Document VjvyVMnD0xvJ3Mnz7L2v95By4

b u f Y l i in n rs TITANIUM PlflMEHT CORPORATION (Subsidiary of National Lead Co.) No Warranty Results of tests and formulations listed herein after are only for guidance in experimental work with butyl titanate and are not recommendations for finished end products derived from butyl titanate. We make no warranty of any kind, express or implied, as to the effects of the use of butyl titanate or the results to be obtained as the use of this pro duct is beyond our control. Responsibility rests with the buyer to determine that the use of butyl titanate is permissible, fit or suitable for his purposes. Price Butyl titanate is offered in experimental quantities at 1.90 per pound, f.e.b. Sayreville, New Jersey. Toxicity A long experience with titanium dioxide shows this compound to be physiologically inert. Any toxicity exhibited by butyl titanate would be expected to come from butanol inasmuch as butyl fcltanate hydro lyzes to titanium dioxide and butanol . Under the type and conditions of use of butyl titanate, any possible toxicity of this compound should be established by the user for his own information. DUP030003560 mmm Butyl Utanate What is Butyl Ififcanate Properties of Butyl Titanate Chemical Properties Rydrolyeis Ester Interchange Stability of Products Interaction with film-forming Materials Vegetable Oils Some Examples of Reactions with film-forming Resins Alkyds Hienolics Vinyls Cellulosics Epoxy Resins As Vehicle or Carrier in Aluminum Paint References PAGE 1 2 3 4 4" 5 5. 6 6 7 l & 12 14 15 DUP030003561 BUTH. TITANATE Many organic compounds of titanium have been prepared, some of which have been mentioned in the literature (8), Work in our laboratories has been concerned with organic compounds of titanium for many years. Of the organic compounds of titanium which have achieved commercial significance - probably titanium phthalate attained greatest importance when it was the additive to contribute chalking resistance to titanium dioxide (TITANOX-A phthalate treated which was discontinued with the advent of the modern chalking re sistant types of TITAHOX titanium dioxide), But during the past few years marked interest in organic com pounds of titanium has existed* Stimulated by work done in Australia (1) and reviewed in the United States (2), the probability is that such readily aroused interest is the natural result of curiosity bound to be evoked by the discussion of any titanium com pound which might be applicable to coatings * The position of titanium in the coating industry as titanium dioxide, the all-dominant white pigment, and one of the major factors in coating progress would seem to impel interest in any other titanium compound. Recent attention has been centered mainly on butyl titanate or titanium butylate depending upon how one wishes to Interpret the amphoteric nature of titanium. Many titanium esters can be prepared as indicated by work done in our laboratories and work reported in the scientific literature {1,3,^,7). But singling out butyl titanate for first attention is probably the result of its greater stability and less rapid hydrolysis as compared with the lower alkyl homologues such as ethyl and propyl. Although higher homologues are still less prone to rapid hydrolysis, the butyl ester is a good starting point because butyl alcohol or butanol is readily available commercially and at a less expensive cost than some higher alcohols. Although the properties (1,2,6) and possible applications (5) of this interesting compound are mentioned in the scientific literature, this discussion will present the properties of butyl titanate prepared in our laboratories on a pilot plant seale plus some of its reactions as we have observed them, 7bu may find in the following pages some feature of butyl titanate such as the delaying of gelation of epoxy resin solutions in the con tainer, that you may wish to investigate immediately. Some new line of investigation for you might also be suggested by the reactions of butyl titanate. DUP030003562 -2~ WHAT IS BUTYL TITANATE? Butyl titanate is a compound derived from the controlled reaction of n-butyl alcohol with a quadrivalent titanium salt. The chemical formula for hutyl titanate is TiCOG^HnJ^ which might more logically denote, titanium hutylate or the butyl ester of orth^titanic acid (Ti(OH)4). Considering the compound as a titanate though may lead to preference for (C^Hq )^!