Document dwkvxp5ML3jzL7Z29QG7EDXR

ORGANIC CHEMICALS DIVISION ESE St. Louis Research Report No. 2488 FINAL REPORT ON APPLICATION WORK ON PRESE*N**T* PLASTICIZERS-1959-PART I Job No. 2-02-750.01-5793-1 March 21, I960 Written by: N. W. Touchette r~ Monsanto ST. LOUIS, MO. DSW 622149 STLCOPCB4096182 Monsanto Chemical CompanyOrganic Chemicals Division St. Louis Research Department DO \70 St. Louis Research Report No. 2488 PINAL REPORT ON APPLICATION WORK ON PRESENT PLASTICIZERS-1959-PART I **** Job No. 2-02-750.01-3793-1 March 21, i960 Written by: N. W. Touchette Work Done by: J. R. Darby N. W. Touchette L. R. Wangler DSW 622150 STLCOPCB4096183 DISTRIBUTION 1. Pile 2. J. R. Darby 3. M. C. Throdahl - Pile 4. Duplicate File 5. Central Technical Files 6. N. W. Touchette 7. H. S. Bergen 8. W. B. Hicks 9. Extra Extra This report contains confidential information which is the property of the Monsanto Chemical Company and which shall be disclosed only to duly authorized persons. The recipient is held accountable for the filing and safe custody of the report which must be returned upon demand. DSW 622151 STLCOPCB4096184 TABLE OF CONTENTS Page I. INTRODUCTION 1 II. SUMMARY 1 III. CONCLUSIONS 1 IV. RECOMMENDATIONS V. PATENT STATUS 3 5 VI. REFERENCES 4 VII. EXPERIMENTAL WORK 4 A. Color Stability Heat Tests on DOP B. Extended Volatility Test for Patent Purposes C. Polyolefins 4 5 5 1. Light Stability of Polyethylene Containing Antioxidants 2. Flameproofing Low-Density Polyethylene 3. Flameproofing High-Density Polyethylene Polypropylene D. Stifflex Curves on S-409, Monoplex S-90 and di(2-ethylhexyl glycolyl) phthalate E. Plasticizers for Nylon F. Water Dispersion Floor Polishes 1. Screening Tests 2. Emulsification of Plasticizers 3. Gel Test on Polyelectrolyte 4. Preparation of Plasticized Polystyrene Emulsion 5. Evaluation of Complete Polish Formulation 6. Industry Test Program G. Non-Fogging Plasticizer for Automotive Upholstery 1. Methods Employed in the Industry 2. Monsanto Infrared Test 3- Contamination by Glycerine 4. Infra-red Test Results 5. Numerical Rating of Fogging 6. Oil Immersion Test Procedure 7. Temperature, Plasticizer, Concentration and Time Effects Upon Fogging 8. Test Results on Monsanto and Competitive Plasticizers 9. Testing of Plasticizers and Resin per se 5 6 9 9 12 12 12 15 15 15 15 15 16 16 17 17 18 18 19 22 24 24 DSW 622152 STLCOPCB4096185 TABLE OF CONTENTS - Cont Page 10. Fog Value of DOP From Several Manufacturers 11. Evaluation of Various Samples of S-409 from Plant Production 12. Evaluation of Chrysler and Ford Specimens 13* Ford's Fade-Ometer Test 14. Ford Program 15 Evaluation of Stabilizers and Lubricants 16. Composition of Santicizer 169 (X-6060) 17. ADM's Admex 747 15. Study of the Ford Test 19* Fogging Characteristics of Mixtures of S-169 and Admex 747 20. Fogging as a Function of Resin . 21. Fogging Tests on Toscony Fabrics' Samples 22. Fog Value on Decyl Tridecyl Phthalate 25. Fogging as Related to Carbon Black, Bisphenol A, HB-40 and Volatility - VIII. ACKNOWLEDGMENT . IX. APPENDIX 27 28 29 30 50 54 54 55 56 38 40 42 43 44 45 45 DSW 622153 STLCOPCB4096186 I. INTRODUCTION Application work on existing plasticizers by the Plasticizer Application Group is a perennial program for maintaining and advancing Monsanto's position in the plasticizer field. Primarily, present products are tested for adaptation to new and varied applications. Secondly, new exploratory plastici zers which show promise in the screening evaluation are given a more intensive examination to determine possible marketability. Thirdly, direct comparison of Monsanto plas ticizers with specific competitive products help determine a plan of action to meet this competition. Finally, the test ing of samples for quality control as well as process modifi cation research Insures that Monsanto's position in the plas ticizer Industry is advanced. Another segment of research on the specialized area of acrylic resin plasticizer in this general area of application work on present plasticizers will be reported as Part II on this job number. II. SUMMARY . This report covers a variety