart a good lustre to the finish. Some products incorporate waxes to increase protection a dura bility of the polish, while others use only an oil that imparts a high sheen for a shorter time. The following formulation can be varied in these respects to obtain the desired properties: UNION CARBIDE Silicone L-45, <350 cs.) 1.250% "Crown" Wax 23 ' Carnauba Wax No. 1 1.025% 1,025% "Hystrene" T-70 1.375% "Sovesol" No. 5 12.000% Deionized H20 82.500% Triethanolamine 0,825% Mixing Procedure: Heat the L-45,waxes, and "Hystrene" T-70 over a steam bath to 195F. until the waxes are melted. Heat the water to boiling, and add the triethanolamine. Gradually, with rapid stirring, add the triethano lamine-water solution to the hot wax solution. Stir until the emulsion reaches 113F,, and add the "Sovasol". Continue stirring until the emulsion Is cool Packager Concentrate 95 - 90% UCON Propellant 12/114, 40/60. or UCON Isobutane 5 - 10% bland/ucc 401 >'< T- ....... -*"*-&'* `-y l-; p# Hair Spray Hair sprays are the largest selling aerosol product. They consist of a resin and resin modifiers, alcohol, perfume, and propellant. The follow ing is a typical formulation, but there are many variations, particularly in regard to the resin, in use today: PVP/VA 60/40 Dibutyl phthalate Perfume UNION CARBIDE Silicone L-45 <100 cs.) UCON Aerosol Alcohol (SDA-40) UCON Propellant 12/11 40/60 3.0% 0.5% 0.2% 0.1% 25.2% 70.0% O'* Hand Cleaner and Ink Stain Remover "Waterless" hand cleaners have been available for several years in both aerosol and conventional packages. An interesting improvement In these products can be made by incorporating components that will remove ink stains. Surfactants have to be carefully chosen, however, for some ink-removing ingredients, such as sodium meta-bisulfite, can cause dis coloration, precipitation, and emulsion instability. Anionic surfactants, and particularly triethanolamine stearate, provide satisfactory foams with or without the bisulfite, as shown by these formulations: BLAND/UCC 402 l ISS5#I,: Stearic Acid Tr iethano1amine Polyethylene Glycol 600-Distearate Lanolin Propylene Glycol CARBITO]$^ Solvent Sodium Meta-bisulfite Deionized Water Perfume I 3.5% 2.0% 5.0% 3.0% 7.5% 7.5% 3.0% 67.5% 1.0% II 5.0% 2.7% 5.0% 3.0% 7.5% 7.5% -- 68.3% 1.0% /'"'s Mixing Procedure; Melt the stearic acid and lanolin and add the CARBITOL (._ J solvent and propylene glycol. Heat the water, triethanolamine, and distearate, and add to the other mixture. Cool with stirring to 40C., add the sodium aeta-bisulfIte and perfume, and cool to room temperature with stirring. Package; Concentrate UCON Propellant 12 = 96% 4% Valve: "Clayton" standard flow foam valve. I bland/ucc 403 w r`> i '' Ifs-jr 41 Brush Conditioner and Preservative The UCON polyalkylene glycols are solvents for many paints and make good conditioning agents for storage of paint brushes between periods of use. Both the UCON fluid LB and 50-HB series are suitable, although the latter is preferred, since it is compatible with both oil- ;and waterbased paints, and the brush can be put to use without wiping or rinsing. UCON fluid 50-HB-260, when packaged as shown below, produces a coarse spray that deposits as a quick-breaking foam, and the fluid penetrates rapidly into the fibers of the brush. For long storage periods, a cover or wrapping should be used to prevent drying out of residual paint on the brush UCON Fluid 50-HB-260 Isopropanol UCON Propellant 12 35% 15% 50% Valve Orifices Actuator 018" x ,018" 018"-- 404bland/ucc 1`|-WFitJUArfft-fc rsl**/-^lt.-- fiffTiM>HiH',i<tf`^'-. 1*2 XI Personal Deodorant An aerosol personal deodorant consists of an antiperspirant agerit^ perfume, cosolvent (usually alcohol), and propellant. Auxiliary agents such as a bactericide and glycols are sometimes Incorporated. The finished, product should have a fast-drying spray that produces a nontacky, nonflaking deposit; Perfume Hexachlorophene = 0.25% a 0.25% Aluminum Sulfocarbolate a 2.00% UCON Aerosol Alcohol (SDA-40) * 62.50% UC0N Propellant 12 s 35.00% Valve Orifices Actuator .016" x .0135" with .016" vapor tap .060" MB bland/ucc 405 wfl j4 <$ilck-Breakin)f Poam Although stable foams are usually desired and not always easily obtained, it is sometimes preferable to dispense a product as a quickbreaking foam which yields a rapidly spreading liquid film. The following mixture provides a fast-breaking foam that leaves no soap-like residue, and the degree of stability can be varied to meet the various requirements of different products. Increasing the surfactant and decreasing the alcohol produces a more stable foam, and the reverse makes for a more rapidly breaking foam: UCON Aerosol Alcohol (SDA-40) = Deionized Water "Onyxol" 336 "Glycosperse" 0-20 DCON Propellant 12/114 20/80 = 38% 53% 2% 5% Valves Optional, depending on the type of foam ejection desired. BLAND/UCC 406 ik 44 K,, ^ Spray Starch One of the largest-volume aerosol products, spray starches have ' received increasing acceptance because of their convenience and time saving features. The following is a formulation that is adaptable to various valve and actuator arrangements to provide the specific spray pattern and fabric wetting desired: Starch Solution <4 per cent Com Products Company B-771) 89.25% Isopropanol 5.00% Hexachlorophene 0,25% Methyl Parasept > 0.25% Propyl Parasept 0.25% UCON Propane/Isobutane 10/90 5.00% Mixing Procedure: Mix starch with water and allow to stand overnight. Heat to 98C. and stir to disperse starch. When cool, add the preserva tives dissolved in isopropanol. Homogenize the mixture and package it. BLAND/UCC 407 45 L.' Touch-Op Floor Polish Standard latex floor polishes can be pressurized with nitrous oxide to provide a means for renewing worn or spotted floor areas between periods of regular polishing. Application of the product as a spray,followed by manual spreading gives the best results: Latex Polish (Polyvinyl Chemicals CW-1 or UBS Chemical Co. RHW-0424-3) Nitrous Oxide Valve Orifices Actuator 100% =* to 105 psig at 70F. o 0.100" x^.030" n Mechanical Breakup r, V Ifcxoep5vo\f it f BLAND/UCC 408 4 46 \ , M. Wax for Wood Floors A polymer for use In polishes for wood floors is supplied by Polyvinyl Chemicals,Incorporated, as "Neocryl" B-705. The polymer ts reported to form "dry-bright" polishes in combination with conventional waxes and resins but, unlike conventional polishes, dries to a gloss without buffing. This makes the product attractive for aerosol packaging, since full advantage can be taken of the convenience of spray application without the need for mops and buffers, or the labor associated with polishing conventional waxes. The polymer is incorporated into a concentrate designated WP-70 by Polyvinyl Chemicals, details of which are available from the supplier. Aerosol packaging consists of: WP-70 Concentrate = 60% UCON Propellant 12/11 50/50 or Propellant A * 40% Valve Orifices * .080" x .018" Actuator 3 .016" Container * Unllned, sideseam tinplate r cXoERpOytj 3l?V fXEROj ,C(?F YI ir XERO bland/ucc 409 ,,-rf F?-COPTJ 47 N; Window Cleaner Window cleaners must remove not only dirt and dust but also greaseltfce soils. This requires a mixture of both solvents and surfactants, and accounts for the wide variety of such cleaners on the market. It is gener ally desirable not to leave a film after the cleaner is used, but surfactants, which constitue a good part of the residual film, are necessary for effective soil removal. The following mixture represents a balanced combination tAich is efficient and leaves essentially no film; TSRGITOL NPX Ammonia (23% A<pieous) Isopropanol Deionized Water UCON Propellant 12/114 35/65 or UCON Isobutane 0.3% 1.0% 3 35.0% 60.0% 4.0% Valve Orifices Actuator Container 100* x .030" MB Tinplate, phenolic lined XtRO COPY 410bland/ucc 48 V. THE AEROSOL LABORATORY Very little specialized equipment is required for an aerosol laboratory. Two items that are essential, however, are a crimper and a pressure filler. These are used for sealing and pressurizing the container and are available from Aerosol Machinery Company, Westbury, Hew York; Builders Sheet Metal Works, Inc., New York, New York; Colton Kiefer Division, Cedar Rapids, Iowa; and General Kinetics, Inc. Atlanta, Georgia. Other equipment is mostly optional but often very helpful. Glass compatibility tubes such as those supplied by the Fischer & Porter Company provide visual observation of what happens when propellant and product are mixed and, when properly handled, are safe to use for this purpose. Cold filling can be accomplished with a conventional freezer by immersing a coil of copper tubing in an aqueous glycol bath in the bottom of the freezer. The tubing is attached at one end to a cylinder of propellant outside the freezer and to a valve at the other end. As propellant is drawn through the coil it is cooled below its boiling point and is ready for cold filling. A supply of representative valves is convenient, although, the extent of the inventory will depend on the number and type of products being handled. The same applies to a container inventory. If glass bottles are to be filled, a spin-type crimper will be necessary for them, since glassbottle valves are different from metal-container valves. Hoses> connectors, pressure gauges and valves for transferring propellant from storage cylinders to filling equipment are available from the suppliers listed above. In addition, each October issue of Aerosol Age contains a buyer's guide for the aerosol industry where a supplier for almost any piece of aerosol equipment can be found. BLAND/UCC 411 r^ 1M M|li" /m 'v I 49 Beyond this, standard*itenfs such as are found in any laboratory will be necessary. Requirements for scales, balances, pH meters, ovens for storage testing, chemicals (particularly formulating materials), gas chromatographs and other analytical instruments will depend on the function and scope of laboratory activities. BLAND/UCC 412 r 50 VI. PRELIMINARY DESIGN OF AN AEROSOL FILLING LINE INTRODUCTION This section describes a general approach to the design of facilities for filling aerosol containers. Although equipment sizing and construction details will vary with the specific product being handled and the volumes Involved, the approachdescrlbed below will be useful for reference. The recommendations that follow cover receipt of raw materials, mixing, the filling line Itself, warehousing and services, operating labor require ments, estimates of Investment, and typical layouts. The purpose is to describe all equipment required to produce a finished product ready for shipment. Should a filler plan to use an existing building or existing storage tanks, the investment can be adjusted without difficulty. DESIGN BASIS Filling facilities are designed for an annual rate of 12,500,000 units (50,000/day) on the basis of one-shift operation and a 250-day year. The container is assumed to be a 21i x 413 can (12-ounce size) with an 11-ounce fill. The recommended equipment will handle smaller containers (down to 202 x 214 cans) with no decrease in units filled per minute. Larger containers can also be handled, although it might be necessary to reduce line speed if a large propellant charge is required. For general discussion, we assume a product which is 40% by weight concentrate and 60% by weight propellant, with the propellant being a pre-mixed blend of UCON Propellant 12/11 50/50. In selecting materials of construction, the concentrate was considered to be similar to a lower 6alcohol such as ethanol or isopropanol. The design is based on a concentrate blend of 90% alcohol and 10% other components and additives. BLAND/UCC 413 w tcrt.Wl^t r- . 51 The facilities described here are designed to package ote base product. However, minor variations (such as the three resin concentrations normally used in hair sprays or the varied fragrances added to room deodorants) can be handled easily. A highly flexible facility for packaging widely varying products would require changes, primarily in the bulk storage and mixing areas. These changes could be handled without difficulty within the general framework described here. The case-packing and finished-product handling system are based on cartons of 12 cans. Provision is made for the special packs and deals which are common in consumer product marketing. The facilities are designed as a completely new Installation in a separate building with no constraints from adjacent structures and existing operations. Such factors must be considered in final planning, but they are not included in this study. In fact, treating the facility as an independent unit clarifies the incremental investment needed for service facilities, warehousing, and the like. Being a new facility, the unit can take advantage of the latest developments in aerosol technology. Such improvements as automatic valve-placing and high-speed gassing with the actuator button in place were impossible until recently. Although the facility is specifically designed for filling one basic product, flexibility for handling other materials has been included wherever this could be done without affecting the cost. The recommendations are based on published data and on experience. They should be used for estimating purposes only,since specific proposals must depend on the needs of the individual filler. The suggested unit Icopvi 414bland/ucc \/j would consist of a single high-speed filling line installed in e new building. We estimate the complete cost of a suitable installation at about $325,000, 'J based on mid-1963 prices (Table VII).In the sections following, each major part of the proposed facility is covered in detail along with a brief discussion describing the method of operation and the reasons for our recommendations. (Table VII) BUILDING As shown on the attached plot plan of the proposed facility (Figure ), we would recommend a building 140 feet long and 105 feet wide with a total floor area of 15,300 square feet, including a small mezzanine. The building would have a structural steel frame with masonry or insulated metal walls and an insulated roof with a clear height of at least 17 feet. Truck docks would be provided as shown on the drawing. To accommodate future expansion, the building can be extended to the north. (Figure 3) BLAND/UCC 415 Table yn Summary of Investment Building Bulk Storage Alcohol tank Propellant tank Sub-total Bulk Storage Mixing Filling Line Unserambler Can-cleaner Can-coder Concentrate filler Valve-inserter Crimper Gasser Water bath Overcapper Labeler Case-sealer Case-coders Conveyors In-line quality control Installation Sub-total Filling Line Auxiliaries Boiler Air-compressor Lift trucks Laboratory equipment Shop equipment Locker room and miscellaneous equipment Sub-total auxiliaries $ 8,000 9,300 2,900 1,800 600 6,900 11,600 16,200 19,000 10,800 5,600 4,400 4,900 300 15,000 1,000 15,000 ~ 5,500 10,000 7,800 3,500 1,500 1,500 Total (Excluding Engineering and Contingencies) 53 $135,000 17,300 24,100 116,000 29,800 $322,200 iXEROj 1 Cop vI BLAND/UCC 416 h Receiving -- 18 Sp. f 40* 36 Pallet Spaces Shipping N a S' \ Propellant Solvent 20 Sp. Filling Room 105' Shop Boiler Room Note-- Office G Lab. Above Locker Rooms Figure 3* Aerosol Building Layout For Typical Filling Line SK-t Scole </|6 *> I'-O- Ln BLAND/UCC 417 55 In a building of this type, we suggest that the bays be as large as possible. In this particular situation, a span of 35 feet would be appro priate. Although longer spans such as this cost slightly more, owing to more complicated steel work, we believe the extra investment is well worth while. Eliminating columns permits more effective space utilization and gives greater flexibility in planning layouts. Based on recent experience, we believe a suitable building can be erected for $8.00 per square foot. This is based on a reinforced concrete <*floor 3*-6" above grade and includes grading, lighting, ventilating,-------- ^ L plumbing and sprinklers, but excludes site^ofT^Jevelopment and any land-, scaping. If topography and soil conditions permit placing the slab at grade level with truck docks depressed, a saving of about $0.50 per square foot should be possible. However, since the feasibility of placing the slab at grade depends on local conditions, we have based our estimate on the $8.00 figure. The building thus far is heated, prime warehouse space. However, special areas such as the filling room, office, and quality control labora tory require additional features. In the case of the filling room, extra ventilation and lighting and a partition to separate it from the warehouse section are all that are necessary. This will provide operator comfort and will make it easier to maintain cleanliness. Tile walls or floors are not necessary in most installations of this type. On this basis, estimated filling room cost Is $9.50 per square foot, a premium of $1.50 per square foot over the basic building cost. fxe*o .copy Tf \XEfcO] Icopy! BLAND/UCC 418 t XCROi COPY ' r?' : /r < C ii ) 'J 56 On a similar basis, the locker room, lunch room, and shop should cost $12 per square foot. The laboratory and office are estimated at $16 per square foot. Based on these unit costs, estimated total cost of the building shown in Figure 3 is $135,000, No allowance has been made for paving, since the type and extent of paving required depend on the specific site. However, these costs can easily be added as required. BULK STORAGE As shown in Figure 3, we recommend two tanks for bulk storage of the major raw materials. These tanks are shown 50 feet from the building, but this distance may be varied to suit local building code requirements for storage of red label products. The tank farm is designed for truck receipt, and separate tanks are included for alcohol and propellant. All tanks and transfer piping can be made of steel. Transfer piping to the building can be on a simple pole-type pipe rack, and a dike should be provided around the alcohol tank. At peak levels of production, alcohol usage would be about 1,900 gallons per day. To meet this demand we recommend a 10,000-gallon vertical, dished-head tank. This tank could readily receive 6,000-gallon truckloads. Occasional receipts of 8,000-gallon.?- loads, which can be made in certain areas without exceeding highway weight limits, could be handled. The tank would be 10'-6" in diameter and 18*10" in height and should include a level gauge and thermometer at the tank. Including a 100-gpm transfer pump with mechanical seal and unloading and transfer piping, we estimate the installed cost a $8,000. If tank car receipts are anticipated, the tank size should be increased to at least 15,000 gallons. The additional 419bland/ucc JicXEoRpOfi! gp. {XEROl Icopy! T iXEPQ* ' COPY'. KERO*) :opy f i*i'inrtTIn-^`iiWjitfiTfii"i 57 capacity would be relatively economical; the tank cost would increase by about $1,500. To handle the peak propellant demand of 1,800 gallons per day, we would suggest a 7,500-gallon horizontal, standard propane tank. Although a normal delivery would be 3,000 gallons, a smaller tank (holding, say, 5,000 gallons) would be too restrictive. The proposed tank would be 84" in diameter and 27* long with a 10-gpm pump to feed the production line. Such a unit with necessary auxiliaries is estimated at $9,300 installed. Should a filler require a flexible plant capable ofJfilling many different products, additional tankage would be necessary. In the normal case, we would recommend duplicates of the alcohol and propellant tanks descilbed above. A duplicate of the alcohol tank would be suitable for most of the common solvents, and the propellant tank, which is rated at 250 psig, could be used for any of the liquefied gas propellants in commercial use today. In a flexible installation, at least one additional propellant tank would be necessary. This would permit the filler to custom-blend UCON : propellants in any desired proportions. If desired, a filler could start with the two basic tanks described above, adding additional tankage as product variety increases. We suggest that tanks be generously sized for flexibility, and because savings from reducing tank size ore relatively small. For example, if the alcohol tank were cut to 6,000 gallons, the investment would be only about $1,000 less. Further details on tank farm design and specific recommenda tions to meet a filler's individual needs are available on request from the Olefins Division of Union Carbide Corporation. fXE*Ol `COPT I e* ' r IfXcEoRpOtj! bland/ucc 420 fiCXQERPOY"1' T 58 MIXING The peak concentrate requirement will be about 2,100 gallons per day. To handle this volume, we suggest two vertical, dished-head tanks with a nominal capacity of 2,400 gallons for mixing the main components. These tanks would be 6*-6M in diameter by 12r high, and we would suggest 304 stainless steel for the mix tanks and transfer piping to the filler. In operation, each tank would hold a one-day supply of concentrate, and mixing could be done in one tank while the other tank was feeding the line. As alcohol formulations are usually easy to mix, we would suggest a pump rather than an agitator for mixing, since a pump should be effective as well as economical. Two pumps should be provided: one with a minimum capacity of 100 gpra for mixing and one with a capacity of 25 gpm for feeding the line. Both tanks should be piped to both pumps and the feed pump should recycle a portion of the concentrate through the tank to maintain a well-mixed blend. For measuring the alcohol component, we suggest a meter system such as the A. 0. Smith T-10-T. Properly maintained meters are more accurate and less expensive than weigh tanks. One meter should be installed in the transfer line from the tank farm as close as possible to the mix tanks. For alcohols, we suggest meters with no brass or aluminum parts and with automatic temperature-correction and an automatic cut-off valve. The temperature-correction will adjust for a 100F, temperature spread, and the cut-off valve will automatically stop the flow when the pre-set volume has passed through the meter. A 2" meter system good for 20 to 80 gpm would cost $650 plus installation. A lj" system good for 12 to 48 gpm would cost about the same. The installation cost of the two 2,400-gallon T* r 421bland/ucc _ j'xcpo* 59 tanks with transfer piping and meters Is estimated at $18,500. To handle minor components such as fragrances, surfactants, and the like, we would suggest a 460-gallon stainless steel tank, 4* in diameter and 6'-6" high. Drummed and bagged materials could easily be added to such a tank and premixed with a portion of the solvent. To facilitate mixing, this tank could discharge to the suction side of the 100-gpm mixing pump previously mentioned. We estimate the installed cost of this small tank, including a transfer pump and piping, at $5,600. Our recommendation of metered tanks with mixing by pump is based on one easy-to-mix formulation (with minor variations possible). If many bulk liquids must be handled, each would require its own meter system for accuracy. Each meter would cost about $900 installed; with a large number of products, a weigh tank might be more feasible. A weigh tank would give complete mixing flexibility, but each filler must determine whether the added cost is justified. Similarly, using a pump to mix the concentrate would not be suitable with some difficult-to-mix materials. Should agitators be required, the installed cost of each 2,400-gallon mix tank would Increase by about $4,000. FILLING LINE A typical working day on a packaging line is 450 minutes long, owing to personal time and time lost in starting up and shutting down. In addition, provision must be made for minor breakdowns on the line, lack of material and similar delays. To allow for this, we have based capacity on 420 minutes per day actual operating time. To fill the required 50,000units/day, the line speed must average 119 units per minute. Since 120 422 blandiucc XCfOvRPOY'' r r" jr 60 per minute is a common break point in aerosol line speeds, we suggest a line which can be rated at this speed after a break-in period estimated at two to three months. The speed rating of 120 units per minute has become almost a standard in aerosol design over the years. However, recent technological improve ments have virtually made this break point obsolete as a limiting factor. Equipment is now available for line speeds of double this figure, and almost any intermediate rating can be handled. Selection of the rated speed is one of the key decisions a filler must make in preparing design criteria for a filling line. Although the line described here will fill 120 cans per minute (since this is adequate for the assumed annual demand), it could easily be upgraded by using larger equipment of the same general type. There are three basic methods of filling aerosol cans with propellant, as mentioned before (cold filling, pressure filling, and under-the-cap filling). Many products use small valves (body size of .016" to .018"), which are not suitable for pressure filling since propellant flow through such a narrow orifice would be uneconomically slow. However, an acceptable alternative in most cases would be to use a valve with a large (.080") pressure-fill body orifice while keeping the small orifice for product discharge. Such a valve could be pressure filled at a rate of about 90 grams per second, thus permitting pressure filling at high speeds. It normally should have no effect on formulation, spray pattern or valve cost. For purposes of this report, we have assumed that valve and product specifications will permit any of the three filling methods to be used. tXEROi {COPY\ V- i BLAND/UCC 423 rxorpflyo)F 61 Although cold filling was the original aerosol method, we do not recommend it for the following reasons: 1. Refrigeration equipment is expensive. 2. Many of the available cold fillers have a maximum speed of 120 per minute, precluding any upgrading of the line. 3. Propellant losses can be sizeable. h. Chilling to -30F. for filling followed by heating to +130F. for testing is not economical. TJnder-the-cap filling and pressure filling both offer significant advantages over cold filling. Although under-the-eap filling equipment costs about 5% more than a comparable crimper and gasser, less floor space is required and set-up time is reduced by having only one machine. Performance of both under-the-cap and pressure filling equipment is improving rapidly and both should be considered by any packager planning a new filling line. The choice between the two is a close one and normally will depend oh local conditions and the products to be handled. For our purpose a pressure filling installation is assumed. It will provide ample capacity without pushing key components of the line. In the following sections, each major item of equipment will be discussed in detail. Although we suggest specific items, in most cases there are perfectly acceptable alternates which might be preferable for reasons of standardization or personal experience. A list of some leading equipment suppliers is included in Appendix "0" to serve as a guide in this area. More complete listings can be found in trade directories md buyer's guides. Most major items of equipment either have excess capacity or can be readily enlarged. bland/ucc 424 XCRO. ~w r tiyt v v^iw-1 Mv .-.