^ as the formula. Regardless of nomenclature the compound which is an organic liquid can be considered to embody the replacement of hydrogen atoms from the hydroxyl groups of four molecules of n-butyl alcohol by a titanium atom. Schematically the compound may be pictured as four butoxy groups surrounding a central titanium atom as in the following in which the symbol Bu stands for the butyl group C4H9. Bu 0 BuO T1 OBu Q Bu Considering spatial relationships, this structure affords titanium an opportunity to enter into coordination reactions since titanium has a coordination number of six. Prom our work, evidence points to the.titanium atom as being the prime factor which contributes the unique properties of this compound while the effect of the butoxy groups is coincidental. DUP030003563 -3- PROPERTIES OP BCTTL TiTANATE Form . . . . . Color ........ Odor . . . . . . Flash Point ...... Boiling point .................. Melting point .... . Density......................... . Liquid Colorless to light yellow Like that of Butanol Determined by free Butanol present Pure Butyl Titanate; 1TCPF. 'Butyl Titanate plus 2# free butanols 130F. Butyl Titanate plus 4-5fo free butanol: 95F. 160-2O/2 m. , 310-314C ./T60 nan Forms a glass below -55C. dH 0,998 Specific Gravity . . . Viscosity..................... . Refractive index , . , 0.9961 O.T99 stokes at 25C. n3| 1.486 Dielectric Constant 3.00 at 20C. Dielectric Strength Breakdown voltage on the order of 40,000 volts has been reported (1) Solubility Benzene Butanol Carbon Tetrachloride Acetone Water Soluble Soluble Soluble Ppt. formed Decomposes - Ppt. formed Analysis T102 23.4 - 23.6# Formula (C^O)^ Ti Molecular Wei^at (theory) 340 DUP030003564 -4- CHEMICAL PROPERTIES OP BUTYL TITANATE Butyl titanafce has been observed to enter into at least two types of -chemical reactions hydrolysis and ester interchange HYDROLYSIS On exposure to water, moist air or substances containing water or hydroxyl groups which accelerate the hydrolysis of practically all titanium compounds, butyl titanate hydrolyzes rapidly. The hydrolysis proceeds rapidly at first and then in stages to yield eventually titanium hydrate and butanol. The extent and rate of the reaction are mainly dependent upon the mole ratio of water to butyl titanate, The reaction can be controlled by the use of organic diluents such as ether* dioxane or butanol. In our laboratories, reactions carried out in dioxane solution, have clearly illustrated the relationship between the mole ratio of the reactants and the product of hydrolysis. A series of polymers of increasing molecular weight seems to be the best description of the products of hydrolysis, as .shown in the following table which summarizes some of this work: Table I Hydrolysis of Butyl Titanate Moles HgO per mole butyl titanate Mixed 0.0 0.5 0,75 1.0 1.5 2,0 3.0 Reacted 0.0 0.5 0. 5 0.98 I.I8 1.58 1.90 . ________Product of Hydrolysis Moles"butpxy Molecular TiOp(^) group to Ti Weight Description 23.4 27.0 33.6 39.0 49.7 5vt6 60.6 4.0 3,2 2.35 1.95 1.20 096 0.85 340 -- ...... 1075 1800 --- Liquid Viscous Liquid Viscous liquid Semi-solid Solid Solid Solid With the exception of the last mentioned above, all of the products were soluble in the usual solvents such as benzol, butanol and ether. DUP030003565 -5- ESTfiilR The other prominent reaction of butyl titanate is that of alcoholysis or ester interchange. One to four of the butyl groups (Cj .Hq ) designated Bu can apparently be interchanged with alkyl, aryl or acyl groups through reaction with alcohols, phenols or organic acids according to the general Idealized reaction; (BuO)aTi / nROH (BuO) TS. (OR) / nBuOH 4-n n This reaction proceeds rapidly without the need for a catalyst, but under certain conditions is reversible. Equilibrium of this reaction is determined naturally by the concentration of the reactants and the relative reactivity of the ester formed in the reaction,, butyl titanate, butanol and the reacting alcohol. Control of the reversibility