of problems concerning the intensive evaluation of Monsanto's plasticizers, both commercial and potential commercial samples in present and projected uses. Color stability upon heating of variously treated DOP samples was completed. The Patent Department requested extended volatility tests on several TEA prepared esters. Several projects on polyolefins including light stability studies and flameproofing of polyethylene and polypropylene were completed. Stifflex curves on several plasticizers were run. An attempt was made to study plasticizers for nylon. The use of Monsanto plasticizers in polystyrene-based water dispersion floor polishes was investigated. The problem of non-fogging plasticizers for the automotive trade was studied. Ill. CONCLUSIONS The following conclusions were drawn from the details of the experimental work reported here. 1. Thermally esterified DOP has greatly improved color stability after high temperature heating and is nearly equiva lent to competitive material. DSW 622154 STLCOPCB4096187 2. 2. Dl(tridecyl glycolyl) phthalate prepared by the TEA process was found to have low volatility upon extended test ing. 3. Polyethylene containing Santonox R as an antioxidant was found to discolor upon exposure to UV light. Continued exposure causes the yellow color to discharge. Several other antioxidants, Santowhite Powder Refined and di-t-butyl-p- cresol, offered antioxidant protection without the problem of yellowing upon UV light exposure. Low-density polyethylene was successfully flameproofed using combinations of Aroclor 5460 and antimony oxide. The Aroclor 5460 offered an advantage over Chlorowax 70 in this application through better retention of physical properties of the flameproofed composition. Aroclor 5460 and antimony oxide could not be used to flameproof high-density polyethylene (Marlex 58) or poly propylene (Profax). Chlorowax JO was not successful withrMar- lex 50, however, a self-extinguishing formulation was obtained with Profax. - 4. The slope of the stifflex curves for S-409, Monoplex S-90 and di(2-ethylhexyl glycolyl) phthalate are very similar in nature. 5. Based upon preliminary work, it appears that the only feasible way to plasticize nylon is by the extrusion technique in which the predried resin pellets are wet with the plasti cizer prior to feeding to the extruder. 6. Santicizer 117 (methyl diphenyl phosphate) and dimethyl phthalate were found to be plasticizers for polystyrene-based water dispersion in laboratory tests. However, when presented to the industry both plasticizers were rejected due to poor leveling characteristics of S-117 and poor removabilitycf di methyl phthalate. Development Department contacts indicated that the formulation used here gave satisfactory performance but the industry has changed to other formulations which are more difficult to level. 7. Santicizer I69 has passed the Ford Fogging Test in a number of colors. Failure resulted when the samples were black and heavy, shades of green and blue. In these applications, Admex J^J, selling at 46 cents a pound, might be useful. DSW 622155 ! STLCOPCB4096188 3. The fogging characteristics of a vinyl composition is not only related to the plasticizer system but also to the resin type, stabilizer and lubricant used in the formula tion. The resin,stabilizer and lubricant system become increasingly Important when used with a low-fogging plasticizer. The Monsanto oil immersion test developed in our labora tory to give accurate and reproducible temperature control can be used to test the various components per se which make up the total formulation. The resin because of the high concentration is very critical; Opalon resins are fair with regard to fogging. Other resins vary; for instance, Geon 103EP is extremely good while Geonl21 fogs heavily. Based strictly on low fogging characteristics, the following formulation appears best: GeonlO^EP or Marvinol VR-50, Santicizer 169 or Admex 7^7> Mark WS and Calcium Stearate. The fogging characteristics of S-4-09 have improved from a fog value of about 20 to about 12. However, these are still higher than Paraplex