-(^i , '-|'>'-*fl*'iMI' . iy'-Ak lH^lX 62 This flexibility costs very little and provides a high degree of insurance against being outgrown. A typical layout of the proposed line is shown in Figure 4. The unscrambler and case-sealer have been placed outside the filling room to minimize lift truck traffic in and out of the main filling area. In addition, we recommend that all electrical equipment in the filling room be explosion-proof, in view of the potential hazard In handling volatile, low-flash solvents. In selecting equipment for the line, we have concen trated on continuous-motion rather than intermittent-motion machines, since aerosol cans tend to be unstable. Although an intermittent-motion, straight-line package installation might be available at slightly lower cost, such lines tend to require more adjustment and maintenance work, and they are not adaptable to convenient upgrading. In addition, they do not give the flexibility of a line in which each component has been picked to meet the individual needs of the filler. Also, except for contact parts in the fillers and the water bath tank, we believe carbon steel is an acceptable material of construction. (Figure 4) I XERO .COPY IP"*' T?TT"e bland/ucc 425 k XCRO 4 COPY' 'i - / r iiOau>ao- - * CJ I Unscrombler Cose Sealer Cose Coders Mixing Area Can Cleaner Pocking Labeler Can Coder Filler nScale Valve Placer Copper o==36" Table Woter Both a 36* Tobies Vacuum Crimper J"L Gosser Scale _Q_ Sproy Test E -,r SutoUaO*n 5 XO BLAND/UCC Schematic Layout Of T ypical Aerosol Filling Line SK-Z Seal. Ve" (*-Q" i i I Figure 4. to OCos ' 64 Unserambler The first major item of equipment Is an unscrambling table. The layout is based on receiving empty cans in bulk. If occasional use of reshipper cartons is made, a portable conveyor can be used to transfer the empty cartons to the packing area. A suitable unscrambler would be the Styl-O-Matic straight line unscrambling table without hood, made by Island Equipment Corporation of Miami, Florida. This unit handles the cans on steel table-top chains (3 chains, each 7M wide) and discharges to an adjacent 4"-wide chain conveyor. It will handle up to 240 cans per minute, depending on container size and the method of loading the unscram-' bier with empty containers. The purchase cost of a 9-foot-long unit made of carbon steel would be about $2,900. Can Cleaner To remove dust and stray fibers from empty cans, we recommend a jar- inverting and cleaning line such as that made by the Chisholm-Ryder Company, Hanover, Pennsylvania. This unit inverts, air-cleans, and re-inverts each container. It should handle 150 to 160 per minute; and we estimate the cost in explosion-proof construction at $1,800. Change parts (twisters for different-size cans) should cost about $125 per set. Concentrate Filler There are a large number of liquid fillers available which can handle the production rate required for the filling line being considered. Required capacity depends partly on container size and partly on the percent of container capacity that must be filled. We suggest a rotary, continuousaction machine to maintain positive container control. One suitable machine is made by MRM Company of Plainview, New York. This machine is a vacuum TT" 1j XCEORpQYj\ KfW'T bland/ucc 427 14 COP*' 65 filler with all contact parts of stainless steel. A 16-stem machine rated at 130 pint containers per minute should be ample. The estimated purchase price of such a unit, including centering devices and explosionproof motors, is $6,900. Change parts for different size cans should cost about $250 per set. Valve Inserter Automatic valve Inserting is a relatively new development. However, there are several machines available which can handle 120 containers per minute. Since two to three workers would be needed to insert valves manually at this rate, automatic insertion is definitely worth while. The RVP-4000 Valve Placer made by PMC Industries, Hackensack, New Jersey, should be suitable. This machine is rated at 140 units per minte. Valves are dumped at random into a hopper that orients and inserts the valves automatically. The hopper will hold 600 to 1,000 valves. The cost of this machine is estimated at $11,600, including explosion-proof construction. An auxiliary valve-positioner to seat valves accurately is available at $1,000. The RVP-4000 Valve Placer will handle valves with the actuator button attached. We would normally recommend purchasing valves with the button, to eliminate the button-placing operation after the gasser. However, should it be desired to apply the button after filling, we suggest a Liberty SprayTip Applicator made by Haumiller Engineering Company, Elgin, Illinois. This machine orients buttons from a feed hopper and will seat up to 160 per minute. Including change parts and explosion-proof design, the estimated purchase cost of this unit is $4,900. Additional change parts would cost $150 per set. BLAND/UCC 428 'FT'"? ' or:>rr*oY It 1XEPO ICOPY! Ji'xCeOSPYo*- 66 Crimper A good machine for crimping valve assemblies is the Model h R.V.C. made by John R. Nalbach Engineering Company, Inc., of Chicago, Illinois. This is a fully automatic rotary unit which draws a 20" vacuum to remove air from the can before crimping. It will operate at speeds up to 120 cans per minute. Including one set of change parts and explosion-proof construction, the estimated cost of this machine is $16,000. Should pro duction demands increase, this unit could be converted in the field to an S-head machine with twice the capacity, and at a nominal cost. Gasser The key piece of equipment in any aerosol line is the gasser. To charge the containers with Ucon propellant, we can recommend the Model 3-9 Gas Jet Aerosol Charger made by Karl Kiefer Division of Cherry-Burrell Corporation with the 290-cc cylinder on each charging stem. This cylinder will handle the 11-ounce container with a single stroke. Should it be necessary to charge more than 290 cc of propellant per can, a simple adjustment will permit two strokes per can for a maximum charge of 580 cc. This would, of course, reduce the machine speed by up to 50%. This machine has 9 stations and has a maximum speed of 250 units per minute at a charging time of one second. However, speed calculations are based on a maximum of 120 per minute. At a charging rate of 90 gms per second, the 11-ounce container will require 2.7 seconds to charge. With this charging time, the gasser is rated at 129 per minute. The machine is rated at 120 cans per minute at a charging time of 2.85 seconds. bland/ucc 429 At the rates specified above, the gasser could be a limiting factor, since it will take 248 days to produce the annual volume specified in the design basis. However, the calculated charging times are conservative, and in actual practice the Model 3-9 might perform noticeably better. This is supported by the'-current trend to faster-charging valves. Actual charging tests are suggested before the gasser is finally sized. The recommended charger, including slack fill detector, can-ejector and over-the-button gassing attachments, can be purchased for about $19,000. Like the crimper, this machine can be modified in, the field to handle increased production. In this case, the conversion would be to a Model 3-18, an 18-head machine which has a maximum mechanical speed of 300 units per minute but whose practical capacity is double that of the Model 3-9 at charging times in excess of 2 seconds. As noted above, the Model 3-9 gasser has only 2 days extra capacity per year with the limiting speed of 120 per minute imposed by the crimper. Should a greater degree of flexibility be desired, a Model 3-12 charger could be purchased for about $3,000 additional. However, field conversion of a 12-head to an 18-head machine is not as simple as from a 9-head unit. Therefore, careful determination of design speed and flexibility requirements is essential to ensure that the proper size gasser is selected. As part of the discussion of gasser capacity, it should be noted that charging time can be decreased (and speed increased) by adding part of the TJC0N-11 at the concentrate filler. However, this would require at least one additional propellant storage tank. In the current situation, the added investment in tankage would more than offset the reduction in cost of the gasser. bland/ucc 68 Water Bath A Styl-O-Matie heat-and-leak test tank made by Island Equipment Corporation can be used to satisfy I.C.C. testing requirements. Based on an ambient temperature of 70F.,an 18-foot long tank is needed. To handle 120 units per minute, cans should move in four lanes. With a conveyor speed of 10 feet per minute, cans would be on 4" centers. The estimated cost of a stainless steel tank with two 7~l/2"-wide stainless steel conveyors, heating coils and controls, and a locally fabricated safety hood, is $10,800. This figure includes a simple air jet system at the discharge end of the tank to remove water from the valve cups. Rotary tables at each end of the tank to divert one lane of cans into four at the entrance and four into one at the exit are covered under "Conveyors." A four-lane, hold-down system costing about $11,300 installed would be required to handle non-magnetic containers (such as glass). Overc apper To apply the standard 1-3/8" plastic dust cover to filled cans, we recommend the Model FAB Fully Automatic Fitment Applicator made by Resina Automatic Machinery Company, Inc., of Brooklyn, New York. This unit is rated at up to 200 per minute. Since the standard machine operates with gripper chains, no change parts are needed. An explosion-proof model will cost about $4,100. The standard machine hopper will hold about 7,000 caps. However, this hopper is about 6 feet above the floor and is difficult to service. To insure smooth operation, we recommend an attached escalator hopper at $1,500 as an accessory. t " ' fw bland/ucc 431 XEROi * COPY' J j*lcn iZ'D-^'yrrr- -i_lTM-:^_ kJ The Resina capper cannot handle full-body caps. The Pneumatic Scale Corporation's Automatic Can Lldder with 3A Sterling cap feeder will handle caps up to 89 mm in diameter. Including an elevator hopper, it should cost $9,800. Labeler A minimum-cost machine for applying wrap-around labels to the cans la the Chisholm-Ryder Model V4 New Way Labeler, This machine is rated at 350 per minute in the 211 size can. Including continuous feed attachment, twisters and other necessary accessories, the estimated puchase price of this machine is $4,400. In installing this machine, the feed conveyor must be slightly elevated (to 44") to avoid the use of a can elevator. Aside from the added cost, an elevator would limit the machine speed to about 140 cans per minute, but the 44" elevation should present no problem. Case Packing Since deal and combination packs are common in the aerosol industry, and since these require frequent changes in ease sizes and packing patterns, the value of an automatic case packer is questionable. Allowance must be made for a packing table, however. Should a case packer be desired, a good unit is made by the Miller Hydro Company, Bainbridge, Georgia, and sells for about $15,000 including change parts. If the ease packer Is considered, it must be remembered that dimensions of corrugated cartons must be very closely controlled. Case Sealer To seal filled shipping cases and deliver-them to a manual palletizing station, we can recommend a Model 52-22 fully automatic case sealer made by bland/ucc 'W . it, mX*. K- - up'ifcf -jr. ir ~; Ii^-Utt-**--->v- k--.-r.w-'- 70 ' "ir Elliott Manufacturing Company of Fresno, California, This unit is rated at 700 cases per hour and uses a pressure glue system with ball-point-type applicators. Although the theoretical requirement is for only 600 cases per hour, a slightly larger machine would provide considerable flexibility for an extra cost of only about $150. A machine to seal both top and bottom flaps will cost about $4,900. If only the top flaps are to be sealed, $500 can be deducted from this price. Coders Equipment required for coding cans and cases depends on the informa tion required and where it must be printed. For this report, it has been assumed that cans must be imprinted with a lot code on the bottom. To accomplish this, we can recommend a Sideline "Markocoder," Model SIM-2, made by Adolph Gottscho, Inc., Hillside, New Jersey. This is an extremely simple unit which fits over a section of conveyor. It operates from line pressure and is rated at 150 units per minute. It will print one line with a maximum of nine characters parallel to the direction of container movement. Including an ample supply of type, this coder will cost about $600. Additional sets of change parts would cost about $100 each. Coding both sides of each corrugated carton is advisable, as this guarantees that the code can be seen on any pallet load stacked with an interlocking pattern. To do this, two Gottscho Model 602 coders are suggested. These units can be installed at the case sealer and will print a legend up to 8" long. They will repeat the legend every 9". Including type, the two case coders will cost about $300. Should coding requirements be too elaborate for the units described above, suitable coders could easily be provided at higher cost. BLAND/UCC 433 CXOERPYOk w 71 Conveyors The actual conveyor requirement will depend on the final layout of the filling line. For handling cans, a 4-l/2"-wide chain-type conveyor made of steel, such as Island Equipment's Styl-O-Matic Can Conveyor, is recommended. This type of conveyor is fully compatible with all equipment in the filling line. If glass containers are to be handled, non-metallic chains and guides would be desirable. Between the spray test hood and the rotary tables at the entrance to the water bath, the chain conveyor width should be increased to 7-1/2" to permit diverting the single line of cans into a double line. Each line of cans should feed one 36" table. The tables, in turn, will form four rows of cans for the test bath. At the end of the test bath, another 36" rotary table should be used to re-form a single row of cans on a 4-l/2"-wtde conveyor for further operations. A skate-wheel-and-belt conveyor system should be used to move filled cases from the packing table to the case sealer. A short length of belt conveyor should be at the end of the case sealer to facilitate the work of manual palletizing. A portable conveyor system can be provided between the unscrambler and the packing table should it be desired to use reshipper cases. A conveyor system such as described above, including can conveyors, rotary tables, and conveyors for cases, is estimated at $15,000. In-Line Quality Control In the proposed filling line, there should be three quality control stations. After the filler and after the gasser, "over-and-under" scales should be installed to eheckweigh containers at random. After the second checkweigh station,, a locally fabricated sheet metal spray test booth jxEROl BLAND/UCC 434 72 with an exhaust duct should be installed for spot testing valve action. These three quality control stations can be installed for about $1,000. If a flammable hydrocarbon propellant such as Ucon isobutane is to be used, all valves should be tested before the water bath to remove propellant from the dip tubes. The original spray test booth could easily be modified to handle this. With flammable propellants, the gasser and the spray test booth should be walled off from the remainder of the line, and a leak detector installed to minimize the hazard. Since the layout in Figure 4 has this pofction of the line in the southeast corner of the building, necessary modifications can be made at low cost. Installation Cost All prices to this point have been purchase prices of the equipment with necessary accessories included. To Install this equipment in accordance with the layout in Figure 4, the cost would be $15,000. This figure Includes the power supply to the drive motors,which, for this layout, would total approximately 15 horsepower. BLAND/UCC 435 Z>RPYO |f IXEROl .COPY! *'4r ('xCEORPOYl, AT 1 XCRO', } COPY --isr 73 WAREHOUSING The warehousing facilities shown in Figure 3 will provide a net usable storage area of 3,200 square feet, not counting the aisles shown in the sketch. In addition, a receiving area is provided on the west side and a shipping area on the east with two truck doors at each end. Estimated normal daily shipments and receipts is two to three truck loads each. However, to allow for LTL shipments and receipts and to avoid bottlenecks, four truck spots are recommended. Of the total net usable storage area, 800 square feet should suffice for raw material storage. These materials would normally be stored one and two pallets deep from the aisles. This space should be ample for a two-day supply of cans, a one-week supply of caps, valves, and knocked down shipping cases, and a one-month supply of labels, chemical additives, and miscellaneous items. The space allowed for raw material inventory, particularly of empty cans, is minimal. However, a filling line of this size using standard aerosol cans should be able to schedule can delivereies closely. The buffer stock of cans would be to protect against an occasional missed delivery or emergency change in production schedule. The layout provides 2,400 net square feet for finished good storage, with materials stored up to three pallets deep from the aisles. Based on a maximum stacking height of 12 feet, this area should hold a maximum of 640.000 cans. However, the effective capacity is only 90% of this, or 580.000 cans. If more than 90% of the total space is used for storage, excessive re-handling normally results. A finished-product storage area of this size should be ample for twelve days* output, and should provide sufficient inventory for an orderly production schedule. bland/ucc 436 fxEPO'f ,copr ! SP ' * T {{CXORPOY'' JBf T7' . -T . i TV.f*-Ttvfll-^7. Ti-. -iiln- tfn'ii'- -i . 1, .-- lid**, -H 4U<>'J 74 AUXILIARIES An appreciable amount of auxiliary equipment must be installed in the areas indicated in Figure 3. A boiler and air compressor should be installed in the boiler room at the east end of the building. A 100-horsepower, 60-psi gas-fired package.boiler should cost $5,500 installed and should be adequate for building heat and process steam. A 75-horsepower air compressor for plant and process air would cost about $10,000 installed. This is a rela tively large compressor,but the gasser requires a great deal of air in its operation. One lift truck would be adequate for warehouse handling. A 3,000-pound electirc truck with battery and charger would cost about $7,000. Electric power is recommended, since the service would probably be very intermittent. The truck chosen should be a narrow-aisle type. Although trucks are avail able that will operate in aisles less than 8 feet in width, the aisles in the preliminary layout are 10 feet wide to give flexibility. In addition, two hand pallet trucks should be provided, at a cost of $800. The laboratory shown on the layout is intended for quality control, not product development. Basic tests on raw materials (such as color, odor, specific gravity, and refractive index) could be made here. Likewise, finished cans could be tested for moisture, specific gravity, pressure, and effectiveness of crimp. Basic equipment and shelving for retained samples would cost about $3,000. This does not include a chromatograph. A chromato graph with recorder would cost an additional $2,500 to $3,000. Shop equipment including a drill press, hand tools, work bench, and shelving would cost about $1,500. Lockers, lunch room equipment and office equipment would also cost about $1,500. , XEROl ,-COPY . bland/ucc 437 \ ' COPY /T 75 LABOR RETIREMENTS Total labor requirements depend partially on layout and partially on company policy. Unless policy prohibits, most jobs on aerosol production lines are handled by women. Including indirect labor, the total estimated manpower is as follows: 1 man - Unload empty cans at the unscrambler. 1 girl Checkweigh after concentrate filler. 1 girl - Checkweigh after gasser. . 1 girl - At spray test booth (Note: The three girls assigned to quality control work can also service the line in their respective areas since only a partial inspection is necessary.) 1 girl 1 man 1 man - Inspect for leaking cans at test bath. Service the valve-placer and the capper. Service the labeler and do general line-tending. 3 girls - At the packing table. 1 man - Palletize at the end of the case-sealer. 1 man - Provide empty cans to the unscrambler and remove pallet loads of finished product. 1 man - Receiving and shipping. (Note: ^ This assumes that most shipments are in truck-load lots and that carton addressing, picking small orders, and the like do not consume a significant amount of time.) 1 man - Day mechanic 1 man - Laboratory technician. 1 girl * Clerk. 1 man Mixing operator. 1 man 1 man Night mechanic and set-up man. Supervisor. 438blLaANnDd//UuCcc The total labor requirement listed above includes 8 girls and 11 men. Set-up labor can be based on a rule of thumb of one man-hour per major item of equipment. For the line proposed, about 8 man-hours would be required for a complete set-up. This should be done at night to minimize line down-time. A partial set-up {one in which can diameter Is not changed) would require less time. Although set-up time would not be a problem with only the 11-ounce can specified in the design basis, the limitation was made to simplify discussion of the filling line. In practice, multiple can sizes would be handled,and set-up labor must be allowed. If safety requirements call for a minimum of 2 men in a building, miring could be done at night. In this case, the mixing operator would have to be capable of analyzing a blend to avoid lost time in the morning. summary The preceding sections outline a suggested approach to an aerosol filling line. We believe the approach is a workable one, but testing would be required before final sizing of equipment. As summarized in Table VII, the total installed cost (before engineering and contingencies) is estimated at just under $325,000. This is for the basic equipment; optional extras are not included. To estimate the cost of a higher-speed line, a rough approximation can be obtained from the well-known "six-tenths rule." This is a rough rule of thumb that is reasonably applicable to a complete packaging line of this type. The rule can be expressed by the formula; bland/ucc 0.6 C2 77 a where Cj is the known cost of^filling line with capacity Rj , R2 is the capacity of the second filling line, and Cj is the unknown cost of the second line. Although the hypothetical situation used as a design basis for this report will rarely occur exactly as set forth, the information given above should provide a useful frame of reference in approaching the design of an; aerosol filling line. The basic filling line is quite flexible, being suitable for a wide range of container sizes; line speed can easily increased if necessary. Further assistance and more detailed information is available on request from the Olefins Division of Union Carbide Corporation. ;rXEROl ICOPY\ s. . XEPO] COPY ; BLAND/UCC 440 \ XERO1. * COPY 78 VII. STORAGE AND HANDLING This section presents detailed information concerning storage facilities (g) (Figure 5) for UCON0^ fluorocarbons. The flow diagramAshows the storage tank and recommended accessory equipment. Engineering details are provided in the Section titled "Equipment Specification Sheets." UCON fluorocarbon bulk deliveries are made by tank truck or tank car. Tank trucks are equipped with an unloading pump and hoses. Unloading hoses are discussed here, but they need not be purchased by the customer if the truck can be driven to within about twenty feet of the unloading line connection. In the case of tank car deliveries, an unloading compressor must be provided, and an unloading station is needed so that operators can have ready access to the tank car dome. Air should be evacuated from new storage tanks prior to filling them with fluorocarbon. For locations where general plant vacuum pumps are not available for evacuating storage tank and piping facilities on initial start-up, specifications are included covering both mechanical and steam-jet-type vacuum equipment that may be considered. This equipment can be. brought in on a temporary basis during initial start-up or Installed as permanent stand-by facilities required when system repairs are called for. It may also be feasible to rent a suitable vacuum pump from a refrigeration supply house. `XERO t,COPY 'J .-m i XCRO ^ COP Y bland/ucc 441 i'xcpo' d Figure 5. NOTES: (A) Storage tank vaporizer, vapor lines and steam lines are to be insulated with one-inch thickness of 85% magnesia or equal. Tanks should be painted white after insulation to reduce heat absorption in the summer. (B) Steam lines are to be installed in accordance with customer practice. (C) Shut-off valves under safety valves are to be locked in the open position with a car seal or similar device. (D) Provide a ten-foot length of 3/8-inch copper tubing and a Superior Valve and Fitting Co., quick coupler for refrigerant cylinder valves, DWG No. 5875. This assembly will be used for tAfei start'u? on!y- f-- (E) Elevation of tank above grade should be enough to provide easy access to valves under tanks. /o : AMjf SsUrfc>s/t**t<w 4*. on i N5 ONE-TANK STORAGE SYSTEM FLOW DIAGRAM ^3 To Filling Equipment r A >4 --to EQUIPMENT SPECIFICATIONS' 79 1 - Unloading Hose Assembly To connect to the tank truck and to equalize the pressure between the vapor space in the storage tank and the tank truck. The assembly will consist of the following: (a) One, 1-1/4-in. brass Evertite coupler. Part B, female end with male NPT threads, and Teflon gasket. Purchase with dust plug attached to coupling with a 6-in. length of brass chain. (b) One, 1-1/4-in. x 1-in. bell reducer. <c) One, 1-in.-diameter nipple, 4 in. long. (d) One, 1-in. Henry Catalog No. 2001 ductile iron globe valve with Teflon packing and gaskets. (e) One, 1/2-in. steel globe valve, Henry Catalog No, 453, or equal. . () One, 15-ft. length of 1-in. corrugated metal hose, bronze with bronze wire braid cover. End connections are to be 1-in. NPT pipe nipples welded or brazed to each end of the hose. The hose must be suitable for pressure from full vacuum to 325 psig. Assemble the unit with the coupling and the valve at the same end. Install the 1/2-in. globe valve between the union and the shutoff valve to relieve pressure before disconnecting the assembly. All threaded joints are to be made using Teflon tape as the thread dope. BLAND/UCC 443 80 2 - Unloading Hose Assembly To connect to the unloading pump on the tank truck. This assembly will consist of the following: (a) One, 2-in. brass Evertite coupler, Part B, female end with male NPT threads, and Teflon gasket. Purchase with dust plug attached to the coupling by a 6-in. length of brass chain. (b) One, 2-in. Henry Catalog No. 2301 ductible iron globe valve, with Teflon gaskets and packing.- (c) One, 1/2-in. steel globe valve, Henry Catalog No. 453, or equal. (d) One, 15-ft. length of 2-in. corrugated metal hose, bronze with bronze wire braid cover. End connections are to be 2-in. NPT pipe nipples welded or brazed to each end of the hose. The assembly oust be suitable for pressures from full vacuum to 325 psig. Assemble the unit with the valve and the coupling at the same end. Install the J-in, globe valve between the union and the shutoff valve to relieve pressure before disconnecting the assembly. All threaded joints are to be made using Teflon tape as the thread dope. '-S T* * BLAND/UCC 444 ^. i* a-. sM>> frr - , -i v. - .. 81 3 - Storage Tank No. 1 To store TJCON fluorocarbons Type: Nominal capacity: Nominal diameter and length: Drawings: Horizontal Pressure Vessel Per purchaser's recommendation Per fabricator's or purchaser's recommendation To be supplied by the fabricator Operating pressure: Operating temperature: Set pressure of relief device: Design pressure and temperature: Location: Earthquake loadings: Materials: Corrosion allowance: Erosion or abrasion allowance: Design and construction: Pull vac to 200 psig Ambient 200 psi 200 psi at 135F. Outside Not required Steel None None Welded in accordance with ASME Code and attached specifications ASME Code Inspection & Code stamp: Hydrostatic test: Pneumatic test: Stress-relief: Radiography: Leak test: (Halogen) Required l times max allowable pressure 250 psi If required by ASME Code If required by ASME Code Required BLAND/UCC 445 's_J m 82 Connections, Liquid inlet: Liquid outlet: Spares: Pressure gauge: Gauge column Thermometer: Safety valve: Flanges: Manhole: Baffles: Grounding clips: Gauge-column clips: Ladder clips: Vessel support: One, 2-in., top One, 2-in., bottom One, 2-in., top; One, l|-in., bottom One, 1-in., top One, 1-in., top; One 1-in., bottom One, 1-in. coupling head, lower half One, lj-in., top* 300-lb ASA As required by ASME Code Not required Not required Required Not required Provide support saddles Notes: 1, Tanks located in areas where flammable materials are stored will require safety valve connections larger than lj in. 2. Filling liquid will have a specific gravity of 1.5. OESPTojl --------- _-------- . :- .rCJcORPoYH' T-- " 'V, 11 1 f BLAND/UCC 446 fxERO! J- iIcopt! ****"? ^ - . .... , .............. . 1C0FJV` 84 3B - Liquid Level Gage Assembly To provide visual indication of the liquid level in the storage tank. Make: Type: Fig. no.: Material: Connections: Operating pressure: Operating temperature: Jerguson or equal Armored reflex 620-R-5, visible length to equal or slightly exceed the diameter t>f the storage tank. Steel 1/2 in. screwed Full vacuum to 200 psig 60C maximum Note: Two shutoff valves (Jerguson No. 66U-C) should be purchased with the gage. A support bracket, similar to Jerguson Drawing No. GD-961, should be mounted at the mid-section of the gage by the manufacturer. / BLAND/UCC 447 OicToeproy1i! Sf" fxCRO5 ) COPY _r -rifr'iiiHiwgriA 85 3C - Pressure Gage To indicate the pressure of the vapor above the liquid in the storage tank. Maker Movement: Case: Dial: ir Range.i Bourdon tube: Connection: Ashcroft Duragage or equal All stainless steel, geared 1279, black phenol plastic 4-1/2-in. diameter, white, black figures 30-in. Hg vac to 30 psig Series A, phosphor bronze 1/2-in. NPT, bottom * For "Ucon" Fluorocarbon 11 only. For mixtures containing "Ucon" Fluorocarbon 12 or pure "Ucon" Fluorocarbon 12, specify a range of 30-in. Hg vac to 200 psig.` BLAND/UCC 3D - Indicating Thermometer To indicate the temperature of the liquid level in the storage tank. Make: Range: Dial: Stan length: Installation: Rochester 1748 or equal 25 to 125F. 3 in. diameter, white, black figures 6 In. Install in a brass separable socket with 1-in. HPT threads for the tank connection, 1/2-in. NPT,` threads for the thermometer to permit removal of the thermometer without disturbing the tank contents. 