of this reaction is the most important faotorln working auccessfully wlth butyl Stability of Products Formed from Butyl Titanate through Ester Interchange The reactivity of the titanium ester formed by the interaction of butyl titanate as illustrated in the above mentioned general reaction, decreases with increasing molecular weight of the alcohol which is reacted with butyl titanate. This suggests the interaction of butyl titanate with high molecular weight hydroxyl-bearing materials to yield interesting stable derivatives of titanium. In our work. Indications are that such stability can be obtained as to resist the action of boiling alkali. Thus a whole field of investigation is opened on high molecular weight hydroxyl-bearing substances so Important to industry in coatings, textiles, etc. Investigation of tltanates or esters other than butyl reveals that their reactivity decreases with increasing acidity of the substituent group. Thus acyl tltanates are more stable than phenyl titan&tes which axe more stable than alkyl tltanates of which butyl is now representative as a matter of convenience. Among the alkyl tltanates as we go up the series stability toward hydrolysis increases. If for the reactions you may have in mind you should like to work with tltanates or esters other than butyl we shall be pleased to have you discuss your problem with us. DUP030003566 INTERACTION OF WTTL TWmW WITO_gM~jPgRM6 ORGANIC MATERIAL mrmmv Indications are that any organic compound of high molecular weight and containing hydroxyl or carboxyl groups presents an opportunity for introduction of titanium into the structure through reaction with butyl tltanate. In resins conceived to have a definite structure, up to four resin molecules can apparently be bonded together by a titanium atom. Thus Increased structure of the resin is believed to result as evidenced by 1) increase in viscosity 2) increase In setting rate 3) increase in hardness 4) increase in resistance to water, alkali, softening by oils and solvents with the exception of acetone, glacial acetic acid and some alcohols 5) increase In dielectric strength. All of the above are strong evidence for cross linking of the resin molecules with titanium, particularly the increase in dielectric strength which indicates that more energy is required to separate the resin mole cules which are tied tightly together with titanium. VEGETABLE 0113 The refined unbodied vehicle oils show little or no reactivity , towards butyl tltanate. However, oxidation or "blowing" of diying or semi-drying oils introduces alcohol and acid groups into their molecular structure. Raw oils, of course, contain some acid groups with which - the titanium ester can react. When a sufficient number of such groups are present in an oil, gelation occurs on addition of a small percentage (3 to 5 percent) of butyl titanate. Blending of the tltanate with the oil must be done in a high torque mixer since, otherwise, gelation occurs before a uniform blend is obtained. Castor oil, because of its unique natural alcoholic nature, reacts readily with butyl titanate. We have observed that the addition of ten percent butyl tltanate to castor oil resulted in a marked thickening of the oil While larger additions, thirty to forty percent, gave liquid blends which set to relatively firm, clear, solvent-resistant films. Castor oil-resin combinations have been observed to react similarly to castor oil. DUP030003567  -7~ SOME E3CAMPBES OP REACTIONS Off BPTH, TITAjfrATE WM gim-ffOEMIMG RESITS Alkyda Th following general equation has been postulated for the interaction of butyl titanate and residual hydroxyl and earboxy groups of alkyd resins. -CO CO--OCHg Ci EOH -O-CH2 Ei(GBu)4 / nBuOH Exploration of butyl titanate as an additive to alkyds would seem to be warranted on the basis of securing films having. 1) faster set 2) increased hardness 3) Increased chemical resistance 4) reduced tendency to skinning and wrinkling when thick 5) increased resistance to "sagging" 6) modified body, thixotropic in nature. As an example, for experimental purposes only, as a starting point in exploring the addition of butyl titanate to alkyds, the following results obtained in our laboratory are most interesting. Butyl titanate was carefully added to an alkyd varnish having the following composition, The amount added was 10$ of the varoi3h solids by weight* Alkyd Varnish Fhthalic Anhydride Oil acids TJype of oil Solvent Total non-volatile Viscosity Acid value Acetyl value Driers g60g$ Soya Mineral Spirits 40$ S-T (Gardner-Holdt) 11.4 33,0. 