G-5^ at 6. "~IV. RECOMMENDATIONS It is highly recommended that this type of supporting application work on our present plasticizers be continued and that new and novel uses for Monsanto's present plasticizers continue to be explored. In specific areas it is recommended that further work be done on the problem of plasticizers for polystyrene floor polishes. This work should not be restricted to attempts to improve the position of S-117 and di-methyl phthalate but the area of new compounds should also be investigated. In partic ular compounds of high water sensitivity should be prepared and evaluated. It is recommended that close liaison be maintained with the Sales Department in the use of S-I69 in the automotive trade. V. PATENT STATUS One disclosure (No. 2172) on S-117 in floor polish was filed from the Plasticizer Application Group as the result of the work reported here. DSW 622156 STLCOPCB4096189 4. VI. REFERENCES The Final Report on Job No. 2-02-750.01-5591-II, "Appli cation Work on Present Plasticizers" by N. W. Touchette, (SL Research Report No. 2271, December 25, 1958) contains references to all prior reports concerning application work on present plasticizers. Previous work on the fogging problem is contained in St. Louis Research Report No. 2276 on Plasticizer Test Method Development - Part I, Job No. 2-02-750.01-5598-1, December 1, 1958 by N. W. Touchette. It is anticipated that one additional part of this report will be issued on the work done in plasticizing acrylic lacquers which Is a specialized area of research. VII. EXPERIMENTAL WORK A. Color Stability Heat Tests on POP A series of specially prepared and/or treated D0P samples were tested for color development during per se heating at 205C. for 2 hours. The results In Table I show that thermally esterified DOP is equivalent to Carbide's D0P and nearly equivalent to Eastman's product and to distilled and rewashed DOP (the only other means In the past to upgrade the color stability). TABLE I Color Stability of DOP During Oven Exposure (110 ml of DOP exposed inair circulating oven at 205*C. for two hours) APHA Color Values Eastman's DOP Carbide and Carbon's DOP Monsanto's standard DOP DOP, Laboratory prepared, H2SO4 catalyzed DOP, Laboratory prepared, TSA catalyzed DOP, Esterified with MIcrocel C DOP, Thermally esterified DOP, ozone treated DOP, Distilled and rewashed 15 50 550 475-500 250 125 45 550-575 35-40/ DSW 622157 STLCOPCB4096190 5. B. Extended Volatility Test for Patent Purposes The Patent Department requested additional tests on the volatility of several monomeric esters prepared by the TEA process and identified as follows: di(tridecyl glycolyl) phthalate (SL-16588), hexyl phthalyl hexyl glycolate (SL-16591), butyl 4-/bls(2-ethylhexoxy)phosphinyl_7butyl phthalate (SL-I6592), and tridecyl phthalyl tridecyl glycolate (SL-I6595). The results shown in Table 2 indicate the tridecyl derivative to be low in volatility. SL-I6588 SL-16591 SL-16592 SL-16595 Table 2 Extended Volatility Test 1 Day # Plasticizer Loss 2 Days 6 Day; 1.8 2.3 2.8 4.6 1.9 3.1 1.1 1.5 3-2 1Q.0 6.1 2.1 C. Polyolefins 1. Light Stability of Polyethylene Containing Antioxidants U. S. Industrial Chemicals reported poor light stability of polyethylene (PE) containing Santonox R. The problem was thought to be caused by high processing tempera tures and laboratory work was undertaken to duplicate and explain the problem. Petrothene 205, supplied by USI, was roll milled at two levels of concentration with three antioxidants; Santonox R, Santowhlte Powder Refined and DBPC. A portion of each sample was exposed in an air circulating oven at 250 for 10 minutes. These conditions caused significant yellowing of the control PE. The heat treated specimens as well as unheated controls were exposed in the Fadeometer, Weatherometer and window. The light stability test in the Fadeometer was stopped after 500 hours and the Weatherometer after 600 hours. Results in each unit were comparable. DSW 622158 STLCOPCB4096191 6. The color generated In the heat cycle in the con trol PE was almost completely discharged in the first 50 hours of