3E - Relief Valve To relieve pressure resulting from thermal expansion of the liquid in the liquid-inlet line to the storage tank. Make: Size: Material, body: Henry, Catalog Ho. 560-A, or equal 1/2 in. by 3/4 in. Steel nozzle: Stainless steel disc: Stainless steel spring: Steel Set pressure: 200 psig Operating temperature:: Atm bland/ucc 449 ( \ fERO f 'OPY f 87 3F - Pressure Gage To indicated the pressure in the vapor equalizing between the tank car and the storage tank. Duplicate Item 3C. 4 - Vaporizer No. 1* To maintain positive pressure In the storage tanks and to prime the unlpading pumps. Performance Data \ Material entering, weight per cent, UCON^ Fluorocarbons: Atmospheric steam: Material evaporated, weight per cent, UCON Fluorocarbons: Material leaving (vapor phase), weight per cent, UCON Fluorocarbons: Total quantity, entering: evaporated: leaving: Tube Side Shell Side 100% 100% 100% 100% 400 lb/hr max. 400 lb/hr 400 Ib/hr fxEROi COPY ' "Ft fT T (Continued) IXERO' * copy; " ' bland/ucc 450 XCRO! ` COPY a, ~v. a-.. Bf *iV ;K. tfi^L ..Z&-' ... .... 88 Tube Side Shell Side High temperature: Condensing temperature: Low temperature: Estimated quantity_o heat transferred. 41C 41C 0C Total: Corroding tendency: (for specified constr. materials) Fouling tendency: None None 100,000 Btu/hr None None Physical properties of single compound or the cornpositemixture Temperature: 2QC Molecular weight: 121 to 137 Viscosity, liquid: 0.3 cp Specific gravity, liquid: 1.4 to 1.6 Specific heat, liquid: 0.21 Btu/lb F Density, vapor: 0.606 lb/cu ft Latent heat: 76 Btu/lb Surface tension 19 dynes/cm 100C Operating pressure: Allowable pressure drop: Mechanical design pressure: Set pressure of safety valve: 10 psi - 200 psi 200 psi Atm - 150 psi *Used for outside tanks containing UCON 11. Not needed for UCON 12 and high-pressure blends. bland/ucc 451 fx'Slo'l fxEROi < xr*ROlt .COPrf Jcopy; Jcopy W -------------- pi * --"--"--~------------ - --r ;.;1 ^ -* -- ~ , |L- t.-A-K^f.p.i-* . ikrffi'aS'-J 89 Tube Side Shell Side Connections, Inlet: Outlet: 1-1/2-in, screwed 3/4-in, screwed 3-in. silver- 1/2-in. screwed soldered or brazed Type of unit: Shell and tube, heat exchanger, vertical, with straight tubes, and fixed tube sheet Maximum permissible over-all length: Minimum permissible tube diameter: 30 in. 3/8 in. Materials, shell: heads: tubes: tube sheets: gasket material: Copper Brass Admiralty Brass Teflon-filled Flexitallie Purchase a Ross HCF type heat exchanger, 16 s<r. ft. of heat-transfer surface 4A - Safety Valve To pretect the vaporizer from overpressure in the event that it is valveclosed while filled and the steam heat is left on. Make: Size: Henry, Catalog No. 560-A, or equal 1/2 in. by 3/4 inc, fxSJS'l (continued) bland/ucc 452 iXEROi iCOP'Y! Wr^rr> 'is, ----------- " ".. -:!'v | xni*o | COPT ' W' t ,.Y Vi-*C 90 Material, body: nozzle: disc: spring: Set pressure: Operating temperature* Steel Stainless Steel Stainless Steel Steel 100 psig Atm 4B - Temperature Regulator To control the vapor pressure generated in the vaporizer by throttling the steam flow: Performance Data Tube Side Shell Side Material handled: (Quantity, norm: Molecular weight, vapor: Temperature: Pressure, upstream: downstream: Line size and spec.: 5-10 psi steam 75 lb/hr 18 121C 5-10 psig Atm 3/4 in., steel Note: Temperature in vapor line from vaporizer should be 70 to 105F. Manual adjustment of temperature setting is required. Purchase Specifications Manufacturer: Model No.: Leslie ME-l-D, with temperature adjustment -v 1- riteHol copy l (continued) BLAND/UCC 453 \\ xCiQtFp'oY11 ..-vr it-.. . ,. :.T>,> -r^/ 91 Body size: Inner valve size: Rating: Operating range: Material, body: trim: 1/2-in., screwed 3/8-in. 200 psi 70-120F Bronze Stainless Steel Furnish with No. 3 stainless steel casing and 10 feet of flexible tubing. hC - Strainer To protect the steam throttling valve of the temperature regulator. Make: Size: Body: Screen: Perforations: Sareo, or equal 3/4-in., screwed 125-lb., cast iron Bronze, monel or stainless steel 1/64 in. approximately fxERO V ' *4copy l W uwg iXEROi i COP Y J BLAND/UCC 454 "fX`EOfRO?1 ,A Kffv Ado'll* L 9? SPECIAL VALVE AND PIPING SPECIFICATIONS GENERAL Maximum Pressure: Temperature Range: 200 psl Atmospheric PIPING Item Construction Fabrication Pipe Material Thickness Elbows, Tees and Other Fittings - Type Flanges - Type Facing : XERD) :copyf Size, incl. Specification To 3" To 3" To 1-1/2" 2" to 3" To 3" Screwed To equal or exceed requirements of the ASA Code for Pressure Piping (ASA B31.1), Section 6, Chapter 2. Steel, butt-welded: ASTM A53 Steel, electric-resistance-welded or seamless: ASTM A53 Grade A or B Schedule 40. To 3" To 3" To 3" Forged steel screwed: 2000 lb. (minimum) or ductile iron screwed: ASA 250 lb. Forged steel or ductile iron, screwed: ASA 300 lb. Manufacturer's standard (continued) fxEROl 1COPY1 BLAND/UCC 455 < XtlPO^ ' COPY f? /& , 4--<uAViul^Kt<;2*iiii.--H 93 Item Size, incl. Specification Unions - Type To 3" Pipe Plugs Bushings Gaskets Dope - Type Type Type Threads To 3" To 3" Gaskets Flange Bolting - Studs To 3" - VALVES Nuts Forged steel screwedi 2000 lb. (minimum). Steel. Steel. Durabla or equal. Teflon Tape: Permocel Itibbon Dope No. 412 thread sealant, or equal. Shellac. Alloy steel: ASTM A193 Grade B7, B7A, or B14. Alloy steel: ASTM A194 Grade 2 or 2H TypeGlobe Check Size Identifi cation 1/2" 3/4" 1" 1-1/2" 2" 2-1/2" GL GL GL GL GL GL l/2"to2" CK Make and Figure Number Henry 320 Henry 330 Henry 340 Henry 220 Henry 230 Henry 240 Vogt 2501-8 Body Semi-steel Semi-steel Semi-steel Semi-steel Semi-steel Semi-steel FS Trim Steel Steel Steel Steel Steel Steel Steel Type of Ends Screwed Screwed Screwed Screwed Screwed Screwed Screwed f1x-ceoRRor if pr... ^ XEROl copy! ftf" - - -'V___ bland/ucc 456 r'' *r CLEANING AND TESTING THE STORAGE SYSTEM To prevent contamination of UCON Fluorocarbons with rust and foreign matter, all interior surfaces of the tanks and interconnecting piping should be dry, clean, and rust-free. This is best accomplished by grit blasting, done as the last phase of construction. Leak testing should be done after the system has been assembled but before the final cleaning to reduce the sources of contamination to an absolute minimum. Leaking Joints can be located by introducing a few pounds of UCON Fluorocarbon 12 Into the system, raising the pressure to 150 to 200 psi with dry air, nitrogen, or carbon dioxide, and checking all joints with a halogen torch or a G. E. Type H-l Leak Detector. Leak detectors can be rented or borrowed from a tank fabricator. The joints using spiral-wound. Teflon-filled gaskets that must be opened for the cleaning operation should be fitted with asbestos gaskets for the test. Spiral-wound gaskets, particularly for manholes, are difficult to replace on short notice. Before sandblasting, all tank nozzles not openend for this operation should be wire-brushed and plugged to keep grit out of the valves and fittings. Tight-fitting wooden plugs are recommended. The tank should be thoroughly vacuum-cleaned and evacuated immediately after sandblasting, since an over night delay would allow some oxidation of the cleaned surfaces. Upon reassembly after cleaning, the system should be capable of holding a vacuum of 28 inches of mercury for eight hours with no appreciable rise in pressure; pressure rise would indicate either a leak or the presence of moisture in the system. If the system is not placed in service immediately after final BLAND/UCC 457 95 cleaning and testing, it should be pressured slightly with dry nitrogen. Air should not be admitted into the system after the final cleaning. If a small amount of lubricating or refrigeration type oil can be tolerated in the UCON Fluorocarbons, the tank fabricator will, at a modest cost, grit-blast the interior of the vessel and apply an oil film to prevent oxidation. Contamination from the interconnecting piping should not be objection able,if only the straight pieces of pipe are sandblasted immediately before fabrication. All traces of cutting oil should be carefully removed from the pipe threads before sandblasting and fabrication. This work can be done by firms that specialize in cleaning equipment of this type. Chemical cleaning is not recommended, since our experience with it has been unsatisfactory. BLAND/UCC 458  Jis ,-r. '- > ' v * ^3* 96 FILLING UCOIT^ FLUOROCARBON STORAGE SYSTEMS FROM TANK TRUCKS Since the tank trucks are fitted with gasoline-powered pumps, filling n storage systems from them will be very simple. In most cases, it will be simply a matter of connecting the hoses and starting the truck-mounted pump* However, the following suggestions and comments should be consideredt (1) Before filling the system, it should be evacuated to a vacuum of 28.5 Inches of mercury, or greater if possible, and held for eight hours. The system should then be filled as soon as possible to prevent leakage of air and moisture into the tank. If it cannot be filled immediately, the vac uum should be broken by introduction of just enough Fluorocarbon (from cylin ders) to produce a slight positive pressure in the tank. (2) If initial filling of the system can be started while it is under vacuum, connect only the liquid-unloading assembly and start the pump. Do not connect the vapor return line until the system is under positive pressure. (3) Unloading hoses for handling very volatile mixtures of UCON Fluorocarbons should be fitted with a small valve near the quick coupling to relieve pressure before disconnecting the hoses. (4) Carefully clean and dry the hose ends before making the connection. (5) Do not start the unloading operation in rain or snow unless the unloading spot is sheltered. (6) Any part of the system opened for repair should be thoroughly cleaned and either evacuated, or purgedlwith the UCON Fluorocarbon It is to handle, before it is placed in operation. bland/ucc 459 ji cxocrp*O*;' p* 97 (7) If It Is necessary for workmen to enter the storage tank, either the tank should be force-ventilated or the workmen should be fitted with air masks, UCON Fluorocarbons are non-toxicbut oxygen is necessary to support life. /' ^ TR |jlWP ixeo* bland/ucc 460 BIBLIOGRAPHY 98 1. "Aerosols: Science and Technology", Edited by H. R. Shepherd, Interscience Publishers, 1961. 2. Pressurized Packaging (Aerosols)", Herzka and Fiekthall, Academic Press, Inc., 1958. 3. R J. Scott and R. R. Terrill, "Aerosol Propellant Blends", Soap and Chemical Specialties, 38, Nos. 1 and 2, 142 (1962). R, J. Scott and R. R. Terrill, "Vinyl Chloride - Fluorocarbon Mixtures as Aerosol Propellants", Aerosol Age 7, No. 1, 18 (1962). .1 5. R. J. Scott and R. E. Feathers, "Aerosol Propellant Blends", Soap and Chemical Specialties, 38, No. 6, 154 (1962). 6. H. P. Coward and G. W. Jones, "Limits of Flammability of Gases and Vapors", Bulletin 503, U. S. Bureau of Mines (1952). 7. J. R. Haase and R. J. Scott, "Azeotropic Aerosol Propellants", Soap and Chemical Specialties, 40, No. 8, 105 (1964). 8. R. J. Scott and M. E. Clayton, "Water-Based Space Sprays", Soap and Chemical Specialties, 40, No. 9, 151 (1964). 9. "The Contribution of Atomic Energy to Agriculture", Hearings Before the Subcommittee on Research and Development of the Joint Committee on Atomic Energy, Congress of the United States, March 31 and April 1, 1954. * ( vEflO k )(>PY | fi-XCEORPOy lV ft fxeSo] \copy, bland/ucc 461 app1 jXCCORPOt ' rw ,- A 99 GENERAL APPENDIX ! V to) 'Y f rxEROi COPT f m fxEROl Icopy: BLAND/UCC 462 i xr.pcrt ] COPY T T # m Appendix A DIMETHYL ETHER/FLUOROCARBON AEROSOL PROPELLANT BLEND By R. J. Scott And R. R. Terrill Technical Service Laboratory Union Carbide Corporation Chemicals Division Tarrytown, New York Paper presented by R. J, Scott December 6, 1961 during 48th Annual Meeting, Chemical Specialties Manufacturers Association, New York, Reprinted from Soap and Chemical Specialties January and February 1962 BLAND/UCC 463 ANY liquefiable gases could, on the basis of vapor pressure alone, serve as aerosol propellants. When factors such as toxicity, safety, cost, and reactivity are considered, the number is narrowed to but a few. Of these, general acceptance has been accorded to fluorocarbons as fulfilling most of the requirements imposed by safety and utility. Other potential liquefied gas propellants are flammable and re quire special equipment for hand ling and storage. For many years there has been an interest in com bining these materials with the fluorocarbons in the hope that the resulting mixture would still be nonflammable, Reed (J) developed one such mixture, known as "Pro pellant A." It consists of 10% isobutane and 90% fluorocarbon 12/11 50/50. The fact that one, useful, nonflammable mixture was defined suggested the probability that others could be determined. There fore, some time ago the technical service laboratory of Union Car bide Chemicals set out to survey the whole field of aerosol propel lants and propellant blends. Our objective was to determine the criteria for a safe, nonflammable blend and, then, devise blends that would meet these standards. We soon found it necessary to separate the candidates accord ing to the intended application. The reason for this is the differ ence in boiling points (and, hence, in pressures) and the opportunity for fractionation when two materi als differing in boiling points are mixed together. Isobutane, for ex ample, would not make a good blend with fluorocarbon 12, be cause it lowers the pressure and tends to separate, producing a flam mable vapor. With fluorocarbon 12/11 50/50, however, the pressure is not significantly changed and the vapor coming off at the begin ning and the end of a fractionation is at all times rich in fluorocarbon relative to the flammable constitu ent. In other words, there is what might be called a "head" and "tail" arrangement, with nonflammable fluorocarbon coming off before, with, and after the flammable component. Such an arrangement is necessary with all propellant blends involving flammable materi als that have significant differences in boiling points. Propellant A is a moderate pressure propellant. The question soon arose as to the possibilities of a high pressure blend for products now utilizing straight fluorocarbon 12, primarily aerosol paints. Di methyl ether attracted our atten tion as a prime candidate for one of the components. It boils at --24 C., has a pressure of 60 psig. at 70 F,, and a K-B value of 91, indicat ing good compatibility with paint resins. The use of dimethyl ether, as an aerosol propellant is not new, it was suggested by Rotheim as far back as 1931 (2). Vapor mixtures of dimethyl ether and fluorocarbon 12 have been investigated by the Bureau of Mines (3), and although it was indicated that a nonflam mable system could be devised, the manner of doing so has not been revealed in the published litera ture. In general, dimethyl ether did not find much use as an aerosol propellant, primarily because it is flammable-and was not commer cially available. When, however, dimethyl ether did become commercially available, a study was initiated to determine if an economically at tractive, safe, nonflammable blend of dimethyl ether and fluorocarbon could be developed. Flammability At the outset, a criterion was established that any blend that was developed would have to be nonflammable in a true scientific sense, and would have to be safe for use without requiring an in vestment in detection equipment and alarm system. Our concern was primarily with factory opera tions, such as storage, warehousing and filling, rather than simply complying with legal regulations on an individual prospect or con tainer basis. The standard regula tory tests, such as flame projection and drum tests, were inadequate AV ERO DPT for our purposes because of their arbitrary nature. To determine true flamma bility of gases and vapors one must turn to the Bureau of Mines, and the concept of explosive limits which it has developed (4). Basi cally, an explosive, or flammability, limit is that composition of a vapor mixture which is capable of propa gating a flame, For any given mix ture there are two limits, a lower and an upper. The former repre sents the point at which there is sufficient flammable material pres ent to propagate a flame; the upper limit represents the point beyond which there is too much flam mable material, or, conversely, not enough air or oxygen present to propagate a flame. Very often, it is observed that a cap of flame forms around the source of ignition in the presence of flammable vapors*, but the flame is extinguished when the source of ignition is removed. Such mixtures have not reached the explosive limit and should not be regarded as flammable, for it is flame propagation that is the key which makes a gas or vapor dan gerous. The Bureau of Mines has published data on explosive limits for a great many materials (4) and they are often quoted in physical property and specification tables. As an inert gas or flamma bility suppressant is added to a mixture of a flammable gas and air, the explosive limits are brought closer together until they meet. This is pictured graphically as a flammability curve. Such a curve has been determined for mixtures of dimethyl ether and fluorocarbon 12 by the Bureau of Mines and is shown in Figure 1**. The vertical axis represents concentrations of dimethyl ether vapor and the hor izontal axis represents concentra tions of fluorocarbon 12. Note that tire points on the vertical axis are the explosive limits in air. Any point inside the curve represents a flammable mixture; any point out side the curve represents a non flammable mixture. Frequently ob*etved with drum Reprinted from Bureau of Mine* Re port of Investigation* 4125 FLUOROCARBON 12, % BY VOLUME FjOf: FLAMMABILITY CURVE FOR VAPOR MIXTURES of dimethyl ether and fluorocarbon 12 The chart is interpreted as follows; In addition to dimethyl ether and fluorocarbons, air is also present in the mixtures and is rep resented by the origin (i.e., when dimethyl ether and fluorocarbons are zero). It is apparent that draw ing a line from any point on the diagram toward the origin repre sents dilution with air. If the two axes are connected with a diagonal line as shown, that line will repre sent mixtures of dimethyl ether and fluorocarbons alone. From it the maximum amount of dimethyl ether vapor that can be mixed with fluorocarbon vapor without form ing a flammable mixture can be determined. sible to determine the maximum amount of dimethyl ether that can be incorporated without producing a flammable mixture at any dilu tion with air. Such a mixture is represented by the intersection of the dilution line with the diagonal, which occurs at SO per cent (by volume) dimethyl ether and 70 per cent fluorocarbon 12. Thus, vapor mixtures of dimethyl ether and fluorocarbon 12 will be non flammable at any air dilution, as long as the initial concentration of dimethyl ether does not exceed 30 per cent by volume. What does this mean in terms of the liquid phase? For this, a straightforward calculation is' made, as follows: In a closed system, the com position of a vapor mixture of two components can be expressed as: F Pi + Pi where A =.Limit in the vapor for the flammable component ex pressed as a decimal P = Total pressure p, = Partial pressure of one com ponent Pj -- Partial I ressnre of the other component Applying Raoult's Law: a M.W' ab _/MAV.r + "M.W, Po, A = - X, PO! x, POj + Xj Po, (2) a- b "i M.W., POj'f " M.W.., ab ab _m.w~ +m:w.; Jm.w., M/ttC_ Consider, for example, the halfway point on the diagonal, which represents a 50.50 vapor mixture of dimethyl ether and fluorocarbon. If a dilution line were drawn from this point toward the origin (which is equivalent to diluting the mixture with air), the line would pass through the flam mable area, and the mixture would, therefore, be hazardous. If, however, a dilution line is drawn tangentially to the flammability curve, as shown above, it is pos where x, = Mole fraction of component one x,, = Mole fraction of component two M W.t = Molecular weight of e ponent one M.\V.,, -- Molecular weight of com ponent two Po, = Vapor pressure of c mpoueut one Fo,, -- Vapor pressure of c mponent two a = Per cent hy weight of com ponent one in the liquid phase b = Per cent by weight of com ponent two in the liquid phase Us** ,1 W*l In IXERO; * COPY. ESI BLAND/UCC 465 f\ XEPO conr Equation (2) simplifies to: a Pt_ M.W., A =-----------------------------------(3) a po,_ b po2 M.W., + 'M.WT' where the symbols have the same significance given above. since: a + b = 100 then: b = 100 -- a Substituting in (3): apoi M.W.,* 1 _ a pOi__ (100 -- a) pos M.W.j + " " MAV".:, ' Solving for a: Fracti' noli n Since dimethyl ether and fluorocarbon 12 differ in boiling points, there was a possibility that the vapor composition might change if a small leak should de velop in a container in which the mixture is present. This would give rise to efficient fractionation and the possibility that dimethyl ether could, at some stage, exceed the 30 per cent limit in the vapor phase. To explore such a possibility, frac tionation tests were run at various temperatures as described in the experimental section. In essence, the procedure consisted of allow ing the mixture to bleed slowly 100 A M.W., po; a " M.W., pot - A (M.WTpo, - M.W., po,,) We now have a relationship expressing the concentration limit for the liquid phase (a) in terms of the limit in the vapor phase (A) as determined by flammability studies. Note that all the other terms are constants for any given mixture. We now substitute in equa tion (4) the following values for a mixture consisting of dimethyl ether and fluorocarbon 12. A = 0.30 (determined from Figure 1) pOj = Vapor pressure of dimethyl ether = 74.7 psia at 70"F. po2 = Vapor pressure of fluorocar bon 12 = 84.7 psia at 70*F. M.W.j -- Molecular weight of dimethyl ether = 46.1 M.W., = Molecular weight of fluoro carbon 12 = 120.9 a = Per cent by weight of dimethyl ether in the liquid phase b = Per cent by weight of fluoro carbon 12 in the liquid phase from a container and following changes in the vapor composition with a gas chromatograph. It should be borne in mind that frac tionation occurs only when leaks develop and allow the vapor com position to change; it does not Table I. Fractionation Data lor Mixture Consisting of 15% Dimethyl Ether and 85% FInorocarbon 12 Par cent by weight.of sample discharged Dimethyl ether in vapor, per cent by volume A. At room temperature (20*C.) 0.0 26.7 1.0 26.9 9.8 26.3 27.6 26.2 47.2 26.7 51 8 26.9 72.3 28.2 80 5 27.5 100(0.30) (46.1) (84.7) ____ (120.9 x 74.7) - 0.30 [ (120.9 x 74.7) - (46.1 x 84.7) ] a = 15.6% This calculation indicates that 15.6 per cent by weight is the greatest amount of liquefied di methyl ether that can be mixed with liquefied fluorocarbon 12 and not yield a flammable vapor at any dilution with air. To provide a small safety margin, it was de cided to adopt a mixture contain ing 15.0 per cent by weight liquid dimethyl ether for further explora tion. 93.5 97.0 0.0 19.4 52.8 65.0 92.5 99+ 0.0 28.6 33 4 77.8 99.0 B. At 0"C. C. At --10"C. 32.7 33.6 27.6 26.8 26.8 27.3 32.2 34 8 24.1 24.5 25 0 25.3 33.5 00 42 0 77.4 88.4 0.0 24.6 32.5 68 8 77.8 B6 7 92 0 98.0 D. At --22"C. E. At --42"C. 23.2 26.3 28 7 37.1 271 26.6 25.3 22.5 24.4 26.9 25.7 30.3 PER CENT (BY VOLUME) DIMETHYL ETHEF IN VAPOR Figure 2. Fractionation curves for mix ture consisting of 15% dimethyl ether and 85% fluorocarbon 12. occur in normal use, such as with drawal of propellant from a storage tank. The data for the fractiona tion tests are given in Table I and are pictured graphically in Figure 2. The vertical axis in -Figure 2 represents the per cent of the con tainer discharged, and the hori zontal axis represents the dimethyl ether content of the vapor. The safety limit is at 30% dimethyl ether, determined from Figure 1 as discussed above. Runs were made at five different temperatures to determine the behavior of the blend under conditions of both pressure filling and cold filling. Note that the initial points on the horizontal axis represent the vapor composition of the blend before fractionation begins, and also rep resent experimental proof of the calculation above. The amount of w XEROl ICOPY[ p; " fxEROl COPY; ^------ j| AA BLAND/UCC 400 \ XERO * COPY T if uj -+>-*--*+-<-ii./i.3-&.-- ,^,-l ._. 4i, dimethyl ether in the vapor is actually a little less than might be expected from Raoult's Law. It can be seen from Figure 2 that fractionation varies with tem perature, and that at about 80% of container discharge the dimethyl ether builds up in the vapor in excess of the safety limit. This means that if a slow leak developed in a storage tank of the blend, for example, the vapor coming from the tank after 80% of the contents had bled off would contain greater than 30% dimethyl ether and would, therefore, be flammable. What is needed here is a "tail" to retard the separation of dimethyl ether as discussed above. (Fluoro carbon 12 forms the "head"). Al though fluorocarbon 114 could serve as the "tail," it is expensive and would be ruled out on an eco nomic basis if more than two or three per cent were required. The only other alternative is fluoro carbon 11, and the amount to be added must be carefully consid ered. A sufficient quantity must be present to suppress the buildup of dimethyl ether, but an excess would lower the pressure of the blend, thus requiring more pro vable II, Fractionation data for mixture consisting of 15% di nt thyl ether, 75% fluorocarbon 12 and 10% fluorocarbon 11 Per cent Dimethyl ether Propellant 11 by weight in vapor, in vapor, of sample per cent per cent discharged by volume by volume A. At room temperature (20C.) 0.0 27.2 28.6 26.7 2.8 3.5 56.6 26.3 69.5 26.5 5.4 9.4 80.0 25.3 10.6 86.2 25.6 16.8 99.0 9.1 79 9 B. At 0*C. 0.0 25.4 2.4 267 26.3 42.7 25.6 3.2 4.0 76.3 26.9 92.7 25.1 10.6 28.1 C. At --10'C. 0.0 25.8 2.1 25.0 25.2 2.8 36.8 25.2 50 3 26.0 3.3 3.7 68.2 25.8 96,5 23.9 5.6 36.5 D. At --22*C. 0.0 24.7 1.9 20.2 24.7 27 38.6 25.2 2.9 52.7 , 25.5 4.3 82 4 , 27.5 8.7 99.0+ 28.5 6.3 E. At --42'C. Not enough came out of the container to get measurements in a reasonable time. PER CENT (BY VOLUME! OF DIMETHYL ETHER IN VAPOR Figure 3. Fractionation curves for mix ture of 15% dimethyl ether, 75% fluorocarbon 12 and 10% fluorocarbon II. pellant to obtain a given pressure when it is mixed with a product. It was decided to repeat the frac tionation tests with a mixture con sisting of 10% by weight liquid fluorocarbon 11, 15% dimethyl ether and 75% fluorocarbon 12. The data for the tests are given in Table II and are shown graphi cally in Figure 3. It can be seen from Figure 3 that the fluorocarbon 11 pulled all of the curves away from the safety limit, and the blend will not form a flammable mixture upon dilution with air even if leaks (and, thereby, fractionation) should occur. Flammability Again The curve in Figure 1 ap plied to mixtures of dimethyl ether and fluorocarbon 12. Fluorocarbon 11 has now been added, however, and the data in Table II show that fluorocarbon 11 does build up in the vapor. It was necessary, there fore, to determine what effect this would have on the flammability curve and, hence, on the 30% safety limit. The fractionation data in Table II show that fluorocarbon 11 in the vapor ranged from a low of 1.9% by volume to a high of 36.5%. At one point a concentra tion or 79.9% was reached, but at the same time the dimethyl ether content had dropped off to 9%, and this point can be neglected in determining the fluorocarbon ratio to be investigated. It was decided to obtain flammability curves for dimethyl ether with fluorocarbon 12/11 90/10 and 50/50 vapor mix tures, in order to cover the range in which fluorocarbon 11 might be expected to be present. A flammability tester was constructed according to informa tion available from the Bureau of Mines (4,5) and is described in the experimental section. In es sence, the tester consists of an ex plosion tube 150 cm in length in which the mixture of gases under test are subjected to ignition from a hot spark. If the mixture is flam mable, a flame will be set off and traverse the length of the tube. The flammability curves which were obtained with the tester are shown in Figure 4. The inner curve applies to fluorocarbon 12/11 90/10 and is identical to Figure 1 which, in turn, applies to straight fluorocarbon 12. In other words, the presence of 10% fluoro carbon 11 in the vapor does not change the flammability curve at all. When fluorocarbon 11 is in creased to 50%, however, as shown by the outer curve in Figure 4, the flammable area is enlarged. This is in accordance with the Bureau of Mines' hypothesis that the efficien cy of a flammability suppressant depends on the specific heat, since fluorocarbon II has a slightly low er specific heat (0.135 cal/g/C.) than fluorocarbon 12 (0.145 cal/ g/C.). Note, however, that the intersection of the dilution line with the diagonal is only slightly altered, changing the safety limit from 30% dimethyl ether to 28%. Thus, even a relatively large amount of fluorocarbon 11 in the vapor does not affect the safety of the blend. fSfEROt ,_COPT [ Fp lx mo! i copy ; M rn r*--r bland/ucc 467 ?0'i XERO1 COPY ` ^ J ft-.*1 ., A-f'<-*.