0.1$ Pb) 0.05$ Co) as naphthenate She properties of this varnish compared with properties of the varnish plus butyl titanate were as follows: Alkyd Alkyd plus abed 10$ Butyl Titanate Color Tack-free Sward Booker Hardness 1. 6 days air dry 2, 6 hrs. water ( . 1/2 hr. water ) . 2 hrs. 1$ NaOH (25a) 5. 2 hrs . mineral sppiirriitts (25C.) Viscosity Llght^ yellow hrs. 10 4 (blush) 4 (blush) Very soft Very soft S-T Yellow 2 hrs. 18 16 15 10 12 S-T Because of the complexity of structure of alkyd resins and their many modifications it appears that each type should be considered a specific problem in itself. In the above example gelation did not occur, but where it does the particular solvent system to control it must be worked out selecting volatile alcohols such as butanol to be added to the varnish. DUP030003568  p&enollos Butyl tltanate apparently reacts with phenolic resins through the phenolic hydroxyl groups, le reaction Is postulated thus: o -OH C&, / {Bu O)4L Qa -0- T1(0Bu )4^ / OBuOH CHg High molecular weight of the phenolic plus the probability of threedimensional polymers being formed should lead to highly stable reaction products. It would thus be expected that phenolics modified by reaction with butyl tltanate should provide films having 1) faster set or cure - possibly eliminating the need for baking at elevated temperatures 2) greater resistance to organic solvents, water, acids and alkali 3) higher dielectric strength. As an example of the effect upon the film properties of a simple phenolic resin varnish modified by reaction with butyl tltanate, the following is offered for illustrative purposes only and not as a recommendation for the production of a finished product. Example of Effect of treatment of Phenolic Varnish ___________ with Butyl Tltanate _______ _ Varnish: Bakelite HR254, 20 gal. oil length. 0 bodied linseed oil {50$ n.v. In xylol*driers o.ljTPb, O.0S>$ do on n.v.) Untreated Treated Butyl Tltanate 10$ of solids by weight Air dried films (overnight dry) 2 mils thick Appearance Color Clear light Yellow Clear Dark Red Sward Rocker Hardness 1. diy film 2. 2 hrs. in mineral spirits 3. 2 hrs. in 0.5$ HfeOB Dielectric Strength* (volts/mil/2-mil film) 15 Dissolved (blushed) 1500 41 25 (no blush) 2400 Mandrel Distenslbility* less than 30$ Adhesion (removal wit* sharp tool) Glass Good Steel Good less than 30$ Good Excellent Steel panels An unusual effect noted above is the intense red coloration which is due to the formation of chromophoric phenyl tltanate . fhis color usually characterises phenolics treated with butyl tltanate. DUP030003569 In the above example in which a simple phenolic resin varnish was used, gelation did not occur. Should gelation take place on blending butyl titanate with a phenolic varnish a volatile alcohol as part of the thinner content will suppress the thickening* Another means of re tarding such gelation involves replacement of one or more of the fbutoxy groups of butyl titanate by phenoxy groups or acyl groups such as the acids derived from linseed oil. Vinyls Because most organic soluble vinyl resins sue pictured with free hydroxyl groups distributed along polyethylene chains these hydroxyl groups may be considered to offer points of linkage to butyl titanate. Butyl titanate may be pictured to react according to the following postulated scheme; CHOH n C3S2 / (BuO^EL CHO %n Ti(OBu)^n / nBuOH immediate gelation however may result in vinyl resin solution so tbal.t Is ugua in the solvent systciu butyl titanate to a TM pi?ovIde alcohol As an example, for illustrative purposes only and not as a recommendation for the production of a specific butyl titanate modified vinyl film former, the following is interesting. A medium viscosity type of vinyl resin of the approximate composition; 90 percent vinyl chloride 4 percent vinyl acetate 6 percent vinyl alcohol was dissolved