exposure. Thereafter, very little change took place. In the samples containing 0.02# Santonox R, the color formed during heating was not as strong and appears to be completely discharged again in 50 hours of light exposure. However, with 0.1# Santonox R, the first 50 hours of exposure caused a yellowing in both the control and heated PE. This yellow ing diminished with further exposure and had completely gone by 500 hours. Santowhite Powder Refined and DEPC were similar in their action In that the color developed upon heat treat ment was less than the control and some bleaching action took place upon light exposure. Window exposure did not show significant differences between any of the samples. - The above results confirm the fact that Santonox R treated PE is light sensitive regardless of previous heat . ' history and that continued exposure to UV light bleaches this color. The use of either Santowhite Powder Refined or di-t-butyl-p-cresol (DBPC) gave protection during heat treat ment without the problem of darkening upon light exposure. 2. Flameproofing Low-Density Polyethylene The evaluation of Aroclor 5^60 as a flameproofing agent for low-density Polyethylene (DYNH) and comparison with Chlorowax 70 In this application wa3 completed. The results indicated that at low concentrations (20#) the Chlorowax is a better flaraeprooflng agent. However, the ten sile strength is significantly reduced. At a higher con centration (50#), the flameproofness characteristics of the two are similar but the tensile reduction of Chlorowaxmodified material is very evident. The addition of antimony oxide does not alter the above results. The heat stability of the Chlorowax-modified samples was found to be very poor. The values of Melt Index, tensile properties and flameproof tests are given in Table 5* The Melt Index and # Memory values were determined using Condition E of ASIM 12J8-57T except that In all cases 9 grams of material was charged into the cylinder. For low melt index materials, about half the charge was extruded by hand pressure after 3 minutes. DSW 622159 STLCOPCB4096192 j, 7. The changes in Melt Index values with increasing amounts of additive are to be expected. The $ Memory values do not show large changes except for the low value for 50 DYNH, 30 Aroclor 5460 and 20 antimony oxide. This particular mix was quite fluid as evidenced by the Melt Index and thus the # Memory probably does not mean too much. Tensile properties were determined on mlnature specimens with the Instron with a Jaw speed of 10 Inches a minute. The yield strength shows little relationship to the amount or kind of additive. Elongation and tensile decrease with increasing amounts of additive with the Chlorowax causing the greatest changes. The burning tests were conducted according to the procedure given in St. Louis Research Report No. 1727. In this test, strips of polyethylene, l,r x 4" with lines scribed l/2w from each end, are hung in an asbestos cylinder 2-1/2" diameter x 5,r length. A bunsen flame, l,r high, is-- used to ignite the specimen. When the flame reaches the first scribed mark, the bunsen flame is removed and the stopwatchstarted. The time to flame-out or burning to the second scribe mark is measured. From the charred area when the sample is self-extinguishing a burning rate in square inches a minute can be calculated. As shown in the table, all specimens except two containing Aroclor 5460 were self-extinguishing, however, the addition of the Aroclor did decrease the burning rate by half. The fact that a particular sample is self-extinguishing does not mean that the specimen is unaffected during the test. In some cases severe distortion plus melting took place. Heat stability tests run in an air circulating oven at 190C. show the Aroclor-modified polyethylene samples to have better heat stability than the Chlorowax samples. Earlier evidence of the poorer stability of the Chlorowax was noted in the molding operation where the Chlorowax samples darkened appreciably. Since this work was completed we have been in formed that an article has appeared concerning the use of Chlorowax 