->-ft FLUOROCARBON % BY VOLUME PART n Performance Factors Table III. Evaluation of Dimethyl Ether-Fluorocarbon Blend Expansion Ratio and Pres with Nitrocellulose Lacquer sure. The expansion ratio of a liq uified gas is the ratio of the specific volume of the vapor to the specific volume of the liquid. It is indica tive of the amount of "breakup" that might be expected from a given propellant. Since dimethyl ether has a considerably higher ex pansion ratio (350) than fluoro carbon 12 (255), it might be ex pected that the blend would con Components of Test Solution, Per Cent by Weight Toluene Nitrocellulose Solvent* Diluent 12 88 0 12 78 10 12 68 20 12 58 30 12 53 35 12 48 40 12 38 50 12 28 60 Appearance of Test Solution When Mixed 1:1 by Weight With With Dimethyl Fluorocarbon 12 Ether Blend __ -- Clear Clear Slightly Cloudy Very Cloudy -- -- Clear Clear Clear Clear Clear Clear Slightly Cloudy Very Cloudy tribute more "breakup" than an equivalent amount of fluorocarbon * Methylisobutyl Ketone = 80% Butyl CELLUSOLVE = 10% Isopropanol = 5% Ethanol = 5% 12. This can be calculated as follows; % additional "breakup" = 100 fluorocarbon 12. However, the blend has a pressure of 64 psig, and more will be required to ob tain a given pressure with a prod taken here of viscosity, evaporation rate and, in the case of paints, the resin or resins being used. Solvent Properties'. Dimethyl where Ej = Expansion ratio of dimethyl ether = 350 Ez = Expansion ratio of fluoro carbon 12 = 255 a = Concentration (% by weight) of dimethyl ether = 15 The second term in the numerator is a correction for the 10% fluorocarbon 11 and, to apply the most restrictive conditions, assumes that the fluorocarbon 11 detracts only from the dimethyl uct calculated as follows: ether has a K-B value of 91, fiuoro- % additional propellant required to offset reduced pressure = 70-64 x 100 = 9.0 70 Adding the two factors, the advantage of the higher expansion ratio and the disadvantage of lower pressure, we have: -9% 16% Net gain = 7.0% carbon 12 has a value of 18, and the blend has a value of 31. Thus, the blend should have better sol vent properties for aerosol paints than straight fluorocarbon 12. This was borne out in tests with nitro cellulose and acrylic lacquers. ether expansion ratio. Substituting Thus, theoretically at least, The data obtained with ni numerical values, we have: approximately 7% less of the blend trocellulose systems are shown in % additional "breakup" 350x0.15-0.1 x0.15x350 255 x 100= 18.5 Table III. Although alkyd resins are normally used in commercial lacquers, they were omitted here This, theoretically, means should be required to obtain the because they are used in so many that approximately 16% less of the spray characteristics equivalent to different combinations, and it is blend should be required to obtain those of fluorocarbon 12. In actual the tolerance of the nitrocellulose a breakup" equivalent to that of practice, however, this will have to itself for the propellants which is * Paper presented Dec* 6> 1961 during 48th annual meeting* Chemical Specialties Manufacturers Asati,, Ntw York* be evaluated with each individual product, since no account has been the point of interest. It can be seen from Table :*of )PY f ' w ! XEROl .COPY * 1 XERO1 jCOPY F"1" | BLAND/UCC 468 | XERO ? COPY g^- III that with fluorocarbon 12, the test solution became cloudy at 35% toluene. With the blend, the cloud point was raised to 50% toluene. This suggests the possibility that some of the active solvent might be replaced with lower cost diluent when the blend is used, but this must be balanced with the evapo* ration rate of the solvent system and the viscosity of the lacquer solution. Again, each product should be evaluated individually. In the case of acrylic lac quers, most of those now on the market consist of a solution of resin in toluene. There has not been a great problem in packaging such lacquers as far as resin com patibility is concerned, but it was of interest to determine if an acry lic resin had a greater tolerance for the blend than for the straight fluorocarbon. The amount of propellant required to cloud 10 grams of a solution consisting of 20% "Acry- loid" B-82 and 80% toluene was: Dimethyl Fluorocarbon 12 Ether Blend 13.8 grams 24.4 grams Thus, with acrylic lacquers, almost twice as much of the blend can be tolerated. This provides a leeway for the filler and formulator, and might permit an increase in solids content if such were de sirable from a marketing and per formance standpoint. was due mainly to the difference in boiling points. The addition of 10% fluorocarbon 11 to the blend prevented this buildup, and the dimethyl ether content of the va por at no time crossed the 30% safety limit. A blend consisting of 15% by weight dimethyl ether, 75% fluorocarbon 12 and 10% fluoro carbon 11 is a suitable aerosol pro pellant for high pressure applica tions, and is safe for use in both pressure filling and cold filling. Experimental Flammability Studies: The Bureau of Mines Flammability Tester which was used in this work is shown in Figure 5 and its opera tion is described in detail in the Bureau's Report of Investigations 4839 (5). The operation of rite instru ment was as follows; 1. The tube was sealed and the system evacuated for 30 min utes to remove moisture and reac tion products from previous explo sions. 2. Sample gases were fed into the system through three-way rut Summary Vapor mixtures of dimethyl ether and fluorocarbon 12 are non flammable as long as the dimethyl ether content is below 30% by volume. This requires a liquid mixture containing no more than 15.6% dimethyl ether by weight, and a blend consisting of 15% di methyl ether and 85% fluorocar bon propellant 12 was selected for further study. It was found that, during the latter stages of an efficient frac tionation, the vapor from the blend could become flammable from build-up of dimethyl ether. This r 1 tael c :i 7 ` T --iJ/?S ; :- } |U1 valves. The amounts were con trolled by pressure readings taken on the manometer which was grad uated to 0.5 mm. The amount of each gas is given by the relation ship: Per cent by volume of sample =- where p = pressure of the sample P = barometric pressure = total pressure After the dimethyl ether and fluorocarbon were in, the system was brought to atmospheric pres sure by allowing air to enter the tube. 3. After atmospheric pres sure was reached, the gases were mixed with the diaphragm pump for five minutes. 4. The pump was then turned off, the glass plate removed from the bottom of the tube and, simultaneously, a spark applied across the gap. If the mixture were flammable, a flame would be set off and travel the length of the tube. The Bureau of Mines is of the opinion that if the flame travels only two-thirds the length of the tube or less, the mixture is non- . ;f Figure 5. Flamma bility tester used in developing di* methyl ether fluo rocarbon blend. i ,a BLAND/UCC 469 1 XEROl COPY fxERO! Icopy; ST 15 xCrO.RPOY .ik V'> f flammable, and this classification was followed. In practice, our flames either traveled the length of the tube or less than halfway, and there was no difficulty in classifying the mixtures. Fractionation Studies: The fractionation tests consisted of bleeding off the vapor from con tainers filled with dimethyl ether blends and following changes in the vapor composition as the con tainers were emptied. To produce an efficient fractionation, the con tainers were bled at a minimum rate of 25% in two hours; most of the data in Tables I and II were obtained at the rate of about 25% in three to four hours. The procedure was as fol lows: Six-ounce containers were sealed with tilt valves and pressure filled with the mixture being studied. A .046" hole was drilled into actuator buttons and capillary tubes inserted into the holes. Screw clamps were placed on the capil lary tubes and the assembly placed on the valves. With the buttons secured in a tilted position, the containers were allowed to bleed off, the rate being controlled by the screw clamps. The containers being run at low temperatures were placed in Dewar flasks filled with the appropriate cryogenic solution. As the containers were bleeding off, weight losses were de termined at periodic intervals and, simultaneously, the vapor compo sition determined with the gas chromatograph. It was Found in early work that taking samples by bleeding into evacuated containers and then analyzing gave widely varying re sults and such a method is not recommended. Acknowledgments The authors wish to express their appreciation to Mr. M. W. Ranney and Miss C. J. Doherty of the Union Carbide Chemicals tech nical service laboratory for the ex tended chromatographic analyses and assistance in determining the solvent properties of the blend, and ' to Mr. S. S. Taylor for assistance in obtaining flammability data. Bibliography 1. W. H. Reed, "A New Pro pellant Blend," Soap and Chemical Spe cialties, 32 No. 5, 197, 1956, 2. E. Rothcim, "Method and Means for the Atomizing or Distribu tion of Liquid or Semiliquid Materials", U. S. Patent 1,800,156 (1931). 3. G. A. Jones and F. E. Scott, "Inflammability of Dimethyl Ether -- Dichlorodifluoromethane -- Air Mix tures", Bureau of Mines Report of In vestigations 4125 (September, 1947), 4. H. F. Coward and G. W. Jones, "Limits of Flammability of Gases and Vapors", Bulletin 503, Bureau of Mines (1952). 5. G, S. Scott, M, G. Zabetakis and A. L. Furno, "Flammability of Mixtures of Individual Paraffin --Hy drocarbon Gases with Air and Added Nitrogen at Subatmospheric Pressures", Bureau of Mines Report of Investiga tions 4839 (January, 1952). {XEROl 1COPY\ bland/ucc 470 IXERO' * COPY 'FT Appendix B VINYL CHLCR IDE/FLUOROCARBON AEROSOL PROPELLANT BLEND By R. J. Scott And R. R. Terrill Technical Service Laboratory Union Carbide Corporation Chemicals Division Tarrytovn, New York Reprinted from Aerosol Age January 1962 ft' - BLAND/UCC 471 'M /oi Introduction L^OR some time, one of the top *" priority projects at the Tarry- town, N. Y., Technical Service Labor atory of Union Carbide Chemicals Co. has been development of propel lant blends that would be both safe and non-flammable, The first phase of the project was to develop a high pressure'propellant blend. To accomplish this, it was necessary to separate the different candidates according to boiling point and vapor pressure. An example of why these factors are important is the experimental work done with isobutane. This material would not make a good blend with fluorocarbon 12, because it lowers the pressure and tends to separate, producing a flam mable vapor. With fluorocarbon 12/ 11 blended in equal amounts, how ever, the pressure is not significantly changed, and the vapor coming off at the beginning and the end of a fractionation is rich in fluorocarbon at all times. In other words, there is what might be called a "head and tail" arrangement, with non-flam mable fluorocarbon coming off before, with and after the flammable compo nent. Such an arrangement is neces sary with all propellant blends in volving flammable materials and significant differences in boiling points. Much research was accomplished on high pressure blends. It was in tended that these products could be used as a substitute for straight fluoro carbon 12, which of course, finds application ' primarily in aerosol paints. Dimethyl ether is a prime candi date because of its pressure (60 psig. at 70F), its boiling point (---24C), and its high K-B value (91). An equally' important research project Conducted at the Tarrytown laboratories was the development of moderate pressure propellants and propellant blends, which now utilize mixtures of fluorocarbon 12 and 11 in products such as hair sprays, in secticides, and room deodorants. The most common, a 50-50 mixture, has a vapor pressure of 37 psig at 70F, and there are not many liquifiable gases with vapor pressures falling in this range. One that does is vinyl chloride with a vapor pressure of 35 psig at 70F and a boiling' point of --13.4C. Vinyl chloride reportedly has been used by itself as a propellant23 and mixtures with fluorocarbons have been mentioned2, but there is no evi dence in the published literature that a quantitative blend has been worked out. This paper presents the results of a detailed study on vinyl chloridefluorocarbon mixtures, which was carried out in the Union Carbide's Technical Service Laboratory, and which led- to the development of a safe, nonflammable blend. Flammability Studies Unlike dimethyl ether-fluorocarbon mixtures, where one of the flammability curves was known', the vinyl chloride curves could not be found in the literature and had to be determined experimentally. In such a case, it is easier to operate a flammability tester with a mixture of two gases rather than three. Accordingly, the curve was located with vapor mixtures of vinyl chloride and fluorocarbon 12, and the effect of added fluorocarbon 11 then determined. The question of what fluorocarbon ratio to use for the vapor was resolved by considering the vapor-liquid equilibria. It can be calculated that the fluorocarbon portion of the liquid phase would have to contain more than 70% fluorocarbon 11 to produce a 50/50 ratio in the vapor. Therefore, a vapor ratio of 50/50 would represent the probable maximum that a 50/50 liquid ratio would produce. Fractionation tests later showed this to be the case.* The flammability curves are shown in Figure 1 and * The apparatus, procedure and technique used for the flammability and fractiona tion studies were the same as those used for dimethyl ether, and have been des cribed previously1. BLAND/UCC 472 xCrO.nPoVj^ ur&rf. -s , Vv ' /-*T'Li ' ,-- are interpreted in the same manner as those for dimethyl ether1. The maximum amount of vinyl chloride that can be tolerated in the vapor is determined by drawing dilu tion lines tangent to the flammability curves, as shown. The intersection of the dilution lines with the diagonal gives the maximum amounts of vinyl chloride that can be present without forming flammable mixtures at any dilution with air. The curves in Figure 1 are unusual in that they are almost dome shaped. This is due to the wide flammability range of vinyl chloride which tends to "spread out" the curve, and which produces a steep slope on the lower side. This, in turn, gives a high angle to the dilution line and a high intersect on the diagonal. Very large amounts of vinyl chloride can be tolerated in the vapor thereby; a larger amount of admixant, in fact, than was found with any other of the many blends we have studied. The inner curve of Figure 1 applies to vinyl chloridefluorocarbon 12 mixtures and the outer curve to vinyl chloride-fluorocarbon 12/11 50/50. The latter shows an effect similar to that observed with dimethyl ether1, i.e., the tip is extended and the flammable area is somewhat enlarged. This is in accordance with the specific heat relationships observed previously (0.145 cal/g/C. for fluorocarbon 12 versus 0.135 cal/g/C. for fluorocarbon II)'and indicates that fluorocarbon II is not as good a flammability suppressant as fluorocarbon 12. It is in teresting to note that the specific heat effect does not show up until relatively large amounts of fluorocarbon are present (i.e., at the tip of the curve). The angle of the dilution line, however, is not greatly altered and the safety limit for vinyl chloride in the vapor is only reduced from 48 to 45%. Nevertheless, the difference between the two curves is significant in flammability work and shows that chemical homologues do not necessarily func- tion in the same manner nor with the same degree of efficiency. It is not advisable to apply a curve for one mixture to another made up of chemically similar con stituents. For mixture1 of vinyl chloride and fluorocarbon 12 the dilution line in Figure 1 indicates that the vapor can contain as much as 48% vinyl chloride without forming a flammable mixture at any dilution with air. A relation ship expressing the liquid phase composition in terms of the vapor for a two-component system has been derived previously1 and can be applied to vinyl chloride-fluoro carbon 12 mixture as follows: 100 A W.W., M.W.J Pp, - A(M.W., Rl - M.W., ft,,) Kubauniitaf 1(X^-4H63.5>(*4,7) (1J0.9><49.7) - 0.4* (1*0,9) (49.7) ' (*2.5)(*4.7) 4** where: a -- Per cent by weight of vinyl chloride in the liquid phase A -- Limit for the vinyl chloride concentra tion in the vapor = 48% p, z= Vapor pressure of vinyl chloride ~ 49.7 psia at 70 C. zz Vapor pressure of fluorocarbon 12 zz 84.7 psia at 70C. M.W. = Molecular weight of vinyl chloride = 62.5" M.W.,, -- Molecular weight of flJVocarbon 12 -- 120.9 ----------------- S-X- T <8? f, + 0, + Pj The above calculation indicates that liquid mixtures of vinyl chloride and fluorocarbon 12 can contain as much as 45% by weight vinyl chloride without the vapor being flammable. This does not take fractionation into account, FLUOROCARBON % BY VOLUME FIS. I FLAMMABILITY CURVES FOR VAPOR MIXTURES OF VINYL CHLORIDE AND FLUOROCARBON i AERO .COPY! tr. AERO . copy ; BLAND/UCC 473 s'xeoo1 ' CQF* X T** ' ' ' .ST xw f _, _ . *_. - fctfr* w 1*- 'W.iAjSfel', however, and it will be severe because of the large dif ference in boiling points and the absence of a "tail"1. __ (See below), When a sufficient amount of fluorocarbon 11 is added to provide a protective "tail," the mixture becomes a moderate pressure blend which is precisely the area now under discussion. The outer curve in Figure 1 applies to the fluorocarbon 12/11 mixtures in which we are interested. The intersec tion of the dilution line with the diagonal indicates that, wth a fluorocarbon 12/11 50/50 ratio in the vapor, a maximum of 45% (by volume) vinyl chloride can be tolerated. To convert to the liquid phase is a little more complicated for a system with three components rather than two, but the principle is the same. Let: As before1, we have a relationship expressing the con centration limit in the liquid phase (a), in terms of the limit in the vapor phase (A) as determined by flam mability studies. All other terms are constants for any given mixture. Note that careful attention to signs in the denominator is necessary when using this relationship. The following values can now he substituted in equation (6): A -- 0.45 (from Figure 1) p#1 = Vapor pressure of vinyl chloride z= 49.7 paia at 70*F, pff,, = Vapor pressure of fluorocarbon 12 = 84.7 psia at 70*F. p*3 zz Vapor pressure of fluorocarbon 11 = 14.7 psia at 70ftF, M.W^ zz Molecular weight of vinyl chloride " 62,5 M.W,., = Molecular weight of fluorocarbon 12 ^ 120.9 M.W.3 := Molecular weight of fluorocarbon 11 z= 137.4 A = Limit in the vapor for the flammable component as determined on the flammability chart. P " Total pressure of the system, pi -- Partial pressure of one component, pj -- Partial pressure of the second component, ps -- Partial pressure of the third component. <2P Applying RuHiii'v Law; . ' p-i * ` *1 ., * *1 SV, * `3 % W a M.W.j M.W.j * M.W.j + M.W.j M.W.j S M.'wT, + M.w7j + M.w.3 _ b M W.j' " _b +___ L, M.W.j M.W.j M.Wj r m.w.. [M.W.j M.W.j M.W j (S0)(O,4S) ^4.7>(62.&)U37.4) + <H.7)(2.5)1ll0.^] 1 Thus, a mixture consisting of 29.4% by weight of liquefied vinyl chloride and 70.6% of liquefied fluoro carbon 12/11 50/50 contains the maximum amount of vinyl chloride which can be incorporated without forming a flammable vapor. Since aerosol propellants are used at different tem peratures, depending on whether a product is being filled or cold filled, it was necessary to determine the behavior of the blend under fractionation conditions at various temperatures. Fractionation Studies where: x = Mole traction ot component one zr Mole fraction of component two = Mole fraction of component three =r Weight per cent of component one in the liqui phase = Weight per cent of component two in the liqui phase = Weight per cent of component three in th liquid phase M.W., -- Molecular weight of component one M.W. -- Molecular weight of component two m.w.; = Molecular weight of component three P., = Vapor pressure of component one P,, -- Vapor pressure of component two P-S -- Vapor pressure of component three Uquauon (1) Minpltfk* u; Pu, M.W,, M.W.3 *Po, M.W.J M.W.j bk.j M.W.j M.W.J * , ^ M.W.j M,W,2 !>, and t are wvlghr pvri'Hnugvit. W can nay a ft t 100 and if h * v (l.ti., h>r fluofwirt*>a 12/11 W5D in the liquid j*io*e) theft . , IW U , Substituting. a M.W.j M.W.j *>, M.W.J M.W,3 * >pu2 M.W. | M.W.j * (iJSiiOHv, M,\V.( M W., Solving fur a M.W., M.W.j + M.W.j M.W.j) SO Po, M.W.J M.W.J M.W.jMdV.j - 1/3 {JMj M.W., M. W.3+ ^M. W., M.W.Jj As explained previously1, when the components of an aerosol propellant blend differ in boiling point, there is a possibility that the components may separate under conditions of fractionation. Just as in the case of a dis tillation, the slower the separation is carried out, the more efficient it will be. It was also shown that, under conditions of evaporation, any propellant blend involving a flammable component should have a "head and tail" arrangement, such that protective fluorocarbon vapor comes off before, with, and after the flammable com ponent. An example of an improperly designed blend without this arrangement would be the 45% vinyi-chloride-55% fluorocarbon 12 mixture calculated above. Frac tionation tests were run on such a mixture, with the vinyl chloride content reduced to 35% to provide a safety margin. The tests were carried out at various temperatures in the same manner as those for dimethyl ether1, and the results are shown in Figure 2. The vertical axis represents the per cent of the container discharged, and the horizontal axis represents the vinyl chloride content of the vapor. The safety line is at 48% vinyl chloride, as determined from Figure 1. It can be seen that all of the curves cross the safety line after about 60% of the container has been discharged. This means that approximately 40% of the amount present will produce a flammable vapor. The shape of the curves in Figure 2 is typical of mixtures which do not 474E>TpROr .' cXoEpRyO jsi f XRO; * COPY BLAND/UCC ' *|x:ro cop ill . PERCENT (BY VOLUME) VINYL CHLORIDE IN ViPOR Flfl.S FRACTIONATION CURVES FOR 27% VINYL CHLORIDE 73% FLUOROCARBON 12/H 50/30 PERCENT IBY VOLUME) VINYL CHLORIDE W VAPOR FIG 4 FRACTIONATION CURVES FOR 4% VINYL CHLORIDE 7% FLOROGARBO* 12/1190/50 FIGS. FRACTIONATION CURVES FOR 22% VINYL CHLORIDE 7B% FLUOROCARBON 12/11 50/50 have a "head and tail" arrangement, and reducing the amount of flammable material present merely raises the crossover point a little higher. Returning to fluorocarbon 12/11 mixtures, the calcula tions given above indicated that a blend consisting of 29% vinyl chloride and 71% fluorocarbon 12/11 50/50 should have a vapor which is nonflammable. It was necessary to examine this mixture also under conditions of frac tionation, To allow a safety margin, it was decided to begin fractionation tests with a mixture of 27% vinyl chloride and 73% fluorocarbon 12/11 50/50. The tem peratures selected were 20C., 0C., and --10C. Lower temperatures do not allow emergence of enough vapor to get readings in a reasonable time. The fractionation curves are shown in Figure 3. The safety limit is at 45% vinyl chloride, as determined from Figure 1. Note that the points on the horizontal axis represent the initial composition of the vapor and constitute experimental proof of the calculations made above. It can be seen that even at room temperature (20C.) the curve approaches the safety line, and at lower tem peratures the curves cross over into the flammable area. The latter curves do not extend to complete exhaustion of the container because vapor emission gradually slows and eventually stops at low temperatures. Since a "head and tail" arrangement is already present, the only cor rective measure that can be taken is to reduce the amount of vinyl chloride. Accordingly, the tests were repeated on a mixture containing 24% vinyl chloride, as shown in Figure 4. In this case, no curve crosses the safety line but the low temperature curves terminate on it. A final set of curves was obtained on a mixture con taining 22% vinyl chloride, and these are shown in Figure 5. In this case, none of the curves crossed the safety line and the mixture can be regarded as safe for both pressure filling and cold filling. The final blend, then, consists of 22% oy weight vinyl chloride and 78% fluorocarbon 12/11 50/50. The fluoro carbon ratio can be altered and the limits for doing so can be determined. Any mixture different from 50/50, how ever, should be fractionated to be sure that vinyl chloride does not build up in the vapor. Performance Factors Expansion. Ratio Vinyl chloride has an expansion ratio of 333 compared to 255 for fluorocarbon 12 and, presumably, zero for fluorocarbon 11. An interesting calculation can be made on this basis as regards the added "break-up" contributed to an aerosol spray by the presence of vinyl chloride: Let Ei = Expansion ratio of vinyl chloride -- 333 E = Expansion ratio of fluorocarbon 12 = 255 E> = Expansion ratio of fluorocarbon 11 = 0 a, = Per cent by weight of vinyl chloride = 22 a3 = Per cent by weight of fluorocarbon 12 = 39 ai -- Per cent by weight of fluorocarbon 11 -- 39 Then, taking weighted averages: % ttfdlilonal "break -up" (B| *, + Bj + B] ay) * (Ej B3 ;) *2 8J *3 X 100 Thus, theoretically at least, the vinyl chloride blend should require less propellant than a mixture of fluoro carbon 12/11 50/50 to obtain equivalent spray charac teristics. This will be limited, however, by the desired evaporation rate, the particular function of the spray and the necessity to replace propellant with concentrate. Polymerization It is known that vinyl chloride can be stored for a considerable time without the presence of a polymeriza- 475 j'xKRO*1 TR BLAND/UCC 1 COPY r M tion inhibitor. It is also known, however, that polymeriza tion is easily initiated by heat, light, oxidizing materials, catalysts, hydrochloric acid, and so on. In view of the many different materials with which an aerosol propellant comes in contact, it is advisable to use a polymerization inhibitor. Three are now in common use: phenol, hydroquinone, and tertiary butyl catechol, in concentrations of 25 to 100 ppm. The most suitable for aerosols use is hydroquinone or the methyl ether thereof. Packaging Tests Typical formulations for a hair spray, an insecticide and a room deodorant have been packaged with the vinyl chloride blend. In general, compatibility was excellent and there were indications that the blend may be less corrosive to tinplated containers than the straight fluorocarbon propellant. Unlined aluminum containers, however, showed some corrosion in individual cases, and it is recommended that the compatibility of aluminum containers be care fully evaluated before using them with products pres surized with the blend. Because of the great variety of products utilizing moderate pressure propellants,-it is not possible to gene ralize on the suitability of the blend for each and every one. The blend is safe for use and handling, however. and the economics make an evaluation with any product worthwhile. SUMMARY Vapor "mixtures of vinyl chloride and fluorocarbon 12/11 50/50 are nonflammable as long as the vinyl chloride content is below 45% by volume. On a liquidweight basis, this corresponds to 29.4%. Because of frac tionation, however, the actual amount of vinyl chloride that can be tolerated is limited to 22%. Because of the high expansion ratio of vinyl chloride, a smaller amount of the propellant blend may be required to produce spray characteristics equivalent to those produced by the straight fluorocarbon. Packaging tests have shown good compat ibility with typical products such as hair sprays, insec ticides and room deodorants. A blend consisting of 22% vinyl chloride and 78% fluorocarbon 12/11 50/50 is a suitable aerosol propel lant for moderate pressure applications, and is safe for both pressure filling and cold filling. The authors are indebted to M. W. Ranney and Miss C. J. Doherty of the Union Carbide Chemicals Co. Technical Service Laboratory for extensive chromatographic analyses applied to the development of the vinyl chloride blend. BIBLIOGRAPHY 1. R. J. Scott and R, R. Terril, "Aerosol Propellant Blends: I. Dimethyl Ether-Fluorocarbon." Paper presented at the 48th Annual Meeting, Chemical Specialties Manufacturers Associa tion, New York, Dec. 19(51. 2. H. Kuebler, "Vinyl Chloride as an Aerosol Propellant," Aerosol Age, 3 No. 9. 26 (1958). 