at 10 percent solids in an 80:20-mixture (by weight) of xylol and butanol. To this solution was added 10 percent butyl titanate, based on the weight of vinyl resin, and the solution was stirred until homogeneous Filins cast from the mixture on steel panels and air dried had the following properties: . Vinyl Resin- Vinyl Resin Butyl Titanate Color Sward Rocker Hardness Mandrel Bistensibility Dielectric Strength {volts/mil/2-mil film) Effects of Solvents Water (100C.) Mineral spirits Chloroform Water white 28 3C$ 2500 SI. loss of adhesion Si. softened Dissolved Water white 35 30^ 2900 None None Softened Many vinyls contain only low concentration of free hydrosyl groups and modifications of such resin solutions with butyl titanate does not present a serious gelation problem. Others, such as the formals, acetals and butyrals, because of a large number of free hydroxyl groups per molecule, are not readily modifiable. Such resins, along with maleic acid modified vinyls, usually gel completely on addition of small amounts of butyl titanate to their solutions. In such cases it is usually preferable first to stabilise the butyl titanate by the addition of amines or amino-alcohols. DUP030003570 -10- Cellulosies Cellulosies, the simplest of which Is ethyl cellulose, are examples . of high molecular weight resin alcohols which are film-formers. 3he addition of butyl titanate to very dilute solutions of ethyl cellulose usually causes immediate gelation, Xhis gelation apparently results from reaction of free hydroxyl groups of the ethyl cellulose with the tetrafunctional butyl titanate leading to the cross-linking of up to four eellulosic chains by each titanium atom. ie reaction may be pictured by this postulated scheme? 0 HCOR \/ z . * v. / CH /\ ROCHg-CH HC0- Ti(OBu)4."*n / n BuOH 0 HCOR \/ CH ex Control of the Reaction A method is available wherein the interaction of butyl titanate with ethyl cellulose can be controlled or inhibited until such time as it is desired that gelation occur. Such control is obtained through utilization of the reversibility of the ester interchange reaction. Sms, in the reaction of butyl titanate with ethyl cellulose with the formation of a eellulosic titanate, butanol Is released as a byproduct* Reversal of this gel-forming reaction is accomplished simply by increasing the concentration of alcohol, e.g, butanol, in the solvent system to the point where the alcohol solvent can compete with the ethyl cellulose for the titanium atoms, Choice of the alcohol depends on the solubility characteristics of the ethyl cellulose. The ethylene glycol mono-ethers and the lactate esters have been particularly useful for this purpose. When gel-free blends of butyl titanate and ethyl cellulose are applied as films, the solvent, including the alcohol, evaporates and the titanium Is apparently free to react with the cellulose resulting in rapid gelation and setting. By this means, hard, clear, water-white, solvent resistant films have been obtained from blends containing as much as 80 parts of butyl titanate to 20 parts of ethyl cellulose. Such films have resisted aliphatic and aromatic hydrocarbons and oils, ester's, ethers, chlorinated hydrocarbons, ketones, with the exception of acetone, and boiling water and alkali. through modification with relatively small amounts of butyl titanate (5 to 10 percent) the ethyl cellulose is converted to a thermoset resin and its dielectric strength, i.e. voltage required for breakdown, is increased. All of these properties may be ascribed to the strong attraction of the titanium atom for the eellulosic hydroxyls or if not to the mutual linking . of hydroxyl groups from titanium and the cellulose complex. DUP030003571 /' -i&: , ' :" , i* 4 Following is an example for illustrative purposes only of the modification of ethyl cellulose with butyl tltanate: Component Parts by Weight Ethyl cellulose* 1 3ylol 6 n-Butanol 3 Butyl tltanate 1 t *mediura viscosity type of ethyl cellulose having an ethoxy1 content of approximately 48 percept She ethyl cellulose was dissolved in the solvent, then the butyl tltanate added slowly with stirring. A smooth, clear solution then re sulted having a viscosity only slightly greater than that of the tltanatefree solution. 2he properties of air dried films (thickness 1 to 2 mils) from this composition cast on glass panels are listed below. Color Sward Rocker Hardness Mandrel Distensibility* Dielectric Strength* (volts/fcll/2-mil film) Effect of Solvents on Films Water (lOOoc.) Ig NaOH (25C.) 1$ HC1 (25C.) 1% NaOl (25G.) Mineral spirits Benzene Chloroform Butyl acetate Ethyl Cellulose Water white 60-70 2300 Butyl TitanateEfcfcyl Cellulose Water white 70-80 30$g 2900 None None SI. softened None SI. softened Dissolved Dissolved Dissolved *Steel panels None None Softened None V. SI. softened SI. softened SI. softened, Softened Similar results were obtained on blending butyl tltanate with cellulose acetate and nitrocellulose solutions. DUP030003572 12 Bpoxsr Resins Epoxy resins react with butyl titanate essentially through ester interchange involving secondary alcohol group of the glyceryl ether. The reaction may be postulated, thus: 0-0n o -OCHg-CH-QH a / Ti (0Bu )4 o-o-0- -OCUg-CHO- H (OBu)4.n / BBUQH n Apparently titanium links so tenaciously to the epoxy resin that special systems must be devised to prevent Immediate gelation on addition of butyl titanate to the resin solution. In some cases the use of solvent systems consisting entirely of alcohols, such as the glycol monoethers or diacetone alcohol, are effective in preventing, premature gelation. tern, clear, solvent-resistant films result on modification of such epoxy resins with butyl titanate. Such films air dry with evaporation of the solvent but mild baking schedules usually improve their adhesion and flexibility. The difficulty in controlling the gelation of simple butyl titanateepoxy resin systems lias been overcome by adding certain compounds to butyl titanate in order to increase its stability. Especially useful are amino alcohols, such as triethanolamine, diethanolamine and B-aminoethyl ethanolamine, and polyamines such as ethylene diamine and diethylene triamine. She amine or aminoalcohol is simply added to the butyl titanate. Butyl titanate thus stabilized appears to offer particular advantages not only over butyl titanate alone but also over conventional amino-type catalysts used in the curing of epoxy resins. The reduced activity effectively depresses gelation which would occur with the simple butyl titanate and permits incorporation of titanium into the resin structure under controllable conditions. Moreover the presence of the titanate reduces the activity of the amine which normally catalyzes the curing of the resin through reaction with epoxy groups. Marked increases in the "pot life" of the resin solution results because the titanate reduces premature gelation in the container. DUP030003573 "13" Following is an example of a composition found to be of interest in our work. Relatively fast cure plus the properties of epoxy resins such as adhesion, flexibility and alkali and solvent resistance were observed. , When applied to steel panels and oven cured at 150oc. for 30 minutes the films were lighter In color than those usually obtained from epoxy resins cured with primary polyamines. Parts Tty Weight Epon Resin 1007 32 Diacetone alcohol Cellosolve Butyl titanate 32 31 2.5 B-aminoethylethanolamine 2.5 Pereas gelation occured in a week when the tltanate was omitted from the above formulation, the complete varnish did not gel in six months although there was a gradual increase in viscosity . Compositions along this line should offer definite possibilities for increasing the npot life" of the resin solution. Oil modified epoxy resins react with butyl titanate to a lesser extent than do the pure resins. However, the varnishes contain apparently a ` sufficient number of free hydroxyl groups to permit cross linking of the resin molecules by titanium atoms. Eie results of such cross linking are 1) faster curing. 