70 in PE. The addition of 3*3$ butyl rubber to the flameproofed compositions supposedly overcomes the losses of elongation and tensile properties. This lead has not been explored in our laboratories. The ultimate utility of the Aroclor-Modifled PE is questionable since the composition really does not resemble PE in physical properties. It is possible that other compositions could equally fill the requirements Intended for modified PE. DSW 622160 STLCOPCB4096193 8. TABLE 3 PROPERTIES OF LOW-DENSITY POLYETHYLENE (DYNH) MODIFIED WITH AROCLOR 54b0 AND CHLOROWAX 70 Control (DYNH) 80 DYNH 20 Aroclor 5460 80 DYNH 20 Chlorowax 70 Melt % In Mem dex1 2 3 ory l.$6 Burning Tests Self Tensile Properties2 Rate Extln *----------- Ten (in?/ Drips guish ~rmElong sile Yield min.) Flame ing 2l3D" "TTl No 5.86 59-0 690 2020 1320 3.0 Yes No 5.9 61.5 583 1640 1450 _3 Yes Yes 70 DYNH 50 Aroclor 5460 11.2 51.5 647 1850 1320 _3 Yes Yes 70 DYNH 50 Chlorowax 70 80 DYNH 10 Aroclor 5460 10 Antimony Oxide 80 DYNH 10 Chlorowax 70 10 Antimony Oxide 50 DYNH 30 Aroclor 5460 20 Antimony Oxide 50 DYNH 30 Chlorowax 70 20 Antimony Oxide 10.5 67.2 130 1175 1195 -3 Yes Yes 3-8 57-2 650 1895 1300 4.0 Yes No 3.6 39.0 655 1905 1445 _3 Yes Yes 19.1 15.0 18.2 63.9 270 1185 1570 Too Brittle for Test Under These Conditions _3 Yes Yes 9Drips no -3 flame Yes 1 Procedure "A" (l90C./2l60 grams) 2 Jaw separation - l/2", speed 10 Inches a minute 3 Did not support flame after removal of burner. DSW 622161 STLCOPCB4096194 9. 5* Flameproofing Hlgh-Denslty Polyethylene Poly propylene The addition of Aroclors to both polypropylene (Profax) and linear polyethylene (Marlex 50) did not cause a significant reduction in the burning rate as had been pre viously experienced with low-density polyethylene. Samples were prepared using Aroclor 5460 at 20, 50 and 40$ plus several combinations of Aroclor 5460 and antimony oxide. When tested for flameproofness using the asbestos chimney test, the Profax-Aroclor 5460-antimony oxide (50/50/20) combination showed a 40$ reduction in burning rate but the sample still dripped flame. Low density polyethylene in this formulation was self-extinguishing. When Chlorowax 70 .was substituted for Aroclor 5460, the resulting formulation was self-extinguishing. Furthermore, substitution of Aroclor 1268 gave similar results to the Aroclor 5460. The results in Marlex 50 were much the same except that not even Chlorowax 70 produced a self-extinguishing for mulation. The reduction in burning rate was less than 10$.- Due to the poor showing with regard to flame proofing exhibited by the Aroclors, no attempt was made to ob tain physical properties of the various formulations. However, it is estimated that the properties were greatly reduced. D. Stifflex Curves on S-409* Monoplex S-90 and dl(2-ethylhexyl glycolyl) phthalate Stlfflex curves were determined on S-409, Monoplex S-90 and dl-2-ethylhexyl glycolyl phthalate at a concentration of 100 phr in Opalon 500 using the Tinius Olsen Flex Tester. The pro cedure (AS1M D1045-51) used nominal 65 mil specimen which were cooled below -60C.for the initial reading. The angle of deflec tion was obtained at five degree intervals after conditioning the specimen for three minutes. The torque was changed to maintain a deflection angle between 20 and 200 degrees of arc. From the torque and deflection angle, the modulus of rigidity was calculated and plotted on semi-log paper vs. temperature to give the range from -60 to +15C. as shown in Figure 1. The curves for the three plasticizers are very similar in slope and displaced only about 5-7C. DSW 622162 STLCOPCB4096195 MODULUS OF R IG ID IT Y PS I IN THOUSANDS)( 10. Figure 1. Stiffness versus temperature of poly (vinyl chloride) plasticized with 100 phr S-409, Monoplex S-90 & di-2-ethylhexyl glycolyl phthalate. DSW 622163 STLCOPCB4096196 11. E. Plasticizers for Nylon The technology of nylon resins has advanced to the stage where previous evaluations of Monsanto plasticizers In nylon can no longer be applied to the present resin, type 6/6. A program was undertaken to reevaluate various plasticizers in duPont's Zytel 