3. H. losaki, "Vinyl Chloride Finding Increased Use in Japanese Aerosols," Aerosol Age, 3, No. 2, 22 (1958), .ICXEORPOY|` 476bland/ucc Appendix C HYDROCARBON/FLUOROCARBON AEROSOL PROPELLANT BLEND By R. J. Scott And R. E. Feathers Union Carbide Corporation Chemicals Division New York Paper presented by R. J. Scott at the 48th Mid-Year Meeting, Chemical Specialties Mannfacturers Association, Chicago, May 15, 1962. Mr, Scott's at Union Carbide's Technical Service Laboratory, Tarrytown, New York, Mr. Feather's in Atlanta, Georgia. Reprinted from Soap and Chemical Specialties Jbne 1962 bland/ucc 477 "?W-T`r r- 7A\r--v RIGOROUS method of studying aerosol propel^allt blends has been des cribed previously. (1,2) This meth od requires that the flammability diagram for the system being in vestigated be first constructed from experimental data. The maximum allowable concentration of the flammable component in the vapor is then determined from the dia gram, and the corresponding liquid phase equilibrium composi tion is established by means of a detailed calculation. The liquid phase must then be adjusted, after careful experimentation, to allow for fractionation so as to maintain nonflammability under any condi tions of use. These principles were ap plied to the development of two propellant blends, one based on dimethyl ether (1) and the other on vinyl chloride. (2) The third area to be investigated was that of hydrocarbon-fluorocarbon combin ations. If any such blends were found safe and nonflammable, the relatively low cost of the hydro carbons could make such mixtures economically attractive. This, the third and concluding treatise of the scries, describes the results of our investigation of hydrocarbonfluorocarbon mixtures. The present paper, along with those on dimethyl ether and vinyl chloride, report a definitive study of aerosol propellant blends carried on over a period of three years at the Technical Service Laboratory of Union Carbide Chemicals Co. Blends developed on the basis of this study, and cur rently commercially available, are nonflammable. They cover the major applications involved in aerosol packaging: The dimethyl ether blend serves for high pres sure applications, the vinyl chlor ide blend for moderate pressures and the butane blend (discussed in this paper) for low pressures. Blends lor intermediate pressures can be developed, but they should be based on the principles laid down in this study, which form a scientific basis for gauging the safety of any propellant blend. Three hydrocarbon-fluoro carbon systems were examined, one based on propane for high pressure applications, another on isobutane for moderate pressures and a third on butane for a low pressure blend. The method and experimental equipment were the same as des cribed previously. (1, 2) For con venience, each system will be dis cussed separately. Propane-Fluorocarbon Propane (B. P. = -42 C.) was evaluated lor a high pressure blend with fluorocarbon 12 (B. P. -- --29.Sc C.) . In this case fluoro carbon 12 forms the "tail," and it was necessary to find a "head." (1) The only fluorocarbon suitable for this purpose is - fluorocarbon 22, which would have to be present in fairly large amounts because of the proximity of its boiling point (--41 C.) to that of propane. In point of fact, propane serves more as a diluent for fluorocarbon 22 than for 12. We determined the flamma bility curve with a fluorocarbon 12/22 vapor phase ratio of 50/50 to see how much propane could be tolerated by such a mixture. The flammability curve is shown as the sol it! line in Figure 1. For com parison, the Bureau of Mines' curve for propane-fluorocarbon 12 is shown as the dotted line. (3) It can be seen that the presence of fluorocarbon 22 not only changes the location of the curve, but also slightly enlarges the flam mable area. This is an exception to the general rule that the extinc tive efficiency of a gas or vapor is proportional tn its specific heat(-l) , since the specific heat of fluorocar bon 22 (0.152 caI/gm/C) is high er than that of fluorocarbon 12 (0.145 cal/gm/-'C). A similar ex ception was found by the Bureau of Mines with ethyl mercaptan and lluonx ai bon 22 vs. fluorocarbon 12(5). The anomaly is probably due to the presence of a hydrogen atom In the fluorocarbon 22 mole cule. Figure 1 is interpreted in the same manner as the other flam- XERO COPY | BLAND/UCC 478 -va i xr:fjo d :no*\i inability diagrams discussed earlier (1,2). The intersect of the dilu tion line with the diagonal repre sents the maximum amount of propane that can be tolerated in the vapor without forming a flam mable mixture at any dilution with air. For fluorocarbon 12/22 -- 50/50, this amount is 20 per cent by volume. To determine the corre sponding limit in the liquid phase, the relationship for a three com ponent system derived previously is applied (2): FLUOROCARBON V. BY VOLUME Figure 1 Equation (V) now relates the ap,, M.W.j M.W.,, ap , M.W.a M.W.,, -f- bp.j M.W., M.W.a (I) cp..s M.W., M.W._, where: A=limit in the vapor for the flamma ble component as determined from the flammability diagram; a = weight per cent of component one in the liquid phase; b = weight per cent of component two in the liquid phase; c = weight per cent of component three in the liquid phase; p.,=vapor pressure of component one; p2=vapor pressure of component two; P,,3--vapor pressure of component three. Since a, b and c are weight percentages: a + b -f c = 100 (II) and; for the system being studied: c=2.1b (i.e., a vapor phase ratio of fluorocarbon 12/22 50/50 corresponds to a liquid phase ratio of 2.1/1.0). (Ill) Substituting equation (III) in equation (II) limit for the flammable compon ent in the vapor to the correspond ing concentration in the liquid phase. All the other terms are con stants for any given mixture. We can now substitute numerical values and solve for "a": Let A = 0.20 (from Figure 1) ; p, = vapor pressure of pro pane = 123.7 psia at 70 F.; p3 = vapor pressure of fluoro carbon 22 = 134.7 psia at 70 F.; p,. = vapor pressure of fluoro carbon 12 = 84.7 psia at 70 F.; M.W., = molecular weight of pro pane = 44.1; M.W., = molecular weight of fluorocarbon 22 = 86.5; M.W., = molecular weight of fluorocarbon 12=120.9; Substituting in equation (V): liquid phase for a safe blend with fluorocarbons 12 and 22 in a ratio of 2/1. This does not take frac tionation into account, which pre vious experience (2) has shown to require some reduction in the flam mable component. Furthermore, such a blend would be more ex pensive than fluorocarbon 12 alone, even though a smaller amount of propellant would be required be cause of the high pressure of such a combination. Therefore, mix tures of propane and fluorocarbon J2/22 were not investigated any further. Calculations for mixtures of propane and fluorocarbon 12 alone are of interest because such mix tures are reportedly being used. We apply the relationship derived previously for a two-comjionent system (1), using the dotted line curve in Figure 1 to determine the safe limit for propane in the vapor: _ 100 A M.W., p.. M.W.j p,,j -A (M.W.,p,,1-M.W., p.,,) where: a = safe concentration limit in the liquid phase; A = limit in the vapor phase = 25 per cent (from Figure 1); M.W., = molecular weight of pro pane = 44.1; M.W.2 =. molecular weight of fluorocarbon 12 = 120.9; Pi = vapor pressure of pro pane = 123.7 psia at 70F,; p.2 = vapor pressure of fluoro- a b + 2.1b -- 100 0.20= _ a (123.7) (86.5) (120.9) 100--a b =-------------- (IV) i (123.7) (86.5) (120.9)+ ^-)-(154.7) (44.1) (120.9) +- 3.1 a = 8.0 per cent (84.7) (44.1) (S6.5) Substituting equations (III) and (IV) in equation (I) Thus, propane has a limit of only S per cent by weight in the carbon 12 = 84.7 psia at 70F. A =. ap,, M.W., M.W.j ap., M.W.2 M.W.3 + (l^ p.2 M.W., M.W.j + 2.1 i!^-p..s M.W., M.W.S 3.1 (V) XERO iCOPri f XERO. ICOPY, BLAND/UCC 479 I xi:ro rr r; ot' y/r i. 7 Substituting number values: data were obtained in the manner 100 (0.25) (44.1) (84.7) " (120.9) (123.7) 0.25 [(120.9) (123.7) - (44.1) (84.7) ] a = 7.6 per cent Thus, the maximum amount of propane that can be tolerated in a mixture with fluorocarbon 12 is only 7.6 per cent by weight in the liquid phase. This does not take fractionation into account which, witii the large spread in boiling poiu's a"-! absence of a ``head,'' is 1 c'v io be severe. There is also v;i!ice for a safety margin i.iVii would ordinarily reduce .K stalling point to about 7.0 per i. 1: is, therefore, questionable whether any significantly economi cal mixture of propane and fluoro carbon 12 can be regarded as non flammable. It is interesting to note, in concluding the examination of pro pane mixtures, that the blend with fluorocarbon 12 had a higher per missible limit in the vapor (25 per cent) than fluorocarbon 22/12 (20 per cent), but a lower limit in the liquid phase (7.6 per cent vs. 8.0 per cent). This is due to the ; molecular weight and vapor pres sure relationships in equations (I) and (II), and points up the neces sity of a detailed calculation in go ing from the vapor to the liquid phase. Isobutanc~Fltiorocarbon Having a vapor pressure of 31 psig at 70F., isobutane may be regarded as a moderate pressure propellant, and, therefore, a candi date for a blend with fluorocarbon 12/11 -50/50. Considerable work on isobutane-fluorocarbon 12/11 mixtures (propellant A) (6) had already been carried out by W. H. Reed. However, Dr. Reed had not defined the flammability curve and we had to determine how closely he had approached the safety limit by his method. Accordingly, flammability described previously (1), and were plotted graphically (Figure 2). An interesting comparison shows that the area inside the curve is smaller than that for propane-fluorocarbon (Figure 1) or for butane-fluoro carbon 12 (Figure 4). Indeed, of all hydrocarbons, isobutane has one of tiie most favorable flamma bility curves when incorporated in propellant blends. In Figure 2, the intersect of the dilution line with the diagonal shows that the safe limit for isobutane in the vajmr is 24 per cent by volume. To determine the corre sponding composition of the liquid phase, the relationship for a three component system with the fluoro carbons in a 50/50 ratio is used (2) It should be noted that the fluoro carbon ratio is important in these calculations and can change the final form of the relationship: fluorocarbon / 90/90,% by volume * Figure 2 Isobutane, therefore, has the high (for a hydrocarbon) limit of 14 per cent by weight in the liquid phase when mixed with fluorocar bon 12/11--50/50. However, frac tionation of the biend is to be ex pected. Dr. Reed found, '7 Rim mability determinations at rum.', temperature, that fractionation lowered the safety limit to approxi mately 32 per cent, and reduced propellant A even further to 10 per cent to provide a safety mar gin. It was of interest to determine 50A [p.jM.W.jM.W.j 4. p.jM.W.jM.W.j] p.,M.W.sM.W.a-A[p.1M.W.sM.W.s- l/2(p.sM.W.1M.W.s -f p,,,M.W.,M.W.?)] a = limit for isobutane in the liquid phase, per cent by weight; A = limit for isobutane in the vapor = 24 per cent; p,, = vapor pressure of isobu tane = 45.7 psia at 70F.; p-.j = vapor pressure of fluoro carbon 12 = 84.7 psia at 70.; p3 = vapor pressure of fluoro carbon 31 = 14.7 psia at 70F.; M.W-! = molecular weight of isobutane = 58,1; M.W.j = molecular weight of fluorocarbon 12=120.9; 1W.W.3 = molecular weight of fluorocarbon 11 = 137.4. Substituting; i[ this limit was sufficient to cover fractionation at cold filling tem peratures. Accordingly, fractiona tion curves were run on propellant A at five different temperatures, as shown in Figure 3. The lowest was --10 C., since vapor emission at lower temperatures was not suffici ent to get readings in a reasonable time. The safety line is the point of intersect of the dilution line with the diagonal in Figure 2. As can be seen in Figure 3, none of the curves touch or cross the safety line, and propellant A appears equally safe for both cold and pressure filling. The importance of a proper "head" and `'tail" arrangement in any blend comprising components of significantly different boiling 50 (.24) [(84,7) (58.1) (137.4) -j- (14.7) (58.1) (120.9)] (45.7) (120.9) (137.4) 0.24 [ (45.7) (120.9) (137.4) - (84.7) (58.1) (137.4) a = 14.0 2 (14.7) (58.1) (120.9) 2 -O i XEBOl COf'v i XERO COPY 480bland/ucc | xr.w',' 141-*- --- ; if Figure 3 points is shown in Figure 4. We fractionated a blend similar to propellant A., with the isobutane content maintained at 10 per cent, but the fluorocarbon 12/11 ratio changed from 50/50 to 35/65. The amount of fluorocarbon 12 present in this blend is not sufficient to form an adequate "head," and the vapor is flammable at room tem perature (curve No. 1 in Figure 4) throughout most of the frac tionation. At 10 C. (curve No. 2) the vapor becomes flammable dur ing the middle stages of the frac tionation. The curve would prob ably swing back across the safety line during the latter stages if vapor emission had not ceased due to the low temperature and large amount of fluorocarbon 11 remain ing. It cannot be emphasized too strongly that a safe propellant blend must be rigorously devised so that the vapor will remain non flammable under conditions of use. Butane-Fluorocarbon With its vapor pressure of 17 psig at 70 F,, butane is a low pressure propellant and a com panion to fluorocarbon 114. With boiling points so close together (-0.6 C. for butane and 3.6 C, for fluorocarbon 114), it was assumed that fractionation would present no problem. Accordingly, flamma bility data were obtained on bu- tane-fluorocarbon 114 mixtures; the curve is plotted in Figure 4. For comparison, the Bureau of Mines' curve for fluorocarbon 12(3) is shown as the dotted line. It can be seen that fluorocarbon 114 reduces the flammable area considerably, due to the specific heat relationship (0.160 cal/gm/ C. for fluorocarbon 114 vs. 0.145 cal/gm/ C. for fluorocarbon 12). It is also interesting, that the curve for butane - fluorocarbon 114 is strikingly similar to that for isobutane-fluorocarbon 12/11--50/50 (Figure 2). If one is superimposed on the other, they appear almost identical. The intersect of the dilution line with the diagonal in' Figure 4 shows that the safe limit for butane in the vapor is about the same for fluorocarbon 12 and 114, at 24 per cent by volume. To determine the FLUOROCARBON % BY VOLUME Figure 5 carbon 114 = 27.7 psia at 70F,; M.W.] ~ molecular weight of bu tane := 58.1; M.W.j = molecular weight of fluorocarbon 114 = 170.9, whence; a =____________ 100(0.24) (58.1) (27.7) (170.9) (31.7) - 0*24 [ (170*9) (31,7) - (58.1) (27.7)] a = 8.5 per cent corresponding liquid phase com position for a blend of butane and fluorocarbon 114, which would find application in uncoated glass bottles, we apply equation (VI), for a two-component system where: a = safe concentration limit in the liquid phase, per cent by weight; A = limit in the vapor phase = 24 per cent (from Figure 4) ; p, = vapor pressure of butane=31.7 psia at 70F.; p: = vapor pressure of fluoro- Figure 4 Allowing for a small degree of fractionation, it appears that ap proximately 6.5 to 7.0 per cent by weight of liquefied butane might safely be incorporated with fluoro carbon 114. However, actual frac tionation tests should be run to de termine the precise amount. This is disappointing, but in line with other hydrocarbon blends. Of more commercial import ance, perhaps, is a blend of butane with fluorocarbon 12/114--10/90, since the latter is frequently em ployed with aerosol perfumes. To determine the safe limit for butane in the liquid phase of such a mix ture, we apply equation (I) where: A = limit for butane in the vapor = 0.24; a s=e weight per cent of bu tane in the liquid phase; b = weight per cent of fluo rocarbon 12 in the liquid phase; c = weight per cent of fluo rocarbon 114 in the liquid phase; pi = vapor pressure of bu- **-------------- : cop r) -'T'? XEROt copy ; BLAND/UCC 481 xHpo COPY < i eroI opy ( & "Jut, >*' tane = 31.7 psia at 70F.; pj = vapor pressure of fluoro carbon 12 = 84.7 psia at 70F.; ps = vapor pressure of fluoro carbon 114 = 27.7 psia at 70F.; M.W., = molecular weight of bu tane = 58.1; M.W.j, = molecular weight of fluorocarbon 12=120.9; M.W.S = molecular weight of fluorocarbon 114=170.9. Again, a + b + c = 100 (VIII) and; c = 9 b (i.e., for fluorocarbon 12/114 10/90) whence: 100-a b =----------- 10 (IX) Substituting equations (VIII) and (IX) in equation (I): be incorporated with fluorocarbons to produce nonflammable propel lant blends. The limits for the various mixtures are as follows; Max. flamma Bland ble component, % by wL in liquid phase 1. Propane-fluoro carbon 12/22-2.1/1.0 2. Propane-fluoro carbon 12 3, Isobutane-Quoro- 8.0 7.6 carbon 12/11-50/50 10.0 4. Butane-fluoro carbon 114 5. Butane-fluoro 8.5 carbon 12/114-10/90 1U Only one of these (No. 3) has been corrected for fractiona tion. Fractionation can lower the safe limit for some of the other blends considerably, particularly for blends of components with widely divergent boiling points. A blend of butane and fluorocarbon 12/114 -- 10/90 ap- Chloride-- Fluorocarbon Mixtures as Aerosol Propellants," Aerosol Age 7, No. 1, 18 (1962), 3. G. W. Jones and F. E. Scott, "Ex tinction of Propane and Butane Flames by Dichlorodifluoromethane," Bureau of Mines Report of Investi gations No. 3908, (June, 1946). 4. H. F. Coward and G. W. Jones, "Limits of Flammability of Gases and Vapors," Bureau of Mines Bulletin S03, (1952), 5. G. W. Jones, M. G. Zabetakis and G. S. Scott, "Elimination of Ethyl Mercaptan Vapor -- Air Explosions in Stench Warning Systems," Bureau of Mines Report of Investigations No. 5090, (1954). 6. W. H. Reed, "A New Propellant Blend," Soap and Chemical Special ties, 32, No. 5, 197 (1956). A= ap.j M.W.j M.W., -)- (100-a) 10 ap,,, M.W.j M.W., (p,,2 M.W., M.W.S) + 9 (100-a) p,,, M.W., M.W.S 10 Substituting numerical values and solving for a: pears to be feasible and is now under development as a low pres- 0.24= a (31.7) (120.9) (170.9) a (31.7) (120.9) (170.9) + a = 11.1 percent (100-a) [ (84.7) (58.1) (170.9) ] 4. 9 10 (100-a) [ (27.7) (58.1) (120.9) ] 10 Here, we find that the ad dition of fluorocarbon 12 to fluoro carbon 114 raises the amount of butane that can be tolerated to 11 per cent. This again demonstrates the need for a detailed calculation when translating from the vapor to the liquid phase. A blend of butane and fluorocarbon 12/114--10/90 is now under development at the Union Carbide Chemicals' Technical Ser vice Laboratory. It is expected to be equivalent in performance to the straight fluorocarbon and will be of considerable economic inter est. Summary In general, only small amounts of the hydrocarbons can sure propellant for aerosol per fumes. Experimental The apparatus, procedure and technique used for the flam mability and fractionation studies were the same as those used for the dimethyl ether blend, and have been described previously. (1) Acknowledgments The authors are indebted to T. C. Hower and K, O. Mahler for extensive chromatographic analyses involved in carrying out the fractionation tests dis cussed in this paper. Bibliography 1. R. J. Scott and R. R. Terrill, "AeroPropellant Blends," Soap and Chemi cal Specialties 38, No. 1, 142 (1962). 2. R. J. Scott and R. R. Terrill, "Vinyl |xeflol ;copy ( XERO'. COPY ; P BLAND/UCC 482 /> cxco;ppoy fir &- - '-J `1 A-.VfiW^ Z-f`: j- ---. i-,. V} Appendix D GENERAL EQUATIONS FOR CALCULATING THE COMPOSITION OF AEROSOL PROPELLANT BLENDS OF INTERMEDIATE PRESSURES By R. J. Scott Technical Service Laboratory Union Carbide Corporation Chemicals Division Tarrytown. New York "4- **mr i'CXOERPOYl' fvm** h BLAND/UCC 483 3i xcio;ri'ov . 121 INTRODUCTION The UCON aerosol propellant blends were developed to cover three major products areas: those utilizing high pressures (such as paints), moderate pressures (such as insecticides) and low pressures (such as perfumes). Many products, however, require intermediate pressures, and although it would not be economical to develop a specific blend for each one, it is possible to adjust the pressure of the present blends by adding more fluorocarbon to them. In this way, it is possible to retain the nonflammability of the blend and at the same time provide a price advantage, although it may be less than that of the parent mixture. Therefore, a simple means of calculating the composition of blends with intermediate pressures would be useful in broadening the application of all the blends. It is the purpose of this report to show how general relationships can be derived for adjusting the composition of any UCON blend to any desired pressure. SUMMARY AND CONCLUSIONS The following relationships show the composition required to produce the desired pressure, in psia at 70T7. Percentages, molecular weights,and mole fractions are incorporated in the various constants, and care should be taken to be sure the correct relationships are being used for a given mixture: I. UCON Propellant P: For lower pressures by dilution with propellant 11: % propellant 12 = 52.5P^ - 803 67.3 - 0.32P/' % dimethyl ether = 10.5P'' - 160 67.3 - 0.32P' % propellant 11 = 7690 - 95P^ 67.3 - 0.32P/ II. UCON Propellant A: A. For higher pressures by dilution with propellant 12; % propellant 12 = 51P^ - 1266 26 + 0.07P' . L.-V, , XERO*'. COPY * ) 3 cXfoTpRyO Tf BLAND/UCC 484  JfXr- 122 % isobutane = 701 - 8P'' 26 + 0.07/ % propellant 11 = 3159 - 36/ 26 + 0.07P/ B. For lower pressures by dilution with propellant 11: % propellant 12 = 31,5/- 481,5 33.5 - 0.17?' % isobutane = 7/ - 107 33.5 - 0.17P/ % propellant 11= 3935 - 55,6P/ 33.5 - 0.17P' m. UCON Vinyl Chloride Blend: A. For higher pressures by dilution with propellant 12: % propellant 12 = 64,7P^ - 2170 21.0 + 0.16P" % vinyl chloride = 1541 - 17.6P/ 21.0 + 0,16P/ % propellant 11 = 2735 - 31.2P/ 21.0 + 0.16P/ B. For lower pressures by dilution with propellant 11: % propellant 12 = 27,3/ - 417,3 38.4 - 0.26P/ % vinyl chloride = 15.4P/ - 235.8 38.4 - 0.26P/ % propellant 11 = 4493 - 68.6P/ 38.4 - 0.26P/ iCOF*Y BLAND/UCC 485 *] COPY ' IY. UCON Fragrance Propellant: For higher pressures by dilution with propellant 12: % propellant 12 = 63.IP'' - 1800 45.7 - 0.096P' % n-butane - 595 - 6.8?' 45.7 - 0.096P' % propellant 114 = 5760 - 66P/ 45.7 - 0.096P/ DISCUSSION The original blends were designed with "head and tail" arrangements to allow for fractionation during use. If the pressure were changed merely by maintaining the concentration of the flammable component and altering the fluorocarbon ratio, the "head and tail" arrangement would.be altered and the mixture could become flammable. On the other hand, if fluorocarbon is added to a blend as such, the flammable component becomes diluted and although the fluorocarbon ratio of the total mixture is changed, the ratio relative to the flammable component is not. Intermediate pressures, then, can be obtained by the addition of fluoro carbon to one of the standard blends, The calculations below show how each standard blend can be so adjusted. I. UCON Propellant P (Pressure = 64 psig at 70F). The pressures of interest here are those below 64 psig, since propellant P is already a high-pressure blend and there would be no point in making it higher. This means that propellant II would be added, and the amount required to obtain any desired pressure can readily be calculated as follows: Present Composition ; 15% (0.326 moles) dimethyl ether 75% (0.620 moles) propellant 12 10% (0.073 moles) propellant 11 Total moles = 1.019 To 100 parts of the blend will be added y parts of propellant 11 to obtain the desired pressure P', so that the total moles of the new mixture becomes (1.019 + y . ), and: 137.4 jXEROt BLAND/UCC 486 P7 = Pl + p2 + P3 - XX p0l + x2 Po2 + x3 Po3 (1) where: p = partial pressure of the individual components in psia at 70*F x = mole fraction of a given component p0 = vapor pressure of the pure component, in psia at 70F Subscripts refer to dimethyl ether, propellant 12, and propellant 11, respectively. Substituting numerical values in equation (1): p' = (0i326)(74.4) + (0.620) (84.7) +(0.073+ y 1(14.7) V137.4) 1.019 + y 137.4 y * 78.0 - 1,02P/ 0.007P/ - 0.107 (3) (2) Equation (3) shows the additional amount of propellant 11, in the same weight units as used for the other components, required to lower the pressure of UCON propellant P to the new pressure, Py. In examining equation (3), it is obvious that the numerator will always be positive, since P/ is decreasing with successive additions of propellant 11. It might at first glance appear possible to have a negative denominator and, hence, a negative value for y. However, the denominator must first become zero upon dilution with UCON propellant 11 (at P' = atmospheric pressure, approximately 15 psia) before it becomes negative. This point would correspond to infinite dilution with propellant 11, and in practical terms the pressure of the mixture would approach that of propellant 11 and never go below it. Thus, a negative value for y would have no physical meaning. follows: The composition of the resulting mixture is then readily calculated as % dimethyl ether = / 15 \ t nn = 10.5P1' -160 1100 + y I 67.3 - 0.32P' copr f !*ero{ icopyi T* i___ tTT r"" { XERO (COPY` P j' bland/ucc 487 XERO$ copy W* " ,-v. - . wS>.. 125 % propellant 12 % propellant 11 75 J 100 = 52.5P' - 803 100 + y 67.3 - 0.32P 10 + y ) 100 = 7690 - 95P^ 100 + y 1 67.3 - 0.32P' II. UCON Propellant A (Pressure = 37,5): "With UCON propellant A, the pressure adjustment can either be upward with additional propellant 12, or downward with additional propellant 11. A. For an upward adjustment with propellant 12: . Present Composition: 45% (0.372 moles) propellant 12 10% (0.172 moles) isobutane 45% (0,327 moles) propellant 11 Total moles = 0,871 For the addition of y parts of propellant 12 to 100 parts of the blend to obtain the desired pressure P', the total moles become (0.871 + y ), and: mj P- " xlP0l+x2 Po2 + *3 Po3 where the symbols have the same significance as above and the subscripts refer to propellant 12, isobutane and propellant 11, respectively. Substituting numerical values: /o. 372 + y \ 84.7 + (0.172)(45.7) + (0.327)(14.7) _V________ 120.9/ 0.871 + 120.9 y = 0,871P/ - 44.16 0.701 - 0.008P/ (5) (4) Here, when P/ is approximately 51 psia (which is the pressure of propellant A), the numerator becomes zero and no propellant 12 is to be added. As P increases, the denominator approaches zero at 85 psia, which corresponds to infinite dilution with propellant 12. yopY i l xepoi mi.COPlf| IT itCXOERROY]. BLAND/UCC 488 l XCRO The percentage composition of the new mixtures can be expressed as: % props''ant : 2 % isohu+.r c r/-v, " (%:J.Xoo - 51 P' - j 266 V/ 26+0. GT?* o -oo . d' : ; / 701 - ?>?' 26 - ' \ i------- v :>o --y I gt - - 6 -r Op ;r' B. 1\ r . 'j - (0.372)(84.7) + p.I72)(45.7)+-|o.327 + y \l4,7) 0. 871 + V 137.4 j y = 4-hi6 - 0 S7I? : -----------------' . 0.0C7f/ * .107 (7i The same considerations apply here as with equation (3), i ,e,. as bee on as lower, the denominator approaches zero which is equivalent to infinite dilution with propellant 11. It is interesting to note that equations (5) and (7) differ primarily in sign. The precentage compositions for the lower-pressure mixtures are: V% propellant 12 =./ 45 (_ 100 + y j 31.5P" - 4SI.5 ssTi-^oTi'/F^' % isobutane = ( 10 ^ion = 7p' - 107 (lOO + y / 33.5 - 0.17P' % propellant 11 =/ 45 + y \ Vtv + y /j 3935 - 5E.6P/ 33.5 * 0.17P' *ZL>'r' bland/ucc 489 . I--- - III, UjCON Vinyl Chloride Blend (Pressure - 36.5 psig at 70F) Propellant A, the pressure of the vinyl chloride blend can be adjusted-mtfcBry^upward or downward. The downward adjustment is probably of greatest interest, particularly for the large hair spray market, but there may be occasion for an upward adjustment also and calculations for both will be given. A. For an upward adjustment with additional propellant 12: Present Composition: 39% (0.323 moles) propellant 12 22% (0.352 moles) vinyl chloride 39% (0.284 moles) propellant 11 Total moles = 0.959 Adding y units of propellant 12 to obtain the desired pressure P/, the total moles become (0.959 + y ) and: 120.9 P' = (o.323 + y \84,7) + (0.352)(49.7) + (0.284)(14.7) V l20j) 0.959 + --------------------------------------------- 120.9 (8) y * 0.959P^ - 49.1 0.701 - 0.008P' (9) The same considerations apply here as with equation (5). The percentage composition of the higher-pressure mixture is: propellant 12 = f 39 + y yioo \100+y 64.7P/ - 2170 21.0 + 0.16P'r vinyl chloride =* if 22 ^100 _o 1541 - 17.6P/ \ 100+ y 21.0 + 0.16P" propellant 11 = /f 39 N}l00 V, 100 + y 2735 - 31.2P/ 21.0 + 0.16P/ XEROj COPY | **CXOERRYO- sl\ ST ...T j XERO t COPY, BLAND/UCC 490 47P B. For a downward adjustment with propellant 11: P7 = (0.323)(84.7) + (0.352)(49.7) + /O.284+ y ^14.7 \ 137.4 / 0.959 + y 137.4 y 49.1 - 0.959P 0.007P" - 0.107 (11) The percentage compositions of the lower-pressure mixtures are: -f% propellant 12 =1 39 _ 27.3Py -417.3 v 100+ yI100 = 38.4 - 0.26P'"~ % vinyl chloride = p_\ 00 = 15,4/ - 235.8 ylOO + yj 38.4 - 0.26P/ % propellant 11 = / 39 + AnO - 4493 - 68.6P/ 1100 + yj 38.4 - 0.26P/ (10) IV. UCON Fragrance Propellant (Pressure = 20 psig at 7QF) This blend is a low-pressure propellant, and the only adjustment of interest would be an increase in pressure with propellant 12: Present Composition: 9,15% (0.076 moles) propellant 12 8.50% (0.146 moles) butane 82.35% (0.482 moles) propellant 114 Total moles * 0.704 p/ = [0.076+ y \84.7 + (0. 146)(31.7)+ (0.482)(27.7) \ 120.9 )_______ _ 0.704 + 120.9 (12) y = 0.704P/ - 24.4 0.701 - 0.008P/ (13) I XEROr r' '4 COPT * BLAND/UCC 491 xt.ro ` COPY' --* The percentage compositions of the new mixtures become: % propellant 12 63.1P^ - 1800 45.7 - 0.096?' n-butane 595 - e.81^ 45.7 - 0.096P' % propellant 114 = 5760 - 66P" 45.7 - 0.096P' fxSeTi w- BLAND/UCC 492 m xt;o  . .*.1 : 4. m^-A'WvW.J. Appendix E UCON Propellant 12/11 VAPOR PRESSURE VS. TEMPERATURE 130 rrpr fc ;.XCEoPPOr IT rgywrr BLAND/UCC 493 XOCORf'YO'- 731 Appendix E UCONI2/UC0NII Fluorocarbon Propellant Blends V{ Vapor Pressure vs Temperatere, F 400 UCON 12 ^ 300 PERCENT BY WEIGHT 200 a> o> 3 O cn ro: c ot_> o3 O' </> a(_> o. V) -O c 3 oa. <3(iaunOD> u. o a. o > ci KERO "7"'C hi v, "P bland/ucc 494 Appendix F UCON Propellant A and Vinyl Chloride Blend . VAPOR PRESSURE VS. TEMPERATURE "O^r |ke:ro fc i!CXOERPOV CXOERPOY '; BLAND/UCC 495 i xr.RO; COP r Appendix F 133 VAPOR PRESSURE, POUNDS PER SQUARE INCH GAUGE TEMPERATURE, F ;COPY t J< buand/ucc 496 `;XcCoRpyO' v > Appendix G UCON Propellant A and Vinyl Chloride Blend DENSITY VS. TEMPERATURE EftO { OPY t rXERO) ;CQPY [ -f |xero; jCOPY` M' BLAND/UCC 497 * XEROi 1 COPY Appendix G UCON_ PROPELLANT A AND VINYL CHLORIDE BLEND DENSITY VS TEMPERATURE, F TEMPERATURE, F XERO1 iCOP YI Hi? bland/ucc 498 Appendix H UCON Propellant 12/Propane 90/10 VAPOR PRESSURE VS. TEMPERATURE 136 XErtOl COPT ! XERO; copy ; bland/ucc 499 XCOE?RJOY ' ^ *l." Appendix I UCON Propellant 12/Propane 90/10 SPECIFIC GRAVITY VS. TEMPERATURE "" W'!" xero; COPY wr BLAND/UCC 501 xr,RO : cop f AdOO t ,o:ix | ZOS oon/QNvna OTT 001 06 ` AodaOsOx J 08 ^4^^*aj.'vV4 " ajn^Baadoidi 0L 09 *a( 08 Ofr oe 06* I AiO ) OH3 56`( \ 00'1 80' C/i 1 or "r3n. !;i r\ ST' -<T> . c ... jr- ! 0Z` sz* OS' / SNVJO'Hd NODH/ZI MODQ dO 01/06 V >JOd H'anxvHadPMaj. snsaaA aj.iavho oihiohjs XIpuaddy Appendix J UCON Propellant 12/Isobutane SPECIFIC GRAVITY VS. COMPOSITION IXEttOl ;cqpy: BLAND/UCC 503 f'xtIRO COPY Appendix J ?''? g { 4 TABLE IV A REVIEW OF COMPOUNDS TESTED FOR AZEOTROPES WITH FLUOROCARBON III * CO s a coo ot o Cl / Second Component Vinyl Chloride Isobutane Fluorocarbon 142b Isobutylene L-Butene 1,3 -Butadiene n-Butane cis 2-Butene trans 2-Butene Vinyl Methyl Ether Fluorocarbon 133 Fluorocarbon 21 Neo pentane Ethyl Chloride Ethyl Chloride, Fluorocarbon 21 * Compactions are tn weight %. Results of Study Azeotrope discovered No azeotrope found No azeotrope found No azeotrope found No azeotrope found Azeotrope discovered Azeotrope reported previously (3) No azeotrope found Azeotrope discovered Azeotrope discovered Azeotrope discovered Azeotrope previously reported (8) \ V No azeotrope found Azeotrope previously reported (7) Ternary azeotrope found Remarks * 28% Fluorocarbon 114 -14.2C. Boiling Point 75 - 80% Fluorocarbon 114 -6 to -7c. Bolling Point 59% Fluorocarbon 114 -2.2C. Boiling Point 65 -70% Fluorocarbon 114 -2 to -3C. Boiling Point 60% Fluorocarbon 114 -4.2C. Boiling Point 63% Fluorocarbon 114 +0.5',C. Boiling Point 723 mm: 75% Fluorocarbon 114 0.0C. Boiling Point 83.3% Fluorocarbon 114 1.4C. Boiling Point 83.7% Fluorocarbon 114, 8.5% Ethyl Chloride, 7.8% Fluorocarbon 21 0,8C, Boiling Point 1Uv--0"Jl 4 TABLE V PROPERTIES OF FLUOROCARBON 114 AZEOTROPES Azeotrope Toxicity Flammability Vinyl Chloride Low Flammable 1,3-Butadiene Low Probably Flammable n-Butane Low Flammable t-2-Butene None Probably 1 Flammable Methyl Bromide Very high Probably Flammable Vinyl Methyl Ether Low Not Known Fluorocarbon 133 None Nonflammable Fluorocarbon 21 Ethyl Chloride Fluorocarbon 21, ethyl chloride CD 5 z o oo 506 None None None Nonflammable Nonflammable Remarks Possesses bad odor, butadiene will polymerize Possesses bad odor May polymerize Hydrolysis of Fluorocarbon 21 would be problem in aqueous system Hydrolysis may occur in aqueous systems POa* 161 D. Ternary Systems It is possible to extend all the concepts presented above to a -system in which three components comprise the mixture of interest. The existence of ternary azeotropes is well known and these are almost always found to be of the minimum boiling type. It was, therefore, decided to investigate certain specially selected fluorocarbon systems for ternary azeotropes. Because such a large number of possible ternary combinations can be conceived, it was necessary to use a set of selection rules. These are listed below: 1. At least two binary azeotropes should exist between the three components if a ternary azeotrope is to be expected. 2. No compounds of high reactivity, toxicity, or cost were considered. 3. The composition of the azeotrope was estimated by plotting the system on a ternary diagram and drawing dilution lines from the known binary azeotropic compositions toward the opposite apices. The point of intersection of the dilution lines indicates the srea in which an azeotrope is most likely to be found if one were to exist in the system. If one of the components is flammable and the flammability curve is known, it should also be possible to assess the flammability of the mixture from the pre dicted compositions. The method described In Item 3 is applied to some systems of interest in Figure 6, where fluorocarbons 21 and 114 represent the lower apices of a ternary diagram, and third components are shown at the top. Consider, BLAND/UCC 507 162 for example, the n-butane/fluorocarbon 114/21 system. The two binary azeotropes: butane/fluorocarbon 114 80.5/19.5 and fluorocarbon 21/114 35,7/64.3 (ratios In mole per cent) are plotted on the corresponding sides of the diagram and dilution lines are drawn to the opposite apices. The two dilution lines cross at the point where the composition of the system in mole per cent is 57% butane, 28% flurocarbon 114, and 15% fluorocarbon 21. This value is found to be in fair agreement with the azeotropic com position determined: 57.8% butane, 33.2% fluorocarbon 114, and '9.6% fluorocarbon 21. (Figure 6) If one applies the selection rules to fluorocarbon 12 systems, the following binaries are of interest: Fluorocarbon 22/Fluorocarbon 12 Fluorocarbon 152a/Fluorocarbon 12 Dimethyl ether/Fluorocarbon 12 Any azeotrope with fluorocarbon 22 would have too high a pressure to be of much value as a propellant, and it was found that no ternary azeotrope exists in the systems: fluorocarbon 12/22/152a and fluorocarbon 12/22/ dimethyl ether. The ternary systems which offer the most promise would be those involving fluorocarbon 114, since so many binaries are known. The binaries used to construct three-component systems are listed below: 508bland/ucc 163 Predicted Ternary Azeotropes A Vinyl Chloride Fluorocarbon 114 Fluorocarbon 21 B ' 57% n-Butane 28% Fluorocarbon 114 15% Fluorocarbon 21 C 26% Ethyl Chloride 48% Fluorocarbon 114 36% Fluorocarbon 21 BLAND/UCC 509 164 Fluorocarbon 114/n-Butane Fluorocarbon 114/Ethyl Chloride Fluorocarbon 114/Vinyl Chloride Fluorocarbon 114/Fluorocarbon 21 Some of these binary azeotropes are flammable by themselves; however, it was thought that ternary systems might be found which would be nonflammable by virtue of dilution of the flammable component. In the case of binary azeotropes that were nonflammable, it was anticipated that more of the flammable components might be incorporated into the ternary mixtures. The prediction of the composition of the possible ternary systems is shown in Figure 6, where the fluorocarbon 114/21 binary is held constant and the other three binaries are plotted against it. Thus, in the vinyl chloride/fluoroearbon 114 and 21 system, the point of intersection of the dilution line for the vinyl chloride/fluorocarbon 114 binary and the fluorocarbon 114/21 binary represents the predicted composition for the ternary azeotrope. In this case the system was eliminated from consideration since the predicted composition was far above the maximum (2) allowable level of vinyl chloride established by previous measurements and would,therefore, be flammable. Similarly, the n-butane, fluorocarbon 114 and fluorocarbon 21 system, which was discussed above, would be flammable according to the flammability curve C 31 . The ethyl chloride/fluorocarbon 114/21 system was investigated, and a ternary azeotrope was discovered with a mole ratio of 19/70/11, This differed considerably from the predicted composition of 26/48/36. The system could be of value as a propellant for colognes and perfumes, since it is nonflammable and is economically attractive. BLAND/UCC 510 165 SUMMARY In an effort to discover useful fluorocarbon azeotropes, a study of a large number of systems was undertaken. The methods of ebulliometry and distillation were used to detect azeotropes. Some new azeotropic mixtures were discovered; however, only a limited number possessed those properties necessary for a safe and effective aerosol propellant. In particular, the binary mixture ethyl chloride/fluorocarbon 114 with a weight ratio of 16.7/83.3 and the ternary ethyl chloride/fluorocarbon 114/21 with a weight ratio of 8.5/83,7/7.8 appear to be suitable for low-pressure applications. A. Ebulliometer^^ EXPERIMENTAL The instrument was constructed from a Cotrell-type molecular weight apparatus that was vacuum-jacketed and fitted with a thermo couple and a system for circulating methanol cooled by dry ice through the condenser section. Materials were added through the condenser from standard aerosol cans which could be fitted with "tap-a-can" valves and weighed after each addition. The level of liquid in the instrument could be controlled by withdrawing liquid from the sample tube in measured amounts. The condenser section was designed in such a way that the rate of reflux could be observed and the amount of heat applied by the mantle could be controlled accordingly. BLAND/UCC 511 166 B, Distillation A Podbielniak fractional distillation column *80 was used. This instrument was entirely vacuum-jacketed and fitted with a solenoid release to control the reflux rate. Thermocouples placed in the head of the column) the still pot, and the methanol dry ice cooling system were connected to a recorder which monitored all three temperatures. Samples were collected as liquids. C. Gas Chromatograph Analysis of distillation fractions was performed on an Aerograph A-90-P instrument. Known mixtures of the components were used in each case to calibrate the instrument before distillation fractions were analyzed. Ternary systems were investigated by distillation-gas chromatography. 512bland/ucc 167 REFERENCES 1. "Aerosol Propellant Blends" - R. J. Scott and R. R. Terrill, Soap and Chemical Specialties 38, #1 (1962), 2. "Vinyl Chloride - Fluorocarbon Mixtures as Aerosol Propellants" R. J. Scott and R. R. Terrill, Aerosol Age 7, #1 (1962). 3. "Aerosol Propellant Blends" - R. J, Scott and R. E, Feathers, Soap and Chemical Specialties ^8, #6 (1962), 4. "Aerosol Propellant Blends" - Allen B. Reed, Soap and Chemical Specialties 38, #8 (1962). 5. "Checking Aerosol Propellant Blends" - R. J. Scott, M. E. Clayton, and E, L, Ohara, Soap and Chemical Specialties 38, #12 (1962), 6. W. H. Reed, U. S. Patent 2,968,628 7. R, D. Broadley, U. S. Patent 3,047,506 8. "Azeotropic Data II" - Advances in Chemistry Series 35, American Chemical Society (1962). 9. "Ebulliometric Measurements" - W. Swietoslowski, Reinhold publishing Company (1945). 10. B. J. Eiseman - Journal of the American Chemical Society 79, 6087 (1957). 11. W. A. Pennington - Industrial and Engineering Chemistry 44, 2397. 12. W. H. Reed and W. A. Pennington - Modern Refrigeration 53, 123 (1950). 13. J. Fleischer - 0. S, Patent No. 2,191,196 (1940). BLAND/UCC 513 Appendix N A BASIC SYSTEM FOR WATER-BASED PRODUCTS By R# J. Scott and M. E. Clayton Union Carbide Corporation Chemicals Division Technical Service Division Tarrytown, New York BLAND/UCC 514 169 INTRODUCTION Water-based aerosol products are not new; some of them, such as cleaners and polishes, have been on the market for many years. These products are usually in the form of oil-in-water (0/W) emulsions with the propellant dissolved in the oil phase. Upon ejection, this system produces a coarse, wet spray because the propellant is present in low concentration and the propellant-oil droplets are surrounded by water. Such sprays, however, are quite satisfactory for residual-type products where the primary function is merely to deposit a material on a surface. Water-based apace sprays are quite different from the residual type and have become a major factor in the aerosol field. This paper presents the results of a study on water-based space sprays that was carried out in the UCOI^ Refrigerants and Propellants Laboratory. The system that evolved was not adapted to specific products but is offered as a starting point for those interested in developing aqueous products that require relatively fine sprays. DISCUSSION There are at least three systems that can be used for water-based space sprays: 1. A true solution of propellant and aqueous concentrate, 2. A three-phase system with the propellant forming a separate floating layer, and 3. An emulsion of the propellant and concentrate. BLAND/UCC 515 170 The first has already been described in the literature* and the second is disclosed in U. S. Patent 2,995,278, assigned to Mr. Clarence Clapp. The third seems to be receiving the most attention in the industry today and is the one that will be discussed in this paper. It was apparent at the outset that a water-in-oil (W/0) emulsion of propellant and aqueous concentrate would have two advantages: (1) It would produce a finer spray than an O/W emulsion since the propellant can more readily escape and, (2) contact of the container surface and oilsoluble active components with water is limited--since water forms the internal phase, it has less opportunity to hydrolyze active components in the oil phase or to contact the container walls. Therefore, it was decided to work with W/O emulsions as the basis for the system. It was also recognized that a mixture of a fluorocarbon and a hydro carbon would have advantages over a hydrocarbon alone as the propellant. In particular, the density of the propellant phase would be increased which, in turn, should increase the emulsion stability. Since the vapor pressure of isobutane falls in the range of moderate-pressure propellants, it was chosen as the hydrocarbon portion of the propellant mixture. Propellant 12 was chosen as the fluorocarbon because of its resistance to hydrolysis; although Propellant 11 is reportedly being used with aqueous systems, it was not included in the present work because of its hydrolytic susceptibility. The particular fluorocarbon-to-hydrocarbon ratio that could be used was governed by the ICC pressure limitation of 40 psig at *D. C. Geary, "Low-Coat Water-Based Aerosols", Soap and Chemical Specialties, 36, No. 3, 135 (1960). BLAND/UCC 516 171 70F., since the pressure in the containers will be the vapor pressure of the propellant itself, A Raoult's Law calculation shows that a 30/70 mixture of propellant 12 and isobutane should have a vapor pressure of 36 psig at 70F.; experimentally the pressure was found to be about 40 psig. Thus, the 30/70 ratio represents about the maximum amount of propellant 12 that can be incorporated and still remain under the pressure limit for sideseam containers. The density of thiB mixture is increased significantly over that of the hydrocarbon, as can be seen in Figure 1, where the specific gravity vs. composition is shown for all mixtures of Propellant 12 and isobutane. (Figure 1) The final item that had to be considered before starting experimental work was the propellant/concentrate ratio. This was somewaht arbitrarily set at 35/65 in the beginning, but was subsequently changed toward larger propellant concentrations as the work progressed. Having selected the propellants and thAir concentration, an experimental evaluation of surfactants was begun. Use was made of the HLB system to facilitate rapid screening of a large number of surfactants. The lower th HLB number, the more lipophilic is the surfactant and the greater the tendency for it to form W/0 emulsions. Therefore, the surfactants and numbers their combinations were chosen so that those with low HLB^redominated. In all, a total a twenty-four surfactants or surfactant mixtures were tested with a simple 35 per cent propellant - 65 per cent water combination. BLAND/UCC 517 SPECIFIC GRAVITY, 70F Figure 1. 172 173 Varying degrees of emulsion stability were obtained, but in no case was an acceptable spray produced. It was evident that a different approach would be required. It was expected that the addition of a cosolvent that was soluble in both the propellant and water would'Improve the stability of the emulsions and the type of spray that was ejected. The cosolvents that were tried and the formulation changes that were made are listed in the Table, Cosolvents such as isopropanol and hexylene, triethylene, and dipropylene glycols generally improved emulsion stability but not the quality of the spray, A mineral oil (Shell Sol 71), however, produced "transparent" emulsions with fine, colorless and quite satisfactory sprays (mixtures 10 and 11 in Table I), Sttictly speaking, the mineral oil was not a cosolvent for the propellant and water but probably served more as a carrier for the surfactant, and may have altered the HLB of the nonaqueous phase. Other mineral oils would probably perform as well. (Table I) 519bland/ucc TABLE I 174 W/0 EMULSION FORMULATIONS CONTAINING COSOLVENTS Formulation 1. 50% Water, 7% Hexylene Glycol, 1% Emcol 14, 7% Shell Sol 71, 35% UCON 12/Isobutane (30/70) Observations Very foamy, opaque, white emulsion. Snow-like spray. 2. 50% Water, 14% Hexylene Glycol, 1% Emcol 14, 35% UCON 12/Isobutane (30/70) Separates on standing, easily reemulsified. Fair spray. 3. 50% Water, 14% Isopropanol, 1% Emcol 14, 35% UCON 12/Isobutane (30/70) About the same as #2; slightly finer spray. 4. 50% Water, 1% Emcol, 14, 14% Shell Sol 71, 35% UCON 12/Isobutane (30/70) Grayish, opaque emulsion. Fairly good spray. 5. 45% Water, 4.5% Hexylene Glycol, 1% Emcol 14, 4.5% Shell Sol 71, 45% UCON 12/Isobutane (30/70) Grayish-white, opaque emulsion. Foamy spray. 6. 40% Water, 14% Hexylene Glycol, 1% Emcol 14, 45% UCON 12/Isobutane (30/70) Opaque, white emulsion. Poor spray. 7. 49% Water, 1% Emcol 14, 50% UCON 12/ Isobutane (30/70) Grayish-white, opaque emulsion. Tends to foam at button. 8. 53% Water, 10% Triethylene Glycol, 1.8% Span 80, 0.2% Tween 85, 35% UCON 12/Isobutane (30/70) 9. 54% Water, 10% Dipropylene Glycol, 1% Emcol 14, 35% UCON 12/Isobutane (30/70) Emulsion separates quickly. Poor spray. BLAND/UCC 520 Thick white emulsion, separates slowly. Poor spray. ^ 10. 44% Water, 1% Emcol 14, 10% Shell Sol 71, 45% UCON 12/Isobutane (30/70) 11. 46% Water, 1% Emcol 14, 5% Shell Sol 71, 48% UCON 12/Isobutane (25/75) Translucent appearance in container. Very fine, almost colorless spray. Grayish emulsion. Very fine, almost colorless spray. 175 The last two mixtures in the Table are summarized below as recommended starting points f r the development of 'water-based apace spray products: Component Shell Sol 71 Etncol 14 Water UCON Propellant 12/Isobutane 30/70 TJCON Propellant 12/Isobutane 25/75 Concentration, % by Weight I II 10% 1% 44% 45% ---- 5% 1% 46% -- 48% The reason for the two propellant ratios is the pressure limitation of 40 psig at 70F, The 10 per cent oil in the first mixture lowers the pressure well below 40 psig, but with only 5 per cent oil in the second mixture, it was deemed advisable to alter the propellant composition. As far as the spray qualities are concerned, there is not much difference between the two. BLAND/UCC 521 m Appendix 0 EQUIPMENT SUPPLIERS 176 BLAND/UCC 522 177 EQUIPMENT SUPPLIERS Actuator Button-Placers Container-Cleaners Haumiller Engineering Co. PNC Industries, Inc. Ball-Feeders J. G. Machine Works, Inc. Bottle-Testers J. G, Machine Works, Inc. Bottle-Crimpers Chisholm-Ryder Co., of Pa, Island Equipment Corp, Machinery Service Co. MRM Co., Inc. Standard-Knapp Div,, Qnhart Mfg. Co. Coders J. G. Machine Works, Inc. Adolph Gottscho, Inc. Can-Unscramblers Horix Manufacturing Co. Industrial Marking Equipment Co., Inc. Kiwi Coders Corp. Island Equipment Corp. Standard-Knapp Div., Emhart Mfg. Co. J. G. Machine Works, Inc. MRM Co., Inc. Pneumatic Scale Corp., Ltd, Cappers Conveyors Island Equipment Corp. Leeds Conveyor Mfg. Co. Consolidated Packaging Mach. Corp, Pneumatic Scale Corp. Ltd. Resina Case-Packers Burt Machine Co, Chisholm-Ryder Co. of Pa. Miller-Hydro Co. Standard-Knapp Dlv., Emhart Mfg. Co. Crimpers Consolidated Packaging Mach. Corp. Kartridg Pak Co., The Nalbach, JohnR., Engineering Co., Inc. J. G. Machine Works, Inc. Drive Units J. G, Machine Works, Inc. Case-Sealers Labelers Chisholm-Ryder Co. of Pa. Elliott Mfg. Co. Burt Machine Co. Chisholm-Ryder Co., of Pa. Standard-Knapp Div., Emhart Mfg. Co. MRM Co., Inc. Textile Machine Works New Jersey Machine Corp. Standard-Knapp Div,, Emhart Mfg. Co. BLAND/UCC 523 178 Liquid Fillers Colton, Arthur, Co,, Div. of Snyder Corp, Elgin Manufacturing Co. Horix Manufacturing Co, Kiefer, Karl, Machine Co,, The MRM Co., Inc. Nalbach, John R.f Engineering, Co., Inc. Product Fillera J. G. Machine Works Inc. Propellant Accumulators J. G. Machine Works, Inc. Propellant Fillers Economic Machiner Co., Div, of George J. Meyer Mfg. Co. Kartridge Pak. Co, The Kiefer, Karl, Machine Co., The Propellant Reclaimers J. G. Machine Works, Inc. Pumps J, G. Machine Works, Inc. Purgers J. G. Machine Works, Inc. Test Tanks Island Equipment Corp. Nalbach, John R., Engineering Co., Inc. Valve-Inserters Consolidated Packaging Mach. Corp. Machinery Systems Inc. PMC Industries, Inc. Burt Machine Co. 410-03 E. Barclay St. Baltimore 2, Md. Chisholm-Ryder Co. of Pennsylvania Hanover, Pa. Colton, Arthur, Co. Div. of Snyder Corp. 3400 E. Lafayette Ave, Detroit 7, Michigan Consolidated Packaging Machinery Corp. Subs, of International Paper Co. 1400 West Ave. Buffalo 13, N. Y. Economic Machinery Co. Div. of George J. Meyer Mfg. Co. 60 Fremont St, Worcester 3, Mass. Elgin Manufacturing Co, P. 0. Box 73 Elgin, 111. bland/ucc 524 179 Elliott Manufacturing Co. P. 0. Box 469 Fresno 1, Calif. MRM Co., Inc, E. Beth Page Road Plainview, Long Island, N. Y. Adolph Gottsch, Inc. 6 Evans Terminal Hillside, N. J. Machinery Service Co. P. O. Box 14067 Louisville 14, Ky. Haumiller Engineering Co., Elgin, Illinois Horix Manufacturing Co. P. 0. Box 9324 Pittsburgh, Pa. Machinery-Systems, Inc. 2800 Sisson St. Baltimore 11, Md. Miller-Hydro Co. Bainbridge, Ga. Industrial Marking Equipment Co., Inc, Nalbach, John R., Engineering Co., Inc. 655 Berriman St, 6139 W. Ogden Ave. Brooklyn 8, N. Y. Chicago 50, 111. Island Equipment Corp. P. 0, Box 38-279 Miami 38, Fla. New Jersey Machine Corp. 1500 Willow Avenue Hoboken, N. J. J. G. Machine Works, Inc. 14-20 Poplar Ave. Little Ferry, New Jersey PMC Industries 293 Hudson St. Hackensack, N. J. Kartridg Pak Co., The 800 W. Central Rd. Mt. Prospect, Illinois Pneumatic Scale Corp. Ltd. 77 Newport Ave. <8Uincy 71, Mass. Kiefer, Karl, Machine Co,, The Div. of Cherry-Burrell Corp. 937 Martin St. Cincinnati 2, Ohio Kiwi Coders Corp. 4027 N. Kedzie Ave. Chicago 18, Illinois Leeds Conveyor Manufacturing Co. East Haven, Connecticut Resina 572 Smith Street Brooklyn 31, N. Y. Standard-Knapp Division Emhart Mfg. Co., Portland, Conn. Textile Machine Works Packomatic Div. P. 0. Box 1382 Reading, Penna, 525bland/ucc Appendix K OCON Propane/Isobutane Blends VAPOR PRESSURE VS. COMPOSITION 142 {XZROl i COPY T~ BLAND/UCC 526 f , r f.r> r *>. Fr / V o> ropr I Vapor Pressure, pounds per square inch gauge Appendix K 100 280 260 240 220 200 180 160 140 120 100 80 60 40 20 VAPOR PRESSURE VS. COMPOSITION UCON Isobutane-Propane Blends % Isobutane by Weight 80 60 40 20 0 0 20 40 60 80 100 % Propane by Weight ^ *4' JXERO .COPY. r\ v--*'? iXEROl I COPY m bland/ucc 527 f, XOtO^Rf'OY Appendix L tJCON Hydrocarbon Propellants VAPOR PRESSURE VS. TEMPERATURE bland/ucc 528 EPO opr fxERO' {copy; COf'Y Appendix L VAPOR PRESSURE VS. TEMPERATURE UCON Hydrocarbon Propellants Vapor Pressure, pounds per square inch gauge V p- /xfo5 COPY ' ?***--ry bland/ucc 529 !) cV:Jo7iP*TO e,. Appendix M AZEOTROPIC AEROSOL PROPELLANTS By J, R. Haase and R. J. Scott Union Carbide Corporation Chemicals Division Technical Service Laboratory Tarrytown, New York BLAND/UCC 530 i xr:ro' _ f'OPV 147 INTRODUCTION Azeotropes have two unique properties that make them attractive as potential aerosol propellants. First, under evaporative conditions, .an azeotrope functions as a single entity and does not fractionate. In the case of aerosol propellant blends, fractionation was a common characteristic*"1-5^, and some of their economic advantage had to be sacrificed to avoid the hazards which it caused. The second useful property of azeotropes is their vapor pressure; i. e., most azeotropes have vapor pressures higher than those of the individual components. In the case of propellants 11 and 114, for example, propellant 12 is often added to provide sufficient pressure for a given application. Azeotropes of propellant 11 or 114 with other compounds could have vapor pressures sufficiently high to reduce the need for propellant 12, or reduce the total propellant requirement in a product. Considering the potential value of azeotropic systems as aerosol pro pellants and the fact that several systems involving fluorocarbons were knowrl6,7,8) * was apparent that a definitive investigation of fluorocarbon azeotropes would be of considerable interest. Such a study was carried out in the UCON^ refrigerants and propellants laboratory. It should be noted that, although this paper is concerned primarily with aerosol propellants, any of the mixtures discussed below that possess the requisite properties would be equally suitable as refrigerants. BLAND/UCC 531 j*rXonRvO *; i4s DISCUSSION A. What Is an Azeotrope? The relationship between the vapor pressure and concentration of components in an ideal solution is given by Raoult's Law: where: pA o *APA The vapor pressure of component A in the mixture. The mole fraction of component A in the mixture. The vapor pressure of pure component A under the given conditions. The total vapor pressure of a system can be expressed as the summation of the Raoult's Law expressions for each component: p * PA + PB + ** + pn These relationships are represented graphically by the broken lines in Figure 1. In practice this relationship is very seldom observed except in the regions where x^ approaches zero or one. Real systems give curves resem bling the solid lines in Figure 1, with either higher vapor pressures than predicted (positive deviations) or lower vapor pressures than predicted (negative deviations). The magnitude of these deviations from ideality varies over a wide range. They may extend to a point where the total pressure of the system reaches a maximum value above that of either pure component. . The vapor pressure - composition curve for a system with extensive positive * deviation is shown in Figure 2. Figure 3 (which has * Our discussions will pertain to systems with positive deviations, since these are by far the most common. CxeSo") i COPT1 -w : { XPO } 5 COPY bland/ucc 532 * XUPO ; C0*y 149 an inverse relationship to Figure 2) shows the boiling point - composition curve for the same system. Temperature - composition curves for liquid and vapor are shown in Figure 4, where it can be seen that, at the niminum, the composition is the same for both phases. Thus, liquid mixtures for which this relationship holds (ones in which the liquid and vapor have the same composition at equilibrium) are called azeotropes. (Figure 1) (Figure 2) (Figure 3) (Figure 4) ERO k ORr t bland/ucc 533 J XCRO i COPY Figure 1 Vapor Pressure-Composition Curves for Ideal and Nonideal Systems Figure 2 Vapor Pressure-Composition Curve for a System with Extensive Deviations from Raoult's Law 150 Positive rpov (f F5 XERO; COPY , *1 BLAND/UCC 534 cor '< Figure 3 Boiling Point-Composition Curve for a System with Extensive Deviations from Raoult's Law Figure 4 Vapor Liquid Equilibrium Curve for Azeotropic System EROfc or* y ( .'CXOEPRYOli nr 150A BLAND/UCC 535 ji cxro:Rpyo- ^ .151 The magnitude of deviations from Raoult's Law must also be considered in relation to the boiling point separation of the pure components involved. Figure 5 shows a series of boiling-point curves in which one component is kept constant while the second component is varied over a series of homologs. As can be seen from Figure 5, when the boiling points are close together the azeotrope is rich in both components (e. g. Methanol/Ethyl Iodide system). If the boiling points are far apart, the azeotrope should contain more of one component than, another (e. g. Methano1/Isopropyl Iodide system and Methanol/Methyl Iodide system). Further, when the boiling points are separated by a large amount relative to the extent of the deviations from Raoult's Law, azeotropic activity may disappear altogether (e. g. Methanol/ tert-Butyl Iodide system). Thus, the formation of azeotropes is related to both the boiling point and chemical structure of the two components. These considerations are useful in selecting systems for investigation when, for example, a fluorocarbon is the fixed component and the homologs are flamma ble. In order that the resulting mixture be nonflammable, it may be neces sary to have a low concentration of the homolog, and one would look for candidates with boiling points significantly higher than that of the fluoro carbon. (Figure 5) (XERO pCOP T V VJ.MH {* CXEORPOY1,, T bland/ucc 536 ri> COPYxj;ro Boiling Point * ,0 XEROl COPY ! BLAND/UCC 537 TxnRO COPY ** * *5' 153 B. Detecting Azeotropes There are several methods for detecting azeotropes, the classical one being fractional distillation. Others include ebulliometry, Vapor-pressure measurement, and examination of vapor-liquid equilibria. After a review of the possible methods, it was decided to use ebulliometry as the primary tool for our investigations. Binary systems of interest could be quickly screened by observing the change in boiling point when the higher-boiling of the two components was added to the lower-boiling. As a check on results obtained by ebulliometry, some of the systems were distilled, and the first fractions collected were checked by gas chromatography to verify the com position of the azeotrope. The use of this approach made it possible to cover the systems selected for investigation quite rapidly and accurately. Although it was recognized that the composition of an azeotrope is pressure-dependent, our investigations were all carried out at atmospheric pressure, since changes in azeotropic composition are not significant in the relatively small pressure range involved in aerosol packaging. If a greater pressure range were involved, the desired information could be obtained by vapor pressure - composition measurements at various temperatures (i.e., pressure levels). C. Systems Investigated At the outset of the study a selected list of compounds was prepared in order of increasing boiling point. This list was in turn prepared from a general list of all compounds in the boiling point range of -45C. to +50C. taken from the literature. Most compounds which possessed undesir- BLAND/UCC 538 1 XERO' > CQP'*' 154 able properties such as high toxicity, reactivity, or cost were eliminated to give the inal list shown in Table I. A few compounds which did not meet these standards were retained to provide some indication of general activity toward azeotrope formation araoung the fluorocarbons. (Table I) The principal aerosol propellants are fluorocarbons 11, 12, and 114. Candidates for binary systems involving each of these fluorocarbons as a fixed component were selected in accordance with the considerations dis cussed above. 1, Fluorocarbon 12 Study All systems in the proper boiling-point range (-43C. to 0C.) were investigated, with the exception of 1,3-butadiene. The results of this study are reviewed in Table II. Only two azeotropes were discovered which were not previously known; one with allene and the other with methyl acetylene. Neither of the azeotropes would be suitable as an aerosol propellant, since these hydrocarbons possess high reactivity and are present in large enough proportion to make the azeotropes flammable. A consideration of mixtures' of the other components with fluorocarbon 12 further points up the lack of a practical propellant azeotrope. In the case where the azeotropes are nonflammable, the economics are unfavorable, while in other cases where some economic advantage is apparent, they become unacceptable because of toxicity or reactivity. An exception is the dimethyl ether j CxOePoYo I-XcoRpOy:, bland/ucc 539 \ cxocppoy TABLE 1 SELECTED LIST OF CANDIDATES FOR AZEOTROPE STUDY 155 BOILING POINT C. -42.2 -40.8 -38 -34.4 -32 -29.8 -24.7 -24.2 -23.7 -23.3 -13.4 -11.7 -9.2 -6 -5 -3 -0.6 4-1 4-2.5 3.6 3.6 6 6.0 8.9 9.5 12.2 21.0 23.8 25.0 28 29.9 31 31.5 32 34.6 35.4 36.2 36.4 38 38.4 40.1 47.1 COMPOUND Propane Fluorocarbon 22 Fluorocarbon 115 Cyclopropane Allene Fluorocarbon 12 Fluorocarbon 152a Methyl Chloride Dimethyl Ether Propyne Vinyl Chloride Isobutane Fluorocarbon 142b Isobutylene 1-Butene 1,3-Butadiene n-Butane cis 2-Butene trans 2-Butene Methyl Bromide Fluorocarbon 114 Vinyl Methyl Ether Fluorocarbon 133 Fluorocarbon 21 Neopentane Ethyl Chloride Acetaldehyde Fluorocarbon 11 3-Methyl Butene-1 Isopentane 1- Pentene 2- Methyl Butene-1 Methyl Formate Furan Ethyl Ether Isopropyl Chloride n-Pentane 2-Pentene Ethyl Bromide 2-Methyl Butene-2 Methylene Chloride Fluorocarbon 113 540bland/ucc 156 azeotrope, vhich is suitable as a propellant, but does not have the economic advantage of the propellant blend^^. (Table 11) 2. Fluorocarbon 11 Study Table 111 lists the large number of fluorocarbon 11 systems studied. Despite the extensive investigation of this fluorocarbon, no new azeotropes were discovered. There are only two known azeo tropes of fluorocarbon 11, one with acetaldehyde, and the other with methyl formate, both of which have undesirable properties. It Is interesting to note that both of these compounds are highly associ ated in the liquid phase. Evidently, fluorocarbon 11 has a very low level of interaolecular attraction by itself and has little interfer ence effect on intermolecular attractions when present in mixtures with other compounds. Thus an azeotrope would be expected to form only when the second components have an unusually high level of intermolec ular attractions that can be impeded by the presence of the fluoro carbon 11. (Table III) 3. Fluorocarbon 114 Study In contrast to fluorocarbon 11, which shows little azeotropic activity, and fluorocarbon 12, which forms a limited number, fluorocarbon 114 BLAND/UCC 541 4 # TABLE II A REVIEW OF COMPOUNDS TESTED FOR AZEOTROPES WITH FLUOROCARBON 12 Second Component Results of Study______________ Remarks * Propane Fluorocarbon 22 No azeotrope found Azeotrope previously reported (10 25% Fluorocarbon 12 Boiling Point -41.4C. Fluorocarbon 115 Cyclopropane Allene Fluorocarbon 152a Methyl Chloride Methyl Ether Propyne Vinyl Chloride Isobutylene 1 -Butene n-Butane No azeotrope found No azeotrope found Azeotrope discovered Azeotrope previously reported (12) Azeotrope previously reported (13) Azeotrope previously reported (13) Azeotrope discovered No azeotrope found No azeotrope found No azeotrope found No azeotrope found 50-60 mole % Fluorocarbon 12 Boiling Point -34 to -36^. 77.6% Fluorocarbon 12 Boiling Point -30.5C. At 5380 mm: 78% Fluorocarbon 12 Boiling Point -25*XI!. At 2340 mm: 90% Fluorocarbon 12 Boiling Point -0C. 13-14% Fluorocarbon 12 Boiling Point -31.5 to -32.5C. 156A BLAND/UCC 5 4 2 * Compositions are in weight %. TABLE HI FLUOROCARBON 11 List of Compounds Studied Which Do Not Form Azeotropes Butadiene n-Butane trans 2-Butene Methyl Bromide Fluorocarbon 114 Fluorocarbon 133 Fluorocarbon 21 Neopentane Ethyl Chloride 3-Methyl Butene-1 Isopentane 2-Methyl Butene-1 Furan 1-Pentene Ethyl Ether Isopropyl Chloride Vinyl Ethyl Ether n-Pentane 2-Pentene Ethyl Bromide 2-Methyl Butene-2 Methylene Chloride 157 Known Azeotropes of Fluorocarbon 11 Second Component Acetaldehyde Methyl Formate Boiling Point of Azeotrope 15.6C. 20'C. Composition of Azeotrope 55% By Weight Fluorocarbon 11 (8) 82% By Weight Fluorocarbon 11 (8) BLAND/UCC 543 158 forms many azeotropes. The results of the study with this fluorocar bon are given in Table IV. Some of the azeotropes Involving fluoro carbons 114 might be of value. These azeotropes and their properties are reviewed In Table V. The azeotropes involving the hydrocarbons are flammable accordind to flammability curves for similar systems (3) , thus making them undesirable for aerosol use despite the considerable economic advantage. Conversely, the fluorocarbon 133 system is non flammable but offered no improved economics. The azeotrope with fluorocarbon 21 could be of some value, since It would be nonflamma ble and probably economical. Likewise, the ethyl chloride azeotrope, which has been mentioned as a refrigerant (7) , may also have possibilities as a propellant. The reason for the unusual activity of fluorocarbon 114 toward azeotrope formation is probably related to the large number of fluorine atoms present. Evidently the structure of the fluorocarbons 114 molecule makes it very effective in altering the associative forces of other compounds when they are mixed with It. (Tables IV and V) bland/ucc 544 CTl .jttsiiaurri -LL2 :Jua Ji ---- 7i *. . >e.efifl'MC;lNC;.; >fQ0233-h' TEW PBUSH SP.:f!5'07ti ;'14S2 *.201* 89972* ifiHfi ' : e?9 * 30- Sk. PXS380 $OH82bOO-66x3 > .000* .tjsm * .r>'* o/* .. .* * . U SQHt3S30 939tf2 0 1^715 . iiW* sivse iBssttf -' tassm -.i* r.ieoe '*"3616 - .:4>43H ^8J "2i"6 -r-Y: y ; Jr 1 ;r. ;}yu :hsw. i22hsi OC^K^fiOPItlX PUS 1421 r;.2l8f 9Sil7 I22HAJ * ,UCON PROP IttX fll. H0S3* "-.Vi211* SWb^;i22WS ..VCOti .PROP Hj )< Pjrtl5S3 i ~V,J * ."V , -V\; ;T; ' *.:* .*.'^25*) V.5IH fiaWJ UHSBf /frt' 00333-0101 r: S2H -; lOmj ,v"- ;V: CCBOBOW-VcOPP., : "i'` -iBL'm^rUE ~* y\? j : Y* Tv50B '.'16032*321 TOj ** r-. vBUT.-lWOHfD 8HHy0fi005 (. nsf fer-V 1V* '=* ..?7S,* Vl7102 ; WWi r6< '* y - W,03A -Tit 0023H-01()l t> *' --V:. "u/. It'* - ` %' ;* : * ^ ' '' - 4 j. t * , .* 159 37 3C*>$S-C Pi;Soi co 0023^42 0 50M8280X *Y-7IJ WI 'v:I- *'.. 500I 03212 \ 132P TJ A;b0236-0201 159 . 1.^'IBMS, TOTfttl u ; 1 SC: lHDs4$C tySIfiC 1C 00236 ^3 U S0HB290X Y 'Pft 903 vOOO 93212 13JCEJ PWCflHE- 'IW 00236-03011 /1S8 '. 1- ,0625 .TOTALS ;* v SC MOS-ASC PL0S7TCS CI B1ME TOTPL ` 00236' ,1 29 ' '3; l .4 03 Z o g o 9 545 Become-^ ' 00242-1 1 SftC 470^ r : : '. * * .500* 02060 '306| Mil A .fA'00242-01011 WO ` 1 - 2441 ` .TOmi 80A RUSfiEP CO apmoh ;;- . .000* 03767 ;'33SSW Tisis*. ,1 ;*3.!Jfl9V 08295- 332215 ' V cr.'lKO ts '002Y+-010)1 17 1 ?omj .... T.rS: ^ iift- BLAND/UCC 5 4 6 CARSON NEWHAM COLLEGE 13865-01 43205 66790$ 16 mmmmmitm CARTER INSECTICIDECCHEM 13868-01 ,, CRAG SEyiN SPRAT 60 A____________ 22000 22000 11000 21450 44471$ -Jfrl-IACE iMC. 13886-0101*_______________ 22 22 11 L E CARTER CO INC 13892-01 U,. AtflgHg.. ,. ------- ,------,,.L,. *------------ ----- ._______ _350 15355 11702$ & ----- lUimL 19821 '11702$* ..'..,.-.v...<;..;.... L------- :------ 1- ..C ft --V vl 59 - -s -* tv .v.j .* 2100 18952 400 !^ ^ - - `. rrrW ~mr. 55 **' ' 85 55 ' f* ' 21 21 "'It; rTE^-- * * \v*, * - 44 40 84 I/UCC 5 4 7 TAflSCN CHEMICALS INC ' ICC Is PRCP VINYL CHCfli ._______________________ 55774 4776* NiSC UMCENT IF IEO * SS5SS 54572* NEW CA5TL.1N 13863-CK1* 23AC- - -5224-TOT* 13863-01 * 4 THE CARTER EELL NFC CO ISCFRGPANCLAMINE MIX 4 43ZC5 23855* SPRINGFLD.NJ 13883-C 1014 C55C- - -2311-TOT* 12EE3-G1 _______ CARTER HOTEL CRUG STCRE ISGPRCPANCL ANHYDROUS* rv\; '. - " ' 42C62 23855* vi CLEVELAND.CM 156e6-C101* 114C- - -3211-TOT* 13EE6-01 CARTER 1NSECT1C1GEECHEM 138EE-C1 CRAG 5EVJN SPRAY 0 * 22CCC " 21448 . 54471* 12320 WALLACE .NC 13888-C1C1* 22 22JC- - -4111-TOT* 12 L E CARTER CO INC________ > ACETCNE - .7 -11212 117C2* rs\. : EUTANOL EUTYL AlC * 13E52-C1 15355 117C2* N EITYL ACETATE * 15E21 1J7C2J EUTYL CELLCSGLVE * " U5C7 U7C2* CELLCSGLVE * 42C 15512 117C2* CELLOSCLVE ACETATE * 5E 15552 117C2* [, C1IS08UTYL KETONE * 27853 117C2S ETHYL ACET DEN 85-SCi* 22325 117C2* 4CC tc 1SCPRCPANCL ANHYDROUS* ---------------------------- ilEii___LULti. ISCFRGPYL ACETATE 55S* CD 42245 117C2* f z METHYL ARYL ALCGHCL t 465C3 117C5* o METHYL ETHYL KETCKE i TZC _____________ 4fl 11.7 C2* KE1HY 1SCELTU KETCKEI ICE 472C7 U7C2* -EM2E54 I-EAIL15_Ui_E 1_*_ 53E54 117CZ* PM3553 III DUACZt C2 * ______________ S3S53 U7C2* CSA CUSTOMER REFEREJsJ tIST MONTHLY *-* AUG 1750 385 12 44 1750 378 3500 . 765 i34 41 1 1 * 4 4 _SfL 5250 1142 6 1 40 - - >, 16 * * *. ' >>r' fy*y ^ 1 'V-1 '" 355 39 '-` - 4 ' ^ *- . '' - r* v . * ' >. ' A< *\. -;r-5- - '?&&} 595 A'"' 400 * 58 820 *r &>. , 188 ' 'y , ? r? 880 172 4 ' ` 370 v 59 400 60 - V -TV' ' > 420 93 370 60 400 62 820 189 2200 429 370 59 400 60 720 720 ioa 108 7120 820 360 54 720 1C8 66SQ 870 OCT NOV DEC 1 OEC Y 1750 377 14 3 PAGE 14 25 35 * * -4 80 33 4 4 4 23 23 46 1667 * * , * *i * 4 4 * .* *. 4 * -4 *- 4' 4 /V'-, 22000 11611 22 12 44 44 - 60 r 24 24 : 32 44 44 60 24 24 32 Oin O 350 32 2100 189 440 86 \\ ' 355 355 33 33 1ft 0* 19 l; * * l 4 2 4. i 4 4 1 l 4' 1 4 1 4 19 1 4 l 4 2 4' 1 4 4 1 i : ; 1 4 1 4 '> ' ' ' ' ^ 36C 360 360 4 4 54 54 54 1 1 70 7 7 7 10 L11 BLAND/UCC 5 4 8 CBWX PEC 200 0 18224 84*228 SENTRY CMC F-73-M * i iSOPRORANOL ANWYBROU 430*2 845738 080PVLENS 61VCOL 2ND Mtsai HTTORr 84782 545728 MCON FLUORQ 12 POOP * l*r. l.-V OCQN PROPELLANT 114 95574 563608 PCOH PROP VINYL CHLOR# xxnsi!: :: :- si ivv it-."' M- .'^ rJ:'-' . fe?ii111f&t !V,<>C- 310 132 150 s- f. y f IX ** C ^Cplllfc :' " -; -,$* >5; '>" C. :itj; ''-?'%fi*'s--( 3500 2444 1750 3500 1750 58 X^pTv -. -' ; !' >-; -' 1750 B7 72 1750 1750 , - *S, , $ >M) fV; ! *-\ VC < ^*1i* :k% vCsS>Ccfl * 26 26 31 *... 'V';'';'-I ,--rm" i-M-t-:. ---VC * -.. --,< 8 * "!- -X t i ' i#>; j:- 0 PROP PM3T94 VIN CHL0 95774 BB376* NEN CASTL.IN 13863-0101# 5250 5250 1750 1750 5250 1132 1144 308 379 1133 *66 3 26 :-m ISGPROPANOLAMINE MIX # 43203 JJ3591 SPRINGfLO.NJ 13683-0101* zgr^y-u.1:.^ ,ly'-..J O'-ia. il! "A"-!**W!;'V "i. I W I ' IJJIAI ILAUJ.UjajJ^JU JUMIIPI FXL PR 3522 759 4 feet 1761 300 2 3511 757 4 1750 364 3 80 33 * ^'%f- 30 6 36 J S1^ \tTI- ; '^ 30 6 36 ** 15 31 3 10 b; ??;-f ** ** 1 1 || BLAND/UCC 5 4 9 J I I N BUTYL ACETATE # 400 15821 MM31S* 64 i BUTYL CELLOSOLVEI 410 ffHmt-'V # 'A- . .. W r ;_2J____ 19312 MH31S0 42 CELLOSOLVE ACETATE # 1726 19552 HH31S0 293 OIISOSUTYL KETONE # ' 27053 MH31S4 (ETHYL AC6T BEN 400 i- ______________ 32339 IMMS8 40 PM3640-PH3134 98* 1 # 32393 JJ359* ISOPROPANOL ANHYDROUS# 1328 43002 HMJ > 9? 400 64 '.- ' ' - 400 64 440 B6 8174 1390 723 B 528 * * - 400 60 400 64 410 '45 480 42 3655 494 410 ^ 95 ' - ` ' M#4'- . 4500 581 7300 550 55 11 11 6 ,4- 8** 10 10 22 - - 5 1 16 1 j 'v- * 5 1 16 1 ` u -"1 13 It 2 n; - * '" ': Jd 1 16 1* 1 SAR CUSTOMER REFERENCE LIST __________ CONTINUED___________ ____ JAN FEB______BAB_____ APR CARRTONE LABS INC 13861-01 WAY WET AIR IE LA 1288 1--01 CIA 196 1214 TOTAL! CARSON CHEMICALS INC 13863-01 __ ACETONE_____________ * .000* 11212 112GD* C6WX PEG 200 JL .000* 18214 1126E* SENTRY CMC F-15-H i * .000* 15034 123DR* CELLOS12E CMC P 15 H * * .000* 19043 45164! SEV1N 97.5 OHS # * .809* 21431 lllllt SEVIN 50 CTN ______ f_ * .410* 21438 11111$ ISOPROPANOL ANHYDROUS* .000* 43062 11200$ PROPYLENE GLYCOL INO * * .000* 11612 112GD$ .310* 82105 11110$ UCON FLUORO 12 PROP i * .414* 95538 1230$ UCON FLUORO 114 PROP * '* .616* 93562 1230$ U PROP PH3794 YIN CML# * .208* 95114 U3CDI NEW CASTL IN 13863-Old* 590 5224 TOTAL$ 58 24 87 11 1150 3*7 2 * -446 165 1750 364 2 1 <12 330 3300 742 4 1 3500 128 4 1 CARTANS BABY NEWS STORES 13875-01 --KARON CONTAIN NO EPOXi * .000* P 64 22 342HK$ ...... SN LEANER CA I3B75-0101# 233 TOTAL* CARSON REED CORP -_____ U. SOLVENT HCP PH4814# * .415* 95189 186H1* SOUTKFLD WI 13880*0101# 900 5112 TOTAL* 13880-01 53 22 * * CART STOP ............. METHANOL SYNTHETIC # * .092* 45205 386H3* .......-NYACK--______NY 13881-0101# 900 2132 TOTAL* 13881-01 358 33 * * AB CARTER MILL OEVICES D 13682-02 .......... _ U .LB..11A1................. _ * .363* 94602 186H1* ------- GASTONIA--NC .L16.62r.C20 UL 900 4123 TOTAL* m ILY POUNDS AND DOLLARS JSUL JUL AUG SEP___ DILI_____ NQY 1000 410 AMSl 809 as? 330 165 1750 344 2 * 3750 779 5 1 3500 726 4 1 3500 674 5 1 1750 364 3 1 3500 728 4 1 DEC 1966 VBE 1395 DEC YTD___YEAH RUN POT 2 * 1 _1_ Jts_ 4 4. i 4* 44 4* 4* 5250 34 34 ?6 26 1113 6 6 5 5 38 38 30 81 1 996 44 44 ** 4* *4 *4 44 *4 452 4 4 164 4 4 *4 * 4** BLAND/UCC 550 1,. * _j tfltwcis to. - : v; TraSnri rurNEivrME>OL res 4000* K1T1F ik amn.i&i-oiDi ; du tcuzotarKooino1 j; imwhjiv ' ;BrtEKinolniiK;,;i " ^.OOO* . . ,-.x, routMKEtt M13*O-01i>lj W: ..-ZHriMTAtj v**. Ltf 39 CSTKS >i 4.^17* . outnr 3a JUDJUi FL 13MI-0101 Sa* ,*. r, 'l*;.;, /^1_..T0^ . . ...... . C4RS0R OenCAI^S IK:> . ; 13*3-01 r ree 2do y. :./- (-.' .ooo^imi tiara i. aaienzE xncm n 1 ; * , >^000* 1WJ1I4M 1 \.'VV'- ^SEYIf " 77.3 0ns siooo * **.1iZH11J3377 r 11171 ;. "101 >$EVlf 30 CIS';=- -\i . !.' *^^~)VTT| a, m..*n7*2*k.. c4v*l3.n52 s1 11171 Ai'*/-.wMoo . WRorAwt. /uwviRous .3 nio:uu v i ;^|3^g430tt > 11272 ' m W jSjucou; rw^nw nuzts i ' 'Mg. jRomarsLY semv V_2Cfr*V7l4111*m: .V ROELITl j 892 |03^11170: . . - - rj,, , ,u \ 1.229 *17J*` -1**!' niTl44OLMIIC com i .330.#CD5.1lim UCM FROF X2. 'I u*c6M* MfluOmf0 3ih* ph12o3CfT1i *h000` WZ 123CT: CO 5 ti/FROF :Fn37f3. vji cnl V;203* 9J771J 12301) 31 MS/! II lJ*3-01OL o co / 200 . 3211 10740 ' o MRSOMS ISC . 13*9-01 UTILITY RCE774CL3 l 01 _* .*- F19S3' HJRffc ... 01 WTO CO 13147-0MU V S#4 TOTH' ; !' -Q* m. 159; k'/V '' ; 4= . . . ' SAR CUSTOKR* REFERENCE List ^''ttoNTHLY POtiNDS AND tfLERfiS .. V'~'v r'Jr.*rm-... HHR 'APR HflV "^KJN JUL^TRUB UffP :; ;7 * \ *6 ARSON ttHfCAL- INC; 'i38M- iRCTOf.Xj ` ' -si 7;. l vl04f 11212 1123CUt1" 1* ;$EWN.K.5 SO LB CTN I .860I\ 21437. ;limi * SEWN $dCTN / ` * 1 .4501.421438 '411711;,' >. . SEWN'TECH f v / ''' : 1 ; , :-r : .1 ir-.i 1*' l42l % **,, X V . -U8' y. 1IV v 200. * *; V rr \ . . - , ' ' * -1000 860 to i* ' IA. 0001 at452 1117It1. '< ; A. 1 427 - ~ : . 1000. V ' >059 *;V\ i - f A , :v ...: ..77:1 . 1 -f%rvv-f <. . ,v A--A.. 1.2201 41603 - 486H41 : - ISOPROPANOL ANHYDROUS* a VI..0001 43062 112721-'. ,Q \PK3862 198.9 \tl * \.r . * c*;.O8O*-ttO0& 12JC\Jt!; ' UCON PROP FLU0\PH3275I V * * JOOr 5327S \ lgJCLfl l ' - UCON PROP FLUO RH3301I 7 1 .6661 63301 J123CT1 .* * . PIV GLYCOL USP V 964 : ;M991 W6157.1H272I. . 198 . -PROPYLENE_GLY GENTRY: I " i -.84' 1446 282 9686 i 8762 : 808 1 778 '* 1 ; - 1 - v ' T- ,9627i V 768 Vf.; . .w .;v-`; 280 4..v.v -'.-4 .,170 .v-'vv- r> K. - -. ;;r!'V yu U \j .l-VGOOV 71619 `112721.. ' 6W-"3l*0II1.4BA.0I 1 V-mI | :! 1 ,t I .3701 82706 111701 r. '336. TEROITOL m I.2401 84782 TRIETHANOLAMINE CcOMoH"im. ... 1020 . 436 . 1362' -L362. ' \ . >' 603-. 504 -.iV .. : / 808 . !.; / 336 >{/.. 480 ' 115 !jI :vuv.:;-iv4u^^; i " it * \ :iU*., ' /'' 7-V t* * *r1\': . 1--:-0--0--0-1- 48--8--2-0--5- 11122772211' . TRIETHRNOLRHINE 901 1 / 1'.362.68206 112721 '.l U--C-O-N---P-R- O- P -M-I-X- - -P-M- --3-7041 VV"I750: ;Xv2S641 96774 ; 123CUI; 460 ' .H dMU, IN 13963-01011 - 4 1 N- - - 3500: i ` 3500|fl7!iO`VT33 "' ' igl 22 ] '7^4 074' ' - 662 A \4491 11 1 t- lS ? o-. H '. f'556.\t , 5224 .TOTALS- 1 Tr. . .3 0- , r-- is ' WSON NAiiONflL FORE^ .13664-01 f.DOft-70 * Ul.- .'V V Ul.OOO1 *22472 39$M3t\ '' \ : - >: ('* 7 frf'Mi ih. iJ j;* .I , I * A' * - ' , . ...-'..v ul'v 0' -13865-01 t ONW8617NT . 7 S | W^iiivvv g l s*-2* * . :v; v-Vv >: M* < \ -v >- 7l] 1 '.** * ; u s cn ui /V ro ' :........ - ' ' r\ ! . .. S': fllffnifll -/ JWj qgudis^c 13843-0F-` 3f^Ca\C(LV * ,000*. 1563 IW WflRm.ui * .079*' 93098 123CIW T* .. .. 13300 '1^4 APR 'i' UXN PROP FIDO PM3301# s * .000* 53301 123CT1 FRGLMXL USP # "k . - ii . / a "-V ` y* * y ";3 .sk1\**' .'V: * .000* 71415 '112*0* SEVIN SOU 30# BAG *.OCp* 80993 11171* J , ;i.' SEVIN 5CfE30AG f / t1 ( . ., l,-f v -. * .900*..80996 11171* V- ^ STABILENE- FLV REFELNT# 906 1342' ; 959 * .375* 82705 TEperra. m 11170* * i]^ 391 511 170 *..000* 89782 112*0* 'i . TRIETHANOUnnC 951 - * /* - > * .000* 88204 11272* tow prop nrm 379*11 v.1750 5250 2500 *.297* 95779 1230* GIDSTLIN 13843-0101# * 5/5.6 1 5> 221 *1,,** TOT? AL* .932 : *3 1, i ZMRSON OfhlCAt:.' : U3844-C 1 1312 -too v ."a ?;3 . -3 . ii .f TERGITtt -.. # * .000*> 89931 184m* -CNG BCH i CA 13866-0101# . / 453 : l\ .8112 -TOTAL* \ i 1 i jARsw: 13847-C i-: CfCJTOl., J0D00 V '* .109* JPH767 2tlff* 1400 / ' 10000 I 1350 ' , > ,ooo* jpm9.*2iiaj* UVERfC Cp 13847*0101* 374 1 18112 TOTAL* *i r ` *' io -2V # 1 V' 99590 350 - 350 . 350 79 4 rCD TRSffl' 7ERGITCL NPX * .267* 8*1782 TRIJ (13870-C l v .. ' 1 jj f. / ,< ' J zo co 0 * .239* 88205 132GES SAW#*H GA 13870-0101# <11- 1 9231 TOTfU 3LEN A'CARTE ! ` i *1 V*A i'*<v I*-* t i: / % iH v: l * i [13873^ CA CELOSZ fC*t)p-lCOOO-H# 1 i01 *1.160* 19054 322RD* W .GLV02A. 'a t \g i *\ , 1 % 1 ) *&>+ * ' ) ' * . iI : FHV^TrD9TEST San -V 11 13 13 ! *6 - a. * 1.. 3 * 4 V * .. 1020 .' Is ' 1 990 A * .K'' -r 33 1 '.1 9 . : 1* }' . > s* :m t . 7X ... 10 10 ` X r:: 2 32 2 '9 i: '1 f T-"f 12 * . % . " V j, . *.$- t' <49 697i 7, \ ;; ; 69 69 7 '? ' * \. - if *. -t iy A.Vi . ?> 1 1 # % * 4>4 1. 1 . ..* 4-14 1f 4 /- * 4 4^ 44 * s * s * a * a * a b * s * i * a* * b ! d i * S * f s i s i ^ ' g i l - l CONTINUED CSA CUSTOMER REFERENCE LIST MONTHLY #- S JAN FEB MAR APR MAY JUN JOL AUG SEP OCT CHASE PRODUCTS CO 15055-01 PROPYLENE GLYCOL IND # 1440 71612 44877* 241 PROPYLtNE GLY SENTRY # 480 480 71619 33741* PRUPYLENE 0X106 # 90 90 370 71805 44877* IRIETHANQLAMINt COMM # 69 1020 510 88205 44877* TRIETHYLtNE GLYCOL # 88505 44877* UCON FLUORO 11 PROP # 95534 44776* UCON FLUURO 12 KEFRIG# 55537 44675* UCON FLUURO 12 PROP # 95538 44776* UCUN FLUORO 22 REFRIG# 1560 351 69945 - 37358 14198 -7583 2000 545 162475 75511 41967 19281 520 117 29370 5842 109960 28369 265 46195 9310 127465 32983 29460 5802 -286 -60 133 1040 1560 1040 234 351 234 -1000 51435 15100 -218 10130 2953 2000 580 -1000 154175 226580 -1103 39324 57863 2600 585 46080 145280 9280 35359 2000 562 48000 46020 12329 11099 95540 44675* UCON FLUORO 114 PROP # 60 420 116 95547 44776* UCON PROP MIX PM 4053# 95762 44776* ____ UCON PROP VINYL CHLOR# 53 314 103 122940 121260 207600 23719 23704 40196 95774 44776* UCUN PROP P 3EDMET Eo # 95775 447764 UCON PROP PROPANE # 95776 44776* UCUN PROP 1SGBUTANE # 35621 20766 109187 104831 200 51 -1 29183 95865 74432 420 62 44794 68505 78709 95777 44776* UCON HYC BLD PR 3951 # 1654 80 997 5020 4888 1968 4399 3429 -20386 3187 4174 960 95778 44776* UCON PROP 11 FOR URET# 21 141 29240 97060 22722* 5936 BR0ADV1EM.il 15055-0101# 270 60 249 280 60 127 283 411 284 479 2430- - -5411-TOT* 56 13 39 48 a 10 53 65 49 92 _______________ if CHASE MANHATTAN BANK 15056-01 PM1611 EG97 62 # 36151 22934* 516 78 NEW YORK .NY 15056-0101# 043Q- - -2121--TUTS 00 1 * CHATHAM AVIATION CO 15078-01 PM1717 EG95 65 # z 516 36155 22934* MORRISTHN.NJ 15078-0101# 0500- - -2313-TOT* 2 c o 79 l * DEC 1964 NOV OEC YTO YEAR 30160 -19B0 5945 -520 2000 112660 562 28740 180 70 120 98 96060 96580 18465 16634 1 * 1 * * * 2 * 8 2 423 90 6 2 1064 271 * * 1 1 644 125 1 * 1 * * * 2 * 8 2 423 90 6 2 1064 271 * * 1 1 644 125 100 26 33374 1537 162 27 58 80 276 70864 3502 284 51 6 6 1 763 14 l 29 6 2951 513 6 * 1 * 763 14 1 * 29 6 2951 513 11 ** 11 ** 11 * 11 ** PAGE PLAN 2200 570 300 41 750 87 3650 735 *09 POT 1 1 2 138 2 220 0 1 30 0 30 0 75 0 409 5 ] 1\ CHATHAM LABS INC ALUMINUM ACETATE NIA # 13139 66790* RIVERDALE.NJ 15079-0101# 0500- - -2313-TOT* 15079-01 Ml cn 1000 540 1 1 200 3200 4 4 108 1728 2 2 * 344 * 222 CHATHAM MANUFACTURING CO 15082-01 ISUBUTANOL # 1800 3600 42575 33639* 207 559 1800 351 1800 279 3600 558 lbOO 279 3600 10800 558 1674 7200 7200 3600 47 47 11 20 1116 1116 558 7 7 2 . ..J --..CCMILNOIC CHASE PRODUCTS CO CSA CUSTOMER .REFER6l*.C| LIST M.CNTHLV 4-* JAM-., 110.... . M4R . .. iAPR_'i'._MAV 3.1JN JUL . 15C55-01 AUC OCC'N FLUL'KC 12 f'HCP * 12C27C __________ 5_5_5 38 . SAT 76* _ 31685 LCCN FLCCRt 22 KfcFRlG* 145890 116'99Q 22750 3.6303 .. 30234____ 5650 113560 29144 126600 32347 1078.00 27239 26900 695 8 . * 54*15* f LDfillt. J H ft If Kg I 6664b 64676* ULN FLUCRC 114 PROP * ________________ 66662 6477t* LSi:.::,;'::'4|jCC|,-.PKOf1fLUNT 114 * -- WiA S4I76* A, s?. ^ . 4P0 243 120 1200 100 806 3600 27?2 -360 ' 4800 3Ue sep 18310 4 363 OCCN 8SS93 54776* PROP MIX PM 4C53* _ 55762 54776* FRCP P'H1 ie"T " -52C 169340 -244 37660 91760 96680 281860 17846C 262260 91800 273640 17775 .. .18408 .54379 34424 50590 .17693 53079 ST 118625 29465 06C 1965 _NQV . ....Bit.- IflB. 6000 5800 936 . 1481 .. 1206 . 246. 2400 6000 1580 $947 57140 27820 11901 5972 -1820 282080 187280 -4056. 53926 _ 36449 4 * 1 1 17 H . -85 18 1933 370 ' PA6t YiM. PLAN 996 1400 246 357 4' 9 l 1 17 11 85 18 1933 500 370 ...... 97 574 MT J., 1500 ; r- -- 1 17 85 1933 - 55775 547 76* li^l'ii^/ipftftg-JKQPANt: ' * 45776 547761 `i'* -1 UCON PPGP ISGBUTAKE * 35986 5732C 110768 68474 163456 107997 98252 ______ 4 5717 5477 6* _474C N MVC BLD PM 35 51 i 338^ , 5196 3212_______ 7668 5005 4514 :xo;i - n do" 21582-:: iov fc*"" 4776* 'ai'ite'rjyRffI. :''M ' ... ; 57C50 54776* 213664 90395 9822 4148 .553$5! 63263 v.|`50' 946 946 1000 1000 48 48 49 167 167 : U'|; ' '; ^' ' i RISC UNIDENTIFIED 4 55999 54 67 7* UKOACX 1%,-iL:: 15455-01 Cl i .'-243P-* '*l41l-TC7* .. llPROP-l; 95538 54776* OCGN FLUORO 114 PROP * 95562 54776* ,i5055*-ClC2#' - ?54U->-tgi* v1 DIVISION TOT 15C55-C1* 55760-151560 340 J9.G61 -38102 '3lt~ .-267. 68____ $6i; '69V-/ 54 ,. 31fi. 69 267 54 120 300 250 -."L ,.. " ' ' . . 367...... 2Q.5 70 32 6 CO 4b9 ^LpTCp;'- iff' coo 469. 100 83 509 UT '344, :W ; 39 ` ' 509; 177 344 89 39 68 150 42<J :.-33: . 81 - v ' -'"t "''i V -95 -19 -* 411 4456 . >?'- * * * m. , 33 v , '5 620 61 411. 57 l ' 4457 775 -95 -19 -570 -*g#s >;pr4Sf'' ^idr "l TV v,?iMlpo . t :',f r -T7 -v-^9' * * * r;:ir r " ' / r- - *>. V.X -1 - , ;.J703. 775 583 t ___CMS! MANHATTAN BANK ...... 15C56-C1 _ _ ?-it1. -i-fu11 mi.- #' ~ ' ~ .......... ; ^ 2<5Fl* - l.1Lz lllHii2slSfft'RM4Cfc^-i-i.l&tfVIiMf S*&f"e*-C: 11>0f1lU* 043C- - -2121-107* _ -tv?.-.~ t:-....... --V. ' -- -.............. -n.- - -r - chateau aviai ign cc ;:" " 6* 36155 i 2 9 F I 4 "aMOftftl'STWN.NJ 1507-C1C1* C500- - -2313-TOI* 15C76-01 CFA1FAM LAB S INC H'lTATE N1A-' V ' "< Wl39l 4 36 38* IIMffil. 15079-;C 101* . 0542-C627- -2313-TL'T* 1SC79-01 im~ ffflSFJ 7RdC''-l`"if0d 4 72 4320 ' 4212 3672 ' 2 .... .p,, 8. ' 7 1444 :v . ' 460C 24-64 5 2 ' 3000 1620 . -''3 "*2 3Q00 1620 2 .. 4000 2160 4 2 4800 2592 5 3 600C M SO 3240 27 27 6 50 50 3 27 27 0 BLAND/UCC 555 - ; t PM4511 UCON HROP MIX * 95773 547744 -47 UCON PROP PROPANE # 2520 `J5T76 54776* 3*1 V , """" ISUflLJIANE. #:, 74900 193479 -49975 47036 49975 48916 ~ 48689 UCON HVC BLD PH~3951 # 95778 547764 H1SC UNIDENT IFIEfl 6 48865 Ml -* --* 33 UCtIN FLUOR0 12 PROP # 95538 547764 UCON FLUOR0 114 PROP 8 ?>' : 9 5562 947764 MAYHjUIlO ' , 1L 15055--01028 - ;'303004 l--> >54lir-T0T4 * CHASE PRODUCTS CO # 223 741 430 300 515 DIVISION TOT 15055-014 40 102 76 42 100 3242 7530 7623 547 1214 . 84080' 338594' RANDOLPH .HA 15060-0101# 0110- - --1214--TOT4 ; CHAl LAU UAV" LTD jpfWsilJ Irlfirs*$TPtMSiMP wSmMimfa PfAA?plipiy^p im iM1 LEWISTON .NY 15070-0101# 0200- - --3111--TOT4 * .* ** li m f LEX1NDT0N.MA 15076-0101# 0110- - -1213-T074 :lW_ 4 * ... . ___: -..... m**7-i`-M1WmmiSgtigimi '....... IllSiMf SiPi 'W * It! * T----------------------------* CHAIHAH LABS I(JC JL5Q79-0t 7 :i: ACETATE. fA A >6000 : '600(1 6000 flMooo r i 13139 436384 ,<3340 '" 3240 ^3*8$ tlmmSmmBsvJ240 3240 CARBITOL ACETATE # 40 18088 338594 21 03 r" >z o RIVERDALE.HA 150T9-0101# y.::,-:fu3C2r0l^tei>#^K3i|iiA: ;:;*. [{ 5 '_: 66 -3 . .. a: P-;y; 7;' ..; f:j 6 :;-3: 1 C; ,7\ 6 6 7-; 6 66 7 o o S|llf /|'fi ; 60 66 _;. v:;\-:;:. 3m\ ; >;: - 'U ' A * 60 60 60 , .' ~tif 4.-V V >. > iP"P V ; ' \ f; $:&it.iP' 'P"" ,x 'x\% i ~" clif h fiiilflllliftifffe 1 l;| 4| I.C ; iiiSSSia 556 i i L 45 350 CSTKS * 01070 883RCS L 45 60000 CSTKS * l ) MS AUK 126 234 640 12f8 880 598 OCT B80 :.; 440 598 ': 299 NOV 240 546 40 TB Dtv 1967 OfC VTO TEAR 46 Jf~ 72 3 200 2 360 > ':4 * 4'?," ' -;4: - .2... 3 2 '44: PLAN 1 2 3 PQT-: 2 ' :rv ) I at cn UCON FLUORO 11 REFRIG* 95533 0D6MIS UCON FLUORO 11 PROP * V v wr ---------------------------------------------- UCON FLUORO 12 PROP * 103040 95538 BB376* 26234 UCON FLUORO 114 PROP # Wp|:4iOBOTANe66t<12.#:; . ;: * amssk^.1 r~asa^^tiaa?**- PH4315 PH3963 458 2 * 95570 8B376S PN4535 UPROP11 458 628 *>> : ..........ii! UCON PROPA PM3417 ISO* 95772 B8376J PM4511 UCON PROP NIX * 36400 716? wmpo 1661 -100 111234 -676 28185 116 52400 104600 83080 27420 9664*119836 15151 4813 ::i.>4606if2006' 114440 : 4000 1125 516 27806 1078 3313 230360 -1880 103100 638 55829 -1757 24977 1000 260 54840 10159 : 1000 25*9 -97 28060-110069 . 5046 *26633 .. v- . ; ~ : 40" ;*>'& ^;\-jy; 141 . v ir'a*.'. 1400 -74000 614 -16164 600 12 118 1 TT i'-*, ; q# 4 > -4 92940 17608 28020 5836 97146 18497 99360.179900 18065 33Q66 29520 54640 5853 11167 2 0874 16283 >34872" -606 49050 -649 -4 231 56560--5--86--00--5--12--80---------- --------r'..~ -6160 ~212 11215 11618 10167 -1259 55 231 429 272..... J UCON PROP ISO BUTANE * 95777 BB3764 UCON HVC BLOPN3951# i `fi. }i_Sv /!'<' .. 39104 I960 " 15840 599 49402 ~1TM_------- --l:-. ^ ------ * ------*-- ~l~i irfei 5..; S: ;___ ' ' .. . *' ,k :. ? - " -_________________________ ; TS------ imOE 1 1 32 89 89 300 --V. -. ' - K. BLAND/UCC UCQN VINYL CHLORIDE I 95798 B8376* RISC UNIDENTIFIED # ` CHASE SONS 15060-01 SYNASOL PH 3224 44359$ 27 -: - 58 W- 41 7 37 122 2000 -2000 IllfllllS ...... * 66 ^" 59 sr4 *<'* 4:,v:. ;: '9VX :'S. *v:; :v.*- : " 507 "' ^ SCif^ CHASE WALTON ELASTOMERS 15065-01 K-1215 --- ------- # 50i.y (' f'sairyys 7'"y _ . | ^ 1 .! " ^ - " > y. J ^"' t 'j y ', y 1 j "-.' L ' >. " y 1 . i ' ,' 4 *~J'.''" j1 , i j. j | ,y, "s, ."''V " '<'' ' ^T,'--' """.' '.'`"J * ' ................--" 1 y--' 11111 , i ^ _ I, ^ K 1045 K 1347 PAjifo: rMtti&r'.iVS-y'- :-, # 08101 NN2T8S # ^ -V :' ;;. : ,- /' '- ;' ;V X 400 1140 ,-"-'*>-v.'-'- "'^,,!4ti!;i?W^' / 50 143 -'si.-: ,:.. -j.U.^:..! .'.,: -v;.-'^ '--y^ -:. X^:"hm * 1 ' 1::! V HUDSON 7410- ,MA 15065-0101* - -1213-TOTS ** **. :mn-: l ~~ * 2* : ---------------------- =.......... ....... 3 6 ^^Mg*t4lH|^ICAL^C0 INC 1 KBMMiMfiAs**F0AMonf'cM*iii `i TERG NON 15 S 9 84698 006K1S MINNEAPOL.MN 15067-0101# 460 98 * CHATEAU-PAYLTD 15070-01 SORBIC * 82522 2Z6M4S LEWISTON ,NY 15070-0101* * ** * ii 3 ____ 15076-01'.. '''___ U LB170XY26 PM2305# 94364 CC2FUS :XINTON.MA 15076-010 WliisSK ALUMINUM ACETATE NIA * 6000 13139 SS238S 3240 CARB1T0L ACETATE_______*__________ ^1 1 *Z313*,^rolw-,j#?^-V.y5'jl''' 6000 3240 ' '':';ii'-:'' " ' : --`.31'''' '.,-v'i'i' /?,i-' j ttv-3-C^r'; -.v-:>ri: ^--ti':- ' 2600 3600 1404 1944 18 10 "'V '. -tU:.' ''j.-' . : ' -'; : .".' i`- 'i^:'' '' 'V:V ";,' . - ; '. - - "S: -i~ ,. 1' 2 ,.' ' .'-ji'-1- - "-i 'V:;j'r':--'.jS j.: '.-fil.' ; - :i.-.. :*- 4iv:-siht! 18 48 50 10 26 10 CHATHAM MANUFACTURING CO 15082-01 ISOBUTANOL___________ * 14 42 BLAND/UCC 5 5 8 SAR CUSTOMER REFERENCE LIST....... MONTHLY FOUNDS AND DOLLARS - -.......... -.................. .......... -.......... .JAB.-FEB____ MR____APS.___ MY . ..BUB____JUL_____AUfi____ SEE____ QC T. CHASE CO 15053-01 - ..........SEVIN 5Q CTfcl........ ..I LOCO ....................... ................................................. ................................ 15CP... * .A10* 21438 11171$ 410 615 ..............2_ ETHYL.HE ISARCH___ _______A . .. ______ ____________ ______________ 3ML _ ___________________ ... * .137* 370CS 23355$ 75 .SMFGM. _ ..FL_.15.C52-.CI.C1*..,.............. .1______________ .... * _________________ 2. 300 4322 TOTAL$ * *1 DEC 1966 PAGE 1528 1____ PEC... YTO YEAR PLAN POT 3 1 * * .. .1... 1 3 1 * * 3_ 1 2 1 3 1 CHAS E'PRODUCTS c'6"'"............ 15055-01 ' ' ...------ L.A5..35C-EEIK.S#. ... .AC__________________________ *1.553* 01070 123HS1 72 ...........J. A5.BQilC0._Cm.5_______ 1L MU *1.570* 01370 123HS$ .. 691 _ _ _2P0_ _________________ 360 _ ____________________________ B80 1323 440 2 2 l 1 664 2 2 2 *. * 2 2 **3 ---------- LE 46.--------------- ------------ --I.____ . * .582* 01815 123HS* ___________AM....... AAO. . AAC_____AAQ.. _ 132Q 277 260. 259 260 779 1320 778 2640 1320 1540 752 ..... 3520 . 12 2007 6 .12 . 6 ............. L E Jifi. 1____________ _____ ____ 4.4 Q___ 44ft 17Afi_ .440. * .600* 01861 123HP$ 277 277 1109 259 _____ 440 259 2200 1298 1760___________ 1038 _____ 880 8 8 4 4 502 5 5 3 L E._162 ...J__________________________________________________________________ ________ _______ ______________________________________ * .000* 01862 123HS$ .J .LE..A63___________ . * .000* 01663 123HS6 1_____I_____ 4 .1 .522_________ _____________ A * .000* 02522 I23HSS CBWX PEG fcOOG___________f_ * .000* 16241 12 3C T$ * .809* 19051 386H3* .ETHYL ENE--GLYCQI______ JL .. * .000* 35202 12 3C1$ _I5.0P.RQP ANQL. AJ1EYDROUSi___ 1100__ 100 971 81 1_____ L il ___ 5... ^_1.0_ * .000* 43062 123CTS BQRPKQL IRE____________JL__ * .475* 60604 123CTS PROPYLENE OXIDE ____ J___ Ml 219 *_____ * ** __1_ 1_____ ____ * .000* 71605 123CT$ XJAB.ILEME FLY BERELCLTI___ * .000* 82705 166M1 $ JEfijEL.BQCLJMBJ> * .AA6* 84834 123H$$ ---------- TSJEIEAMQL AMJBE-.ECyHtLJL. .JLC2JL________ * .243* 88205 123C7* 280 2 TR1 ETHYLENE GLYCOL___ 1 84 84 37 38 4* 44 1020 5LQ_ 3 3 6 6 224 113 * 4 1 4 * .000* 88505 123CT$ 1 BLAND/UCC 5 5 9 .000* 95533 186M1$ UJCQR-ELUORO. 11 PROP___ 1 * .000* 95534 123SUS 350 1000 67 UCON FLUORO 12 REFRIEU_____________ * .000* 95537 123SU$ * .242* 95538 123SUS -l -126 . .UCON. FLUORO 114 PROP. I____________________ * .960* 95562 123CU$ _PMA215-JELBLLLAN.EEE22i________________ -1900 -361 33100 8028 31 7 __ 2.5.. . 4 24 4 !L_ 050 3000 7 198 4 ___25_ too 4 13 * .000* 95568 123CT$ ..UCON. P-RQP.RlTS.J'Ji. .4.053f ____________ -_AAQ * .172* 95762 123CU$ -83 -183 -17 -250 36940 37 ...... .32_ 2000 3000 6825 6 6 382 CHASE fcuuntTURIV c6 u somuu pb toi .314* *3212 IWll! 0UCLAS fll 15054-010L 900 . - 5152 TOTA^! A X. OtS TOPER REFERENCE LIST FE * MR' RPR BAY A$ PRODUCTS CO 15055-01 L 45 3J0 C5ICS I 1.3pOV 01070> L23KS! L 45 WOOO-CSTlS I .000* 01370 123K5 L 4* ____ .552*230 I .534* oi**l 123MPS <-L 4*3 .. i .000 * 014*3 123HS L 522 i *2.5*7* 02522. 123CT W* PEC *000 .I .900* 14291 123CT: CELL0S2 HEC flP-09-W .791* 19091 12301) ISCPROPAROL UNWOUSI. 1.000* 430*2 123a .UCOR PROP nil Pft3275 I .212* 53275 123a nORPMOt,IK *1 .000* *0*04 123a PROPVUK OX HE 1 .204 * 71405 1UH1: STA4ILDE FLY REPELRTi *..000 * 42705 14*nil TERC ROR im 1 .000* - 44439 123KS1 TKjrrMMUAiK com t *'.000* 44205'123QJ1 /UCOR REF 11 RET IT ' I .000 * 95533 14*ftli UQJR PROP 11 1 ,0OO* 95934 123SU1 UCOR REF 12 RET fllSC I .000 * 95537 123SU! UCOR PROP 12 ' i .201*\ 95534 123SU! -12 UCOR fUlORO 114 PROP t. *..000 * 955*2 123CU1 ' UCOR PROP nil PBU35 i .000* 955*4 Q3ai UCOR PROP tux Prt 4053i .149 * 957*2 123KS1 UCOR PROP* PB3417 ISOl .000*. 95772 123ai UCOR PROP IS04U7ARE I ,040* 95777 1230J! l/COrPROP HYffi P/1395L OOP* 9577 8 123QJ! 'SB -3*74 4 3ITMLY POURB ARi ROLIARS jui jul Aut . sep orr EC 19*9 ,, PACE 1549 EC-.Jfn- YEAR PtAR MT V; u.\ r'V 440 v< 1144 440 224 17*0 497 l 22 r1 ** 33 v,. 5v i1 -.k9. , L 21140 4449 374 77 ib 21 4, b^ -591 -579 3*1 T4S*0 322*0 32799 1550 5*22 344 1100 : r* 37 37. 200 MOO 7 7. 4* boo 107 107 M2 JX)C ^20 -20 51- 2)00 iTOCTawiffi'ljt LIST ~MW ftOrtPHOLUte* x vm*. 60609 12JCTS 'PROPYLENE/OXIOE ,->.`.000* 71005 ia -ST ABILENE FLY REPE___ * .000*- '82705 lB^niS TEfiCIT0L.'Tnti-6 I * .000* `,89839 123HSS T fi.I T-HAH0LAM1 HE COW X * ;000r` 88205 123CUS 'iRlETKYLAniHE X * .574* 88959 18WUS UCON .REF 11 PET IT X 4- * .000* 55533 186M1S \UC0*.PROP 11 x .*-.213* 55535 123SUS * UCON REF 12 DISC CYL X * .000* 55537 123SUS, UCON PROP 12 x *..225* 55538 1Z3SUS, UCON PROP DIX Pri5235j IP5BOO 1 -200! 29339[ 1 i -27! '.f: * .000* 55568 123t?W UCON PROP 115 x * .000* '95579 123CUS ' f- UCON PROP mx pn 9053# V . 185*1 55762 123HSS .'UCON PROP fllX PM 3917X -85 * >.213 * 55772 123CTS UCf>N PROP. PROPANE X ` '.i;OO0<'\55776 -186ms UCON PR ISOBUTANE X *.1000 77 123CUS *uC0n-. DR PN3551X * .0' UCON VI 123CUS ;0R10E X .000 .-.J* 123CTS niSC UNIDENTIFIED X * .000* 95555 586(19$ 7JROAOVIEU IL 15055-0101X 1 * ,I 768 M ' 5911 TOTALS 1 106 : 29 |HASE ftANHATtAN BANK 15056-dl ` Pfiun EC97 * 82 X * .176* 36151 132FTS NEU-YORK NY 15056-0101# 1. 2121 TOTALS CJ :hA$E flANAOEflENT CORP ' ' 15057-d. SAC 970 x * . 500* . 02060 386M3S NEW YORK NY 15O57-01O1X 595 1 , 2121 TPTALS :hase- 8 SONS 1 ' 15060-Cl EX COATNC COWOOI TIES* * .000* P2121 223CKS z o c oo cn O) V7 'V 2933: )UNOS ANO mm l&P urr 96l 217 w imr ,'T* 2m um -1,! 7 ,] 9 J Q !' , 6 1677; i! -1 80 90 n 6 .60 i 9; 39 i- \. 11 '! 21553 . 397^55 2V 9. 22 98; 1000 9 ; 16 ' \ ;1 195-' l*f5 i 799 i` 800 32! 32 [ us; | 100 33300 * 33 r 33* 6235 ,6 j* '6 -I 23287 / '23! -23, 9966,! 9 i : ' 9 . / * Tf- * / * j * ') i >< . 303 } 303 20 I i. !; ' 2000 *` - / ' . ' > . 1 2 119 236 ' 238 .200 9929 1 7 26. -5.6 56 202 v- 516 51 1 1 ; r 11 '- 1 * \ .1 i ** i i * *i X' I.5 - - - __: ..J-i. t-i _________ uiftic '* CONTINUED SAR CUSTOMER RElrERENCE LIST * -JAN' FEB 'MAR' APR HAY >0 280 1 120 r 20 CHASE PRODUCTS CO 15055-.01 ' ' I* ' PROPYLENE OXIDE' * 1..000I 71806 I86NIS TRIETHYLAHINE ' , I 1 -.5671 88454 186*1* .UCON PROP 11. 8 I .0001 8S534 123SU* -366 UCON PROP 12 i 4 i 40260 1 .2211 9553.8 123SU* -785 10713' -977! . UCON PROP 114 ..* 4 l, .0001 -95574 -123011 UCON PROP NIX PR 40531 27840 25540.1 1 .1701 95762 123HSJ -498 5470- 4525 -403 UCON PROP NIX PH 34171 1 .2121 95772 123CTS -395 UCON PROP PROPANE 8 . I .0001 95776 186*1* ` UCON PROP ISQBUTANE I 1 .0001 .95777 123CU1 BROAOUIEW IL 15055-01011 68 26 * 768 1 5411 TOTAL* -2 ' 17 . "4,1 60 45 CHASE-HANHATTAN BANX 15056-01 PN1611 EG97 12 i 1 .0001 36151 132PT* 2 16* m YORX NY 15056-01011 1 946 r 2121 TOTAL* . CHASE MANAGENENT CORP 15057-01 SAG 470 I I- .0001 . 02060 386N3* YORK' NY 15057-01011 ..n945 T 2121 TOTAL* 15- 125 CHASE.t SONS DFO 2005NT 15060-01 P'21321 $ 1 .0001 P1P6T '223CX* DFD 6005NT P21328 1-.0001 PIRQH 223CX1 16 ' DFD, 6603NT P21338 l`A 1 '.0001 PtSTI 223CX* DHDA77028X 55 P2934S 1 .0001 PIWRV 2118T*. 12 HFD84201NT P293U I 1 .0001 -P2NBX 223CXJ LD PEG PRIMARY tCOHH I. 1000 1 .2171 P2132 ' '223.CX* (0 `6 ;2 2 LD PEC POICR PRIMARY I 75 \ 1 2431 P2I33 223CX* \lD PEC 8LACX UPE I . 2901 P2I34 223CX* 203 500 DO PES NATURAL 1V0001 P2931 UPE I 2?3CX* x- LD>E$ SEHI COND s so; pr ?lieT! oo zg co0 01 o> ro :HLY POUNDS AND DOLLARS Jr, jol: bug : r sep : pci: \fw% -47 DEC 1971 DEC, . YTD . YEAR vS I *1 I 40 -.8 .29500 6639 53 : 9 '3.8.. 6 3'1 132 ' 132 l 90 6 - 2 31 31 -i '20 1 .. A/ ~ ' 11: \ : 200 58 :v , '' * 2l 1 22 1 D 1 99 "r ' P 99- ;! 8. 90. 93" '99 ;I i'.8 1 HuannA ;2 Ctf .P I '; T v: 1 - ORE v6 C>  COLGATE PALMOLIVE CO 17949-01 19060 22630t rTs|W% 36770 66790$ ____ HEXVLEME GLYCOL________ g _______________________________ :: ill^fllirawiSy,JlT^^4TCTr^^'>''*"* ^' ,," y1 - v7*'f *?Vi ^~ < 71615 22830$ `ME OXIDE g 15 89947 228308 0HB400 Hi 19 ' rv'.-.'iMif'.imite: . nuiT 1VfiAH gfc-Altt if*; ' #"1 :. * " ' ..'.v -* y 'J V:/ ' & BLAND/UCC 5 6 3 00998 66790088 ?ZSU -6 01503 447768 jftuoau,.i.. 12202 24585 > 1' '1' ^ 7968 400i -2480 J'"'||J'c* r-!"PI^!I 95534 447768 -.meon. fiwnML& mi*j "'. ;r ^aftsaa-.l 95563 447768 J^QM PBQflsqsutame # 16158 ;^ 95778 44776$ BALTi IiMnOunREc,iHnOi; 1i 7f 9/4*9*--0u1m09v#if 104 2684 17569 , ,,,. ,L , .... .. ....u.., ,, ... ..... 21104 w:^W wasi&*& 79 159 105 ' w..\__ ''N' i' {-?*'' 7?' : r.`.J./..U-,?`f?&rsa,frfaC|T$ai'*.<Ss".&.. i5. i.- 26 -{6 -* . -* ^p.ppn-.,..^i ..m.i 46 46 457 457 342 i iTiwW'j" fa . iwi i --.TOH.uk 5tSTOTT mER REFERENCE LIST (TWY 51 ETH 200PF SOM* A f * .000* 31556 123HQI ffORTHLY^OURDS ARO DOLLARS A- : ElH 200PF S050 tf.Y: ; | * .000* 31567 ,i23HSt ETH 200fF SD5C fBP.GR * .071* 31575 123CTI UCOR PROP HYOR PM862I * .056* 52560 123H0I UCOR PROP HYOR Pf15175# * .055* 52562 123HQS UCOR PROP FlUO Pfl32701 * . !W* 53270 123HP* ; UCOR PROP FlUO PH3275I * .170* 53275 123H0* UCOR PROP FLUO PH3268* 1.000* 53280 letmt UCOR PROP FLUO PA3525I 26320 1773 36680 7273 50 8755 372 37320 8115 51780 . 2855 11580 657 '' rX; * * $f * r 4 / 165000 36827 'f. -661 -5115 1 T?.;1 -5880 -112? * .000; 53525 123HPI MORPHOLINE | ;57* 60605 123HPS TR1ETHAR0LAMIRE COfYl * .000* 88205 123HS* 235 561 221 p t -1771 i '* V.y TRIETHAROLAMIRE m $ * 000* 88206 123HS* U L870X PM105T# * .563* 75258 132FSI UCOR PROP MIX PM5305I h- 80 37 *1.000* 75522:123HP* UCOR PROP MIX PM5012 I * .000* ' 75525 123HPS UCOR PROP 11 i; * .000*;.75535 123H0* UCOR PROP 12 I * .236* 75538 123H0S UCOR PROP mx PM5305I *1.000* 75S55 123HPS UCOR PROP mx PA5306I *1.000* 75555 123HP* UCOR PROP MIX PA5152# * .000* 75617 123H0* UCOR PROP mx PD 5072f 36580 786? 1708 -2881 338216508 -887 80302 17572 * ,000* 7576? 123HPI UCOR PROP mx pn 35171 * .000*'?5772 123HPJ UCOR PROP ISOBUTANE % 123H0* UCOR PROP HYOR P7137511 -561 * .000* * 75778 123H0* UCOR PROP R BUTARE i U*CO.0R0P0R*OP7H5Y7O7R7' P1A2W3HOPSli * .038* 75785 123HPX niSC URIOERTlflEO i * .025* 77777 506f15I (fi*W-IR M 25723-05011 617 1 3551 TOTAL* 58075 1605 50 1 ' 158 23 60717 2150 10T 12 13555 -157 -13 165 58 75 35 5 18 BLAND/UCC 564 i * DECf?70 Pirc >o/o /. 1655 TOilR im IW.WJHU 50HB660 `, ^ . * .000* 73302 V] 1 -68 5 , .32 7 251 1700 35 >8 . r5 1 12 r * *' ! *>\ .?* BRADFORD PA 26025?81 l 3151 1 WES *1R0 ORESSR MAC . SAC 570 v^-, . * .000* 02060 1 PRIMARY AflYlVALCO * .228* 13802 1 75 15 15? . 31 # '* 75 '156 300 15 27 15? 31 * ,1 * \ -* 8UTYL CELLOSOLVE *. * .231* W50T;M CELLOS12 -HEC OP10 * .751**17057 1 CELLOSIZ HEC OPIOt * .800* -. 17057 ^1; -1 . -1 .V * > i m. ' A ETHYLERE. CLYCOLiTI *.000* .35167 Vi: ETHYLERE CLYCOL/iv * *. 085* ( 35202(il; i 2 ETHYLHEXAROL * .113* i 37005 Ai: -ISOPROPAROL'?UPf i*` ,000 .` 53056 Ml * * * * }' * : 1' , - l ", '- ; 1 2000 ISOPROPANOL ANNYO* ;; *^067* .^53062^13 *POLYOXiRES,GR<MB* * .000* 70306 M3 POLYOX USR-N-3000; .000* 70323 .55 TEPUIC;PESTIOC-COT , * .000*^85182 Ml 150 . 150 35 1 '. 35 ** * 1*}-. *~ , * LlOO 220 3000; i;4 J6 - ' s , TERGIT0LM5M-3S -S .000*8526213 . 1ERCIT0L;RP-.15 te': * .215*;V:85715 -1I TERC RPX 7111 PM5 . .000*^ 85773 13 TEROITOLWX' 'y -* .210* ,85782 13 702 702 62 7 * ' 500 TRIETHYLENE CLYCOL *.211* 88505 13 TRIETHYL CLYCOL AT * .000* 88506 13 10UST0R . TX 26025-0 172 , 1 7312 TO TERC RPX Till PM5' Tr * .000* 85773 f11 tAflWRC PA 26025'0' 1 766 1 2552 TO1 95 3 * * -10 563 j 82 95 ; 005 1005 3 38 * * 563 263 iO?ll 82 376 TERC RPX 7181 PM51 * .000* 85773 133 :HJCAGO H 1L 26025-0* 156 1 5511 TOT TERCITOL 06 * .000* 65381 161 ; CONTINUED CSA CUSTOMER REFERENCE LlHpONTHLY #-* DEC 1967 m[PAGE 4301 JAN FEB MAR APR MAY ^UN JUL AUG SEP OCT NOV DEC YTD yeaT^ PLAN POT PROCTER C GAMBLE COMPANY 68717-01 PRCPYLEKE GLYCOL USP * 42270 42970 85 85 85 71615 B8342* 5284 5371 11 11 PROPYLENE GLY SENTRY # 43690 39210 41900 42910 43150 43190 42770 42810 340 340 230 340 [ 71619 88342* 5461 4931 5238 5364 5394 5399 5347 5352 42 42 29 ! TERG NON 15 S 9 * 101024 24720 5B540 33680 33120 -7800 66640 33640 344 344 500 520 84698 882001 13199 3095 7756 -831 4126 4057 -955 8163 4121 43 43 67 TERG NCN 45-S-3 * 64708 JJ359S TERGITCIL N0N1 15-S-121 i 84722 006M11 TRIETHANOLAMINE 99X * il ... 86206 BB20D1 40 15 ** ** 700 TRIISCPROPANDLAMINc 1 89255 J43591 UCANE ALKY 11 1 89849 BB2001 j UCANE ALKY 12 # > 1 89350 BB2001 UCANE ALKY 13 * -1784 780 120 B 7 390 67 ** * 11 ** -2 -2 3 1 89851 BB2001 U 8UTYL PHENOL 4T FL # 89952 8B2001 | U 50HB28CX PM 903* *! _ 93212 CC2FT1 U 50H64C0 # 93252 BB3421 _______ U 5QHBIOOO__________ _ * j 93337 B63421 U 50HB2C00 .93352 aaa&UL 2200 561 2820 776 14100 4089 200 88 -6110 -1770 470 178 4000 1020 28200 7755 17280 6307 4000 1020 5000 1275 4000 19 19 15 19 1020 5 5 4 ** * 39 39 12 47 11 11 18 18 66 3 6 22 v 50 U LB1715 COSH GR * 94651 BB342* U DAI905__________________ JL 134200 263300 131860 130720 263240 13QS60 66020 131120 277320 130660 263140 132280 2054 2054 3000 3000 94702 BB200$ 23954 46999 23721 23266 46989 23305 11746 23405 49502 23101 46970 23612 367 367 537 UCON FLUORO 11 REPRIG# :rx-; --___ 95533. BB376* UCON VINYL CHIORJDE # 95738 006Hit 150 * * VALEMIPEHYPE__________ 97139 2Z6H4* HI SCUNIDENTIFIED * 99999 ZZ6UN* CINCINNATI 68717-0101* 1200- - -3261-TOT* UCANE ALKY 12 * 240 35 425 58 194 31 50 250 247 53 -50 -250 366 67 256 46 583 77 907 98 1892 261 1682 . 496 213 88 4 28 699 283 32 '* 1 7572 1058 * 4 1. 7572 1058 5918 923 23639 IB bland/ucc 5 6 5 89850 88200* ONTARIO ,CN 68717-0103* . 1205-2805- -9240-TOT* U LB1715 * 94652 JJ359* NILES ,IL 68717-0104# ;; ,1200- - -5411-TOT* ' CBMX PEG 4000 * 18239 JJ359* 99 '* 500 163 1808 657 2 1 1356 492 1 * 904 328 1 * 904 5 5 328 2 2 155 *22 11 * 18^ i/;# 5 5 1 CELLCSCLVE # 19512 JJ359* TERG NON 15 S 9 * 7360 7360 7360 14720 7360 44 44 12 44 fo * '>,Y ' , 84698 SS3 . 1343 1342 1343 2686 134 1 8 8 2 l?'| ..... ... CSA CUSTOMER REFERENCE LIST MONTHLY.Art CUNT lMjtiJ RUST OLEUM U'lhP JAN FEB MAR APR MAY JJN JUL AUG 75547-01 UCltn PROP MU PR 4o 53# 9 5762 547761 EVANSTON , 1L 753**7-0101# r 1390- - --5411-TfiTi * * 1 1 *1 1 * ... JL... 4 1 RUTH BERRY PUMP CO 75565-Cl U 50H82b0X PM 903# 93212 229FT1 MEMPHIS .TN 75565-0101ft r laOO- - -64 J3-IQU SEP OCT 1530 336 2 * NtlV RUTHERFORD HOSPITAL INC 75571-01 TERG ANI 7 a 64241 333391 MURFREESb.Th 75571-0101# r 1810- - --4532--TOTi RUTHEKFUKO DYE CHEM CO 75573-01 SOOIUM ACETATE ANHY s 2 500 1250 3750 3750 2500 5000 2500 3750 3750 25 00 2500 61004 436471 413 206 618 619 412 824 414 619 619 412 412 i NEW YORK ,NY 75373-010U 3 1 4 4 3 5 3 4 4 3 3 1* 0410- - --2121--TUTS * 11 * 1 * 1 14* 1 RUTLAND fIRE CLAY CO 75576-01 N BUTYL ACETATE 1 15B21 338591 ) ; CARBITOL PM 600 * r 'JV.:.-...-.-' 18017 338551 U1BUTYL PHTHALATE A i 24154 338591 GLYQXAL 40* A : ^ 1" 40751 338591 i >1 * SODIUM ACETATE ANHY A r "i'.'81004 1171 SI RUTLAND .VT 75576-OlOJA ) 0580- - -1153-TOTi GLYOXAL 40X A ; i 40751 339631 . ' ) SOOIUM ACETATE ANHY A r ;,V-. vi---` B1004 338591 GASTONIA .NC 75576-0102A i 0585-0915- -4123-TOT! RUTLAND FIRE CLAY CO U DIVISION TOT 75576-011 1600 -BOO 272 -135 1880 -940 450 -225 28B0 -1440 735 -366 100 42 -41 , -V * ' *. .s 6 -3 1 -i 100 150 150 100 150 100 42 63 63 42 63 40 250 41 , ' *' ' ** *4 4* ** * 4 *4 * 4 6 4 * 4* 4 144 ' , '' '* , 'V V *; - , * * -3 ,, -1 r\ RUTLAND PLASTICS1557^01 DIETHYLENE TRI HIPUKTa 26233 338591 DIETHYLENE TRI COM GRA 26237 338571 l FXL PZR NOOP MFG A 39170 118131 450 106 450 106 1180 277 OEC .1966 PAGE 4357 OEC YTO YEAR PLAN POT 22 *A ______2_ 7 7 5 12 333 25 00 36 36 38 _____ 38_ 412 6 6 6 3 36 36 38 3B A 6 6 _6 . .1 * 1 4 i * * *. >- A' S' 150 60 4 4 * i i A 1 * 4 1 1 A 1 1 A * A 3 1 1 .A * * 1 4 4 1 ___ 2_ 2 3 '- `S 7 1 1. 2 9 ,,v- 2 1 2 A 4 l 3 CSA CUSTOMER REFERENCE LI 3NTHLY -S CONTINUED JAN FEB MAR APR MAY JUN JUL AUG RUST LICK INC _ 75546-C1 ! CIETRYLENE GLYCOL A 2601B 603DJ$ ILPUENChANI A PM4189* 54109 CC2F0* MORPHOLINE * 4 60 60604 CC2FSS POLYARINE T NEW * 261 -- -- ...... ----------------- 70060 CC2FS* POLYAMINE T A t! 70061 CC2FSS POLYAMINE T NV * 70068 CC2FSS 36380 5093 37110 5195 38280 5359 PROPYLENE GLY SENTRY A 71619 JJ359S TEPG NON 15 S 9 * 46U 9 20 84698 D06M1S 90 179 TERG NON NPX A 480 960 480 480 ________ _________ 84782 BB3DJS 107 215 108 107 TR1ET hANQLAHINE COMM A 466 0 480C 4845 88205 CC2FSS 1049 1080 1066 TRIETHANOLAMINE 99? A 88206 CC2FS* U 5CHB66C A 93302 DD6M1S GRANITVLLtMA 75546-0102A 0110- - -1213-TOTS 1 49 *8 1 50 *6 1 51 *8 1 * SEP 460 261 4720 1062 13 3 OCT 1840 359 39 6 NOV LtC 1967 AGE 4625 DEC YTO YEAR PLAN POT 11 11 1 37780 150 150 190 201 14356 30 30 27 920 920 5 H 179 179 1 1 22 11 4620 24 24 1039 55 5 5 12 25 3 5 13 39 257 257 272 351 3 15 51 51 41 RUST OLEUM CORP 75547-01 BUTYL CELLOSOLVt A u 16507 JJ359S CELLCSZ HECOP-15000-HA 50 19061 QQ6M3S 52 CELL ACET URETHANE GRA 2200 19549 JJ359S 462 TETRAETH PENTAM1NE A B5408 MM2PHS UCGN PROP MIX ?f. 4053A 35800 65140 55762 BG376S 6906 12556 FVANSTON .IL 75547-G101A 2 36 65 2420- - -5411-TOTS * 7 13 2200 462 * 880 198 97220 16520 99 19 647 BO II971 65 12 93920 17355 94 17 165500 30596 166 31 63940 -4110 64 -4 100580 } 8586 101 19 10.3400 19107 103 19 1C4980 19399 105 19 * # 5 1 895 151 901 152, * * 5 1 895 i 21 901 152 5 3 1000 195 1005 198 5 8 1000 1013 'I RUST PROOFING S METAL JL55fiS=at. UCAR 101 A 03661 PP3SJS CAHBRICCE.HA 75549-r/101J_ 7410- -1213-TOTS BLAND/UCC 5 6 7 SODIUM ACETATE ANHY * 1250 1250 1250 2500 2500 2500 1250 2500 3750 2500 1250 1250 24 24 40 40 B1004 SS247S NEW YORK .NY 75573-0101* 43 219 216 ____ L_ 436 438 43B 219 438 656 437 218 219 3_________3________ 3_________1________ 3________ 4________ 3________ 1_________L 4 24 4 24 7 40 40 0410- -2121--TOT $ 44 7 RUTLANO FIRE CLAY CO 75576-01 SAG 470 A 02060 NN2RUS N BUTYL ACETATE_________A 15821 JJ359S _800_ 140 440 207 1200 210 400 400 70 76 l^^cC;;. - tC MlVYLMu: '.CO*.;, 6F45* 2 711C &t*.;r#C.t-f* 17 .PR 4513*.H1XMM...JA22_j '^1'W>:' <!7(2 123h11 13*-. 2*103 STCi*& ,|L .7!f 7-015 1 i ...-U9P. '*'" ~%t- TOliti. .25 - Vccac iVt CO....... Ttit't-ll .ItcT; JhU ccp.s..................... P.P7M2 ??>r.n* Y4$^i*hj i'i<t-aci*_ .............. gj^; p`tKV:- total* tjJPvP'P " : -"' - pvp CO <5565-01 SUPrOP^tKiSIM. ......... * .CCC* P1UJ 21U> 'ST^-IFP. .NT..M FLO HC* .nc* pn*2 ;liif'i ;51Y** SUOETat Hi* NAT f .CCC% P 115 3 211AKS -tHFI-l' .IS 755i5-CUt* <*?; '<<t; to tali : !,' LT>tMct eye < tn* co -jp.te-.iy/.if af<m * *??S. Dec* n?4U Y i`.!?2-UU ;t;i i.! tali S CITY CHIP 75574-n ttf U.r 3 ECr 451 f T<1 * ,rr* p< ? < i PC'CCt f f [f.riCf,.. .to liiii -CICU miALt !!l/A`f F m" CIM r.c 75576-51 sup-op'.,(H >i 1 At . s * . 15 f* pun ;iu*i 57VF-PU pi fee .ixp .. * * .CCC* p 17 : t e\ JAMS sit <7 . a 7C*' CTC t C 3Ef*'A K. f0 f7L. ICETAlf, .f .ISO* j;e;i *7355$ EUTT.L . 1.11.51 CL VE ACET9___ * . lit* Utli CA*EJ1CL, PM..6CC . . I , * .2*6* teen 723551 UeiiTYl. Rt-JMLATE......J ._ * .*75* I15* 2335*1 tJLlfC*JU_.A.Cl................ ...3... J * .AC5* AC75} M2f31 lffCJICC-t'-^A . .. * * .-re* i[(f|i -.104393391 _..;_1Q 4 -300,., -51 * .2750.......2500 492 43* -3 . . 3 * .* ..150U J500263 262 2 2............. ___________ '.. . .* - * -173 440., 207 -4CQ___ ,J5^ 76 .75 bland/ucc 568 'im H> *5 ' rS'!,I `-v^ir*- -1SL -* .6275 .2550 .... 1057 437 _.;.j______i__ _ -. i -* ... j-. 'j*. ..I 35J _ 2. 152 ' -j - ____ 1. ;.vis;-, - . .-`p_2__ l..i it. . 11. - ..(`.YV3fc0_ii4,.2 --* t--..,,2. i.--i.t--it.-.t--x..5____ Ht SAA QiSTOm KFOGKX LIST ja m ma am hay 709HK------- 39 V 70UMS AM OOACS JUI JUI MX OCT . OT ' . 19 * 30 40 90 * 1C n a jure 7097-0101 II TOTAL a 91 11098) 1972So 131710 137100 19929 27243 22142 21453 112 191 132 190 a 2t a 22 40 41*20 11999 1445M 1U4940 *27751 27941 140 IK 2737] 119390 19932 14*720 29022 1309a 2a ij 12 *329 142 ' 2* 142 21 121 21 172 -,199 X 27 EC 1549 r~r 0 32ta U90 L440 22*41 279 279 139 1494 1494 23 294 Ad 4979 {UHL -IZL 3 200 38) 14*3 2 0 391 co n. iru him n iu act .3 211AM OT At xm zi un nr mt 3 2iun '*3011 13 TOTAL ;* . .v 0 m i*m 5UWO-J0U m TOTAL 7045-01 525C 7070-01 v.* '\ * 3C a 72573-01 ATE AMT 2500 110M 12197* 937 7073-OftL 3 * in TOTAL ' -1 ,1 v\ 9 i - 250C 931: 0 5000 *n 3 V 1 4 \ 5000 . 123 y 1 2500 931 3 \* <k t` '' ` / ' ' 35900 5929 5000 *75 '5 1 T t 9 I 34 4 519 a l * 5050 '94 5 1 9950 HI 5 1 -2500 -937 -3 *# Xa 5 5 34 a 55 U 44 11 11 11 , 1;1 8 - J a 30' a It 99 9 559 a a 21 *55 9 72574-01 V - 4 V. 1213 1*4A> ' ' * TATE , * ii Tjm ATI iy-.uv., V 017 23m ] COP-SXOOOM 045 31344 in tJ-9 231594 i 11 113434 1*1 190 . 114*1 4CT wen IDO 94 4 , s 910 ] 1117 p 23J 39 U 994 ai 5< 31 1955 90< y V . 932 101 43 A mi * 32j r 4 . 1197 239 i 50 ifii 900 92 mo 2*8 t4 357 92 973 121 \ 59 ) a/ A V AA A 2 \ f >' ft V 973 ' 2 121 A f' A 2 A A AA 9B * 3 133 A \ A A ' \* 11 l1 1 EFERENCE LIST RS Cn3raF= im 7559/-In mi pmul cs ac m # HAH - -----TRTT . M JUL * .000* 11550 323UIS CELLOSCLVE ACETATE # , ./ -' n iio * .2tt* 19552 323ISS CYCLOHEXANONE " * .000* 22052 123IS1 UCAR LATEX 311 * .515* 53513 3ttn3$ * '' V y 205 222 t~~-- \ 119 ! - TERCTTOL 15-S-9 16 * .01]* ; 05690 l,,eant 13 TETRAETH PENTAMNE ' # 963 963 963 * .657* 05508 321IM 303 303 X6 "TOLUENE l 1* 1.000* 87207 323ISO TR1ETHYLAM1NE # 90 ;. i * .667* 08559 3211C6 60 i 1 (ICON PROP MX Ptt 50531 126390 171190 236200 69900 110500 193590 186790 189320 279790 112300 ~ I * .160* 95762 322PM 3 VANSTON IL 75557*01011 631 il 5911. TOTALS : 1-. . . 21528 129 23 30816 113 37 93611 238 ,91 11986 ' 70 12 12991 113 15 25175 165 31 31192 166 32 31833 211 38 96388 281 97 19155 . Ill 20 i P RUTH.6 CO 75565*1 1 < U 50H0280X Ph 9031 -* . 576P 13212. 166*1$ HoustonI) tx 75569*0101* 197 T .7312 TOTALS 1 1 92 . 20 1! * - ,* l V ; DEC 1970 P4/IF IUT i 11 Jit * .* /1 %. 1 * ' 79200 12610 101 * 20 1706 286 1802 315 * .;<* * P * 9* * * 1 '* 1 * 1706 286 1602 315 1751 301 1791 311 ' * ,* * 1751 1801 IUTH >ERRY PUnP CO 75565-1 1 CP PO STYR OOLONG CRY# * .000* . P1713 211AM HI 1(V EXT APPL1AN NT* * .000* P1791 211Art! Hi WP STYR^CP NT # *.000* P1793 . 211AM * HI. I*P EX PACKAGNG NT* * .000* P1796 211AM RUB *00 STY SUB NAT * .000* P1793 211AM PVC CnpQS RGD GR STNOf . * 000* P7711 211APS (1EI1PH1S TN 75565-0101# 597 : 1 . 6113 .TOTALS tUTHRAUff INC 75570-J 1 '(11717 EC95 , 85 # t a61*. 36155 186*11 PITTSBURG PA 75570*0101# 512 ! 1 3151 TOTALS *! "1 \ . b t`V , * \1 , ' A, , 1557 256 2 * '* * 1 '* 1 -. > 't. * * 1 * * 1038 182 1 * 3 -* 1 -3 : # 3'-. v;1 3: * UTHEHPORD DYE t CHE* CO 75573-1 i SOOIUTI ACETATE AKHY .000* 01001 12197S |W YORK NY 75573-0101# 919 1 2121 TOTALS . j 1 1 * . t 99 9 99 * L. rr HE HE (SALE 11 |S8C U |=H1C 11 Hc GP WAN 96 ME 'HOE 13 C >1VI sen PE >KOK 90 iCM PH OU Yf YY YA PY 1 L d CE 01 pf F> A i; !-' -- . . SAR CUSTOMER REFERENCE LIST M' ^CONTINUED 'V JAN PER MAR APR . HAY *U5T OLEUH CWP" j 75547-J0I 'VHCH TYPE SOLVENT RES 300 300 I..4481-97222 321EB 125 125 VYHH'TYPE SOLVENT RES *250 250 | .3471; P7223 ?21ES ZNU "0624: 1 .8421.P9035 321EF 84 . 84 563 663 374- 439 BUTYL CEUOSOLVE i .6761 i||07 323UX CaLOSZHECOP-lSp-H MONTHLY POOWS AND jun; 250 .500 127 222 250 500 84 182. If? 37 25 " ,0001 18061 $N3 Z HEC:QP-44Q0-H MWI 18096 386M3 ELLOSOLVE' . .OOQI19S12 196H1 ELL ACET URETHANE OR 2441 19549. 323UI tNM4446 CiSmAC 99w* ' 446 1794 .109 437. 892 1338 219 328 i .-2441 19552 3231$ 992 218 'A A YCLOHEXANONE . ` ,, UKCiASR MLALTEitXty3M41 3231$ 241 43913 386H3 INE 5 ' MV32* JO* S469fl 18SN1 ETRAETH PENTAHINE .^41^65408 321IC OLUENE .0001 97207 323IS RtETHYLAHlNE 16 12 487 3*14 463 312 44 16 40 41 I .0001 88454 321IC UCON PROP MIX PH 4053 I.1761 85762: 322PC . $VANSTON !L 75547-0101 A 639 / 1`5411. TOTAL 122100- 81820 138900 156840 116360 174160 124060 20399 ' 16728 26230 26859 20802' .31755 22609 122 83 162 159 . 139 176 126 -20 17 34 27 28 . 32 23 132 27 RUSTOL CORP 75548-01 ! CELLOSZ HEC0P-S2000-H II.1801 19065 322RD - .7 * P ROTHr| 75564-01 : U 50HB290X PN 903 ; 1 .3661 83212 186N1 P#'iTV#43ttl RUTH BERRY PUNP CO HI IMP STYR EXTRUS NT ;.^T?ra.N?,,jT I .0001 PI743. 211JT 75365-01 CD 5zo> oco Ol -4 \ 478 175 I >1 JLLARS - :kp" OCT; ..now; .500 ' -225 '375 375 420 293 37 25 375 293 DEC 1971 / dec; YTD. YEAR 2` 2 .1 I 1 1 1I 33 1 2';- 2 II 'I I 50 ; i . 57 i1 1I 446 .;- 892 109 210 6 ' >* 6 1 - ' l'; . 1 -1 1 !. . 32' 45 4 463 * 312 * /Iv . .T 1 I 1 VI . I l I. 1 J I ) I I * 1 I 7534 35067 19238 24299 291 281 155 222 123 160 1756 1756 28 43 20 24 324 324 50 59 1 , I II II II 1I II II I1 II 287 1739 380 * 73$f -si 5CM 0LlStor8StEE fxlpzr hop I .0001 39473 : METHYL CELLOSOLW : I .0001 80604 : PROPYLENE 'OXIDE I .0001 7j8Q5 ; .0$ ANOEL CA 75811 J70 . I 8112 BXR 2620* ' 100 * .4891 P2009 : B)C6 &bOO ' ' 1 I850I '>202 f CXH 1634* l .0001; P3806 CXH -2400 ^,3971 P3011 ; CXH 2432 1 .4101 P3813 CXH 5254 1:6831 P3014-; CXR 0405 V 1 .0001 P3882. CXR 0406; 1 .0001 P3883 ": CXR80406 I .4951 P3884 v: ERL 2774 . 750 i .4751 PS78L BUTYL PHENOLTRES I .0001 P6135 ; EPOXY LIQUID RE6 1900 ; 3142 1 0001 P64tl.,v; THERMOSETTING ACI i .6521: peen.'V. UCAR BIS PHENOL ! -i I .0001' P6923- : VNCH TYPE SOLVE* 1 .3901 P7222 VYHH TYPE. SOLVE* 1 .3381 P7223 : VAGH TYPE SOLVE* I .4961' P7225 : DISP*E6IN OYNH I .2901 P7316 ! PVA OTHR THAN GUI I .0001 P7412 ; PVB RESINS XYHL ' 11.0501 P75I1 : L 45 350 C$TX$ i .oooi 01070 ; 45 1000 C$TXS 12.4381 01100 SAG 47 I .0001 02050 ,r*^. `Zj. 77" ' 40 r\ > _ rPJ ' : v ''r/:i - ' ' < * XX; ' v '7! SAAHKTfWRREF1prtik LIST-'*, rrurnim . JAN lT^ -APR wntmLy fwjf(SM DOLLARS *' ; KB ' DEC 1972HIPAGE 3XL -XL - AUG .'. SEP ^1 HIM.'Vi 3H 1IH i XflffMEl. sag Jsa isrironc : v - . 75596*9 lERcncure- ' # '' T - j . . K- "i ^ r '77 7S'*-- - .000* '89782 323CA* MV; WOI CA755%'0103I .2 V' f . ' */ /; ` *** 653. 1'.6112 TOTAL* 1ST LUX WC - # 3IVZSI0N TOTAL 75596-fll* '* 2 90 ' ' 1 ;.-:9 ` * '>.90 UTCLELft OfpM:::\ * 75597K l".,; OJ12103 v * 17150 !*\322* P3809 '321EF* 1J s '(003 1 WKS TVfE SCLVQff RES# - ?-';4 V v* .910*) .P7221 ..'321FB* WCH TifE SLYENT RES# V ' *;*ifT.-1 * ` 500 * .990* ' P7222 321EB* ' - '"f.- 225 ' WW TVfE SCLVEMT RES# 500 .* .'370* -P7223 321EB* 185 6850 >2398 *, is. ''' . `t '; 29000 7500 500 2*6 : ' ' f "-rf^ T - : '7 ?y. 37 7i7. 7 /* ' ^_t i; 'r - / ,V' ' - Cys v-v. '9 i*- - ; . .' 9 ^7:92 >79 -it '' . 90 9 Hi* 'e , 23900, r^* 7969 500 , `7T- ; 500 295 ' .295 500 500 f1 225 : 225 .500 ' ' , ; 185 '-500 ... 185 ;< -) -*17.** - ' , . 7 *- -. \. .-.-91 O:** sy.*S ' ` , - 1* 29000, 7500 950 '966 500 500 225 225 500 185 7 >'7- a*' * 7 7'- '> (j >1 -99 s1 298:' S- S5mC3J 190 '-f V' 7-> -.. -p. pm GLUEE* ttKEE D-./. 75BUH3 a qp-woh \ r'.79> 490%-322PBI CELLGKLVE' V . I * il59* 19512 323ISI CELL ACET URETHANE CM '25 .19 -'j 7V 4 - , * >. - , > *" /: * .230*' 19599 323WI CEursavE acetate # > aw*. 19552 321151 1 >% 96.. .-; -30 - a .19 w ^'1%^ -iS-v DIACETOC .ALCOHOL' - #A| * .130* 23002 323ISI ;1 :-l2 '* ~:-'2 1 3 -. 1 . 2.. a V71f;,,'1OV*lr '.`;y.1 /. ; v7y < yyV '7.7, r: 7' '<X1v",-i jT"* 777:?^, taamt.pmwuTE :; .000X 29159 323IS* ..OIWUfWWKlC X# *'.000* 25219 339W OIETKVL0C OLlCCL' r, * # v* ;069* *26018 ,33*69* WEH TVPE SaVEKT RES# .55CK P7225.321EB* / j , < 7 s 200 T ,110 --V-- v.Zf. 777;' '% .7V,y -tmethvloetrkwme.wi >`*i;,ooo*.i26233';>'i_;; ff-Hb. 2W10629 .;. -# *'.769* P9035 32191 iwisN BUm ACETATE # >.216* 15821 32313 BOnCCELLOSOLVE ; ?# * .251* 16507 323U ..'563 525 , 939 910 , ' ' . * c-'.o ' " -1 . ` * 1126 878 `^ 1 -, * t/.;- 913 375 ' y 375 : .3 ^.3 ' 319 .. 285 -"v .'255 y-2- :i596 399 *' . r" -t > v-"7 - '* V-.* 630 .208 ,. I : * - t 'Ui* 7.7-7 7:#. .7 7^ 7't -*{ V '.7y;y \7 i ! TX'-' ", . m imisoBum: terapllf X .150*/ 2785?=. FTYWO HPA 85*.UX* ^25DfsSaaotsB2uq[ ./oitet; EitiiwqiE'liMrt ^65**)29UiB22ra , 9203 M.'X }(2 ICC OFAW-H # - '.k* ' y-`; .7 50 ::';50 '77 7 , * y>> ' ; > >L160* 19096 : 38tfl3* . 7 '.' *i* 7- ` * - ;.58 58 l. - '"`V Jr ; ' :^159*,3298975::?2ac; ;CBI AXT1IETHANE Ot# r.996. 996 892 892 892 -.892 : 892 '' 7: `. ,-867. 996 : 892 .-; 8' . -8 ' ' 7"' >7^7 ^/Aomuiwmmtii >_.29> 19599 323UI* , ;li2 111 ? 223 Celloseuc acetate # ;* .250* 19^2 32313 .! /:C E7HM. ACET 99.5XUR CM ^ k 1- *-,622* - 32110; 32313 ^ -V> ICARLATCX391* V < -: .000* V 93913. 3SW3* -/ " *. > - ` TOfHOLIJC - . : : . * ,, ;.:32 223 " V- ' . *>' v 223 . `x-'" 's 91 -205 .223 ::892 223 X,_lVu7A. , -" 7<6:- r 4; : . 9l : 217 ' 7 :r\ - ' -J ,37 7 : 23 Vv'/-* ; , ,, -7 , Vv f , :fL 1' 03 i > T-,*r .223 C "V. ' 7- ** i\\ : 7^' 7 Vyi V- 1 -I v'( y* '1^ J( Si 7>*' ; -77' :f.- ,7. 77{.:7 : r . >,--- *.--V^.> ;^-Mt: / Vr* ,;\-l : -r *1 i . " * ' 7`7.r+\ 7 .! j 1 , - 91 \; ..j .??*: ',* ,7 >*j ., 7; ^ i.' ; 77 `c :Z' 7y 7:. 77 i S; --L ;ETKXetfrpCET#i 1 fEwtae'ctotSt^# ?;0*4 <35202 ;S322P Mti a ^'ETHHlCWNGD^^i# II!>: V177*. 37005 r!323I " 7, ,*,% '2 ETHVt HEXOIC.ACm: i ?*1.0Z69'-60tO9 ;132QE* V ' V <6 FROPVLE* OXIDE / : ; # f i.. 7 * .735* . 71805.! 112SAS TSBI7CL 15*S-9 '# \*: : * .ooo* a%ie .ifitfti* . v;` |:V" > - :/- j.J _ i . - - * . 38 7: > - j i :v 0* - `7.- 3<, " 25 p'.< v''/38 rm 1 }. > Kr-\` - >.. ,. ? . r. - . 1 ' -V 1 y7 * . s ' '9. - . , - iV ..'x* : >'* ' , \ ," ? . - `r 7* .300T 37191 C 322a .2E1KMM1 AisntiTnoi .;>'.! -y "` .> VY ,Vs: >..*000*3ratf!422W* '" `-\ v t'j4, ' * .000* . 39235 y3?3IS* TETRAETH^EWfltUlC * ' 85908^32110 \ ,w fttp mx m .9053# 2mw , 4 1 ' -963 ' 963 ; 963 .306 315 315 372260 221330 -39020 >. 1 . .'963 315 1852 9 ' 121"22 :: -2 890 ;"'9'. ' ! * *' : 2 .y 1 ,. - .090 L800 pPj/p; .ooo FX' P2R OOP FOOD 5R I * ..170* 95762 322TO iWKTM H 75597-0101# ^ao1 *, 8 t 1, -5911-. 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