2) firmer fils, 3) improved resistance to organic and agueous solvents and 4) increased dielectric strength. An epoxy resin varnish consisting of 40 percent Epon Resin 1004, 10 percent WG rosin and 50 percent linseed oil fatty acids (0.1 percent Fb said 0.05 percent Co driers) and thinned to 50 percent non-volatile in xylol was modified with 10 percent by weight butyl titanate. Properties of films formed from the varnish, both with and without the titanate, are shown in the following table which is presented only as an illustrative example for ex perimental purposes as a starting point for the modification of an epoxy resin varnish with butyl titanate. Color Set to touch (air toy ) Sward Rocker Hardness 48 hr. air dry 24 hr. water immersion Epoxy Varnish light Yellow 4 hrs. 12 8 (temporary blush) Epoxy Varnish plus IO& Butyl Titanate Yellow 1/2 hr . ^ 26 18 Mandrel distensibillty >30 percent >30 percent . Dielectric strength (volts/mil/2-mil film) 48 hr . air dry 24 hr, water immersion 2300 1200 2800 2000 DUP030003574 * mmh mamas a s y e h ic d s o r c a b r x b b m c o at xho s Butyl titanate when applied as. a film and exposed to the air at room temperature, hydrolyzes and solidifies. She released butanol evaporates ` leaving a film which, at first transparent breaks up into a friable yellowish powder with complete loss of adherence to the substrate. Work in Australia (1) early indicated that butyl titanate when pigmented with a leafing type pigment such as aluminum powder would form a continuous film on air drying and this film could be heated to bum off the organic matter. Various factors affect the performance of such films applied to steel surfaces > particularly the ratio of aluminum to butyl titanate and the preparation of the surface. Many of these factors have been discussed by Hancock and Sidlow (5 ) . The outstanding property of butyl titanate - aluminum coatings thus far is resistance to high temperatures. The maximum temperature which these coatings will withstand on steel and still provide protection against ordinary atmospheric corrosion seems to be governed by the melting point of the aluminum pigment - about 120QF, Of course, it must be recognized that all organic matter is removed in these coatings by burning off, so that what remains is a coating of aluminum and titanium dioxide in extremely fine particle size. For practical purposes a temperature of 1000F. is the maximum to which such coatings should be subjected. In our work a starting point formula as follows has given promise as the basis for further work on this type of paints Parts by Weight Butyl titanate Aluminum power (Alcoa P-22 or equivalent) Mineral spirits 5 4 4 To improve adhesion, one part of aluminum powder may, be replaced by one part of zinc dust (Hew Jersey Zinc Co. #22 or equivalent), Preparation of Iron or Steel Surfaces In our work we often found it necessary to heat the metai to scme YCo^F. to degas it, then clean thoroughly by wire brushing and sanding followed by a wash with 10$ nickel sulfate. Generally, thorough cleaning of the surface is recommended particularly to remove any mill scale which can be harmful when detached.; Flame-cleaning (8) has been recommended followed by wire brushing. Applications Spraying is generally indicated because brushing is generally difficult and productive or uneven films due to. gelling. "Ikying" or "Curing": After application about 1/2 hour air drying time is allowed' followed by heating usually at not lower than 750F, to remove all organic matter. . Some Precautions to be taken with this Type of Paints Alcoholic and acidic . substances are generally avoided in formulating these paints because of generation of gas in the container upon storage leading to exploding con tainers, Of course, butyl titanate must not be exposed to moisture during bSHullllg DUP030003575 4 -15- REFERENCES (1) Kraitzer, MeTaggart and Winter: The Preparation and Utilization of Esters of Ortho Titanic Acid., Minerals Utilization Section, Rote No. 6, December 1947# Council for Scientific and Industrial Research, Division of Industrial Chemistry (Australia). (2) Kronstein; Paint and yarnish Production, 1950, No, 8 10-15, 20-21 (3) Bischoff and Adkins - J.A.C.S. (1924) 46, 257 (4) Post, H.W, - The Chemistry of the Aliphatic Ortho-esters, Rheinhold Publishing Co., N.Y., 1943 (5) Hancock and Sidlow, J.O.C.C.A., 35, No. 379# 28-39 (6) Speer, J. Org. Chem. aA, 655 (1349) (7) Cullinane, Chard, Price and Milliard; J. Soc. Chem. Did. 6<? S 38 (1950) (8) Barksdale, Titanium, The Ronald Press Company, New York DUP030003576