101. Attempts to use the steam heated roll mill were unsuccess ful due to insufficient temperature to soften the resin pellets. Addition of plasticizer to the pellets caused additional problems due to increased lubricity. The use of the oil heated roll mill at 500F. resulted in sheet formation but discoloration took place quickly probably due to oxidation. Plasticizer addition had no effect upon the discoloration. Micro-techniques of hot plate milling developed by Dr. Sears also resulted in extreme discoloration. One test run was made at Dayton using their l" vent extruder on Zytel 101 plus 2# Santlclzer 8. In this test the--1 pellets were wet with the plasticizer prior to extrusion. No difficulty was encountered in feeding during the run. However, the stock bubbled excessively at both the vent and the die such that a suitable product could not be obtained. The bubbling was believed a result of high moisture- content of the resin since nylon is fairly hydros<Sb#ic and the resin had not been predried. Time did not permit another run to be made. *- ...... It Is expected that extrusion is the proper way to handle nylon resin. It also appears that mixing in the extruder in either one or two passes would be satisfactory. TABLE 4 Evaluation of Plasticizers in Floor Polishes (Plasticized U-2003 - 31*7; Polyethylene emulsion - 11.7; Durez 15546 Solution 7-0) Plasticizer Leveling Glass S-151 DIDA S-160 Methyl benzyl phthalate Butyl cellosolve dicresyl phosphate Poor Poor Good Good Good t --- Good Good Good F . Water Dispersion Floor Polishes DSVV 622i64 1. Screening Tests Previous work in this area (St. Louis Research Report No. 1933) had indicated that S-160 and S-l4l could perform satisfactorily in the field of water dispersed floor polishes STLCOPCB4096197 12. based on polystyrene latex. However, reports from the trade Indi cated that these plasticizers used singly or In combination reduced the gloss of the floor polish. This one property loss could not be tolerated by the Industry. Work was continued evaluating various plasticizers in a two-step program. The first was a test for compatibility with the polystyrene resin by mixing 6 parts of plasticizer and 100 parts cold resin, diluting with 200 parts water and allowing to stand 24 hours. The plasticizers which formed two layers and thus were in compatible after this time period were Santolite MS, S-8, M-17, and M-17/Santolite MHP (1.7/1). The plasticized resin was then compounded with a leveling agent and wax emulsion for tests of the finished formulation for gloss and leveling. Table 4 records the results on additional plasticizers in total floor polish formulations. 2. Emulsification of Plasticizers The apparent limited compatibility of S-M-17 and S-'S could have possibly resulted from incomplete mixing during addition to the polystyrene dispersion. It was thought this problem could be overcome by pre-emulsification of the plasticizer prior to the mixing operation. Limited work was done on attempts to emulsify using oleic acid-morpholine systems. All samples prepared separated into two distinct layers after standing overnight but could be redis persed by shaking. No further work was performed in this area. 3. Qel Test on Polyelectrolyte Based on Springfield's recommendation, a gel test was run using the plasticizer and polyelectrolyte which is added to the polystyrene latex. This suggestion was based on their belief that the plasticization of the polyelectrolyte was more critical than plasticization of the polystyrene. A test similar to the polystyrene gel test was run in which 5 grams of the polyelectrolyte (DX-873-styrene maleic anhy dride copolymer half butylated) are mixed at room temperature with 10 grams of plasticizer. Observations on the resulting mixture are made after 24 hours. It was found that three conditions prevailed at this time: clear gel, cloudy gel and two layers. The clear gel Indicated a swelling type plasticizer and one which would be com patible. Cloudy gel Indicated limited swelling and compatibility while two layer formation was the result of non-swelling and gross incompatibility. It was determined that the plasticizers which formed clear gels were worthy of further consideration as floor polish plasticizers. The,, results of evaluation of various plas ticizers by the gel test are given in Table 5* DSW 622165 STLCOPCB4096198 13- TABLE 5 Plasticizer Evaulatlon for Floor Polishes by the Gel Test on the Polyelectrolyte ' Swelling Type (Clear Gel) Methyl Diphenyl Phosphate Dimethyl Phenyl Phosphate Ethyl Diphenyl Phosphate KP-140 P-600 Methox Dimethyl Phthalate Tributyl Phosphate Diethylene Glycol Dibutyl Phenyl Phosphate DEG /S-8 (1:1) Swelling (Cloudy) Triacetin Butyl Cellosolve Diphenyl Phosphate (S-143) Benzyl Cresyl Phthalate S-8 S-l4l/KP-l40 (1:1) S-131-A-15 Diethyl (1-Hydroxypropyl) Phosphonate Diphenyl Phosphite Butyl Diphenyl Phosphate DEG/S-141 (1:1) Methyl Benzyl Phthalate DEG/Methyl Benzyl Phthalate Non-Swelling (Two Layer) DEP, DBP S-160, S-141 S-151, M-17, B-16 TOP, S-140, S-191, DIDA Aroclor, 1221, 1232, HB-40 CC-35, TPP, S-409 Di(2EH glycolyl) Phthalate DSW 622166 STLCOPCB4096199 14. It will be noted that a number of plasticizers which formed clear gels are those recommended in the trade literature as plasticizers for floor polishes. This fact enhances the reliability of the test. Several potential plasticizers were indicated: dimethyl phthalate, methyl and ethyl diphenyl phosphate and dimethyl and dibutyl phenyl phosphate. The gel test was extended for use with other components of the floor polish. The polystyrene emulsion (U-2003) was carefully air dried to duplicate actual use conditions and ground by hand into a fine light yellow crystalline powder. A few crystals of the ground U-2003 were added to various plasticizers on watch glasses. After standing 24 hours noticeable degrees of change had taken place as shown in Table 6. None of these plasticizers appear to be exceptional plasticizers for the polystyrene. The compatibility with the wax was determined in the __ same manner as the gel test (l gram wax to 10 grams plasticizer) except the containers were heated to melt the wax. The results * shown in Table 7 indicate a decided advantage in favor of ' KP-140 as a plasticizer for the wax. TABLE 6 Compatibility of Various Plasticizers with Dried Polystyrene Emulsion (U-2003) Plasticizer Resin Appearance After 24 Hours KP-140 DIDA MDPP DMP DBP S-l60 S-141 S-143 Slightly swollen. white No change Clear, with some lumps Clear, with some lumps Clear, with some lumps Partially clear Overall cloudy Overall cloudy TABLE 7 Compatibility with Wax (Bareco Petunaula D) (Heated and Stirred Together and Allowed To flool) KP-140 DMP MDPP S-160 S-143 Homogeneous, soft mixture Two layers Two layers Homogeneous, hard mixtures upon stirring) Grainy Mixture (became grainy DSW 622167 STLCOPCB4096200 15. KP-140 and MDPP were both tested by the gel test with polystyrene (Luster 601 Powder) and the leveling agent (Shanco L-1090). Both plasticizers reacted similarly and produced either a clear gel with polystyrene or a clear solu tion with Shanco L-1090. 4. Preparation of Plasticized Polystyrene Emulsion A series of plasticizers were Incorporated in U-2003 at the 6 point level as previously described. The plasticizer . systems evaluated were: KP-140, MDPP, KP-140/S-160 (l/l), MDPP/ S-160 (1/1), KP-140/DBP (1/1), MDPP/DBP (l/l), S-151 and DMP. After standing overnight, the above solutions were compounded with the leveling agent (RSS-0149L) and coated onto black rubber floor tile. After drying very little difference could be noted except that dimethyl phthalate gave better gloss. The difference between KP-140, MDPP and S-151 which was noted in the gel test could not be detected here. __ 5. Evaluation of Complete Polish Formulation The plasticized 11-2003 containing KP-140, MDPP and DMP was compounded into a complete polish formulation as follows: Plasticized U-2003 Polyethylene emulsion (MCT-0804-2) Durez 13546 Solution (RS-C3C-1A) - 51-7 - 11,7 - J,0 These were evaluated on black rubber floor tile and oven stability. The properties on floor tile appear comparable except for dimethyl phthalate which gave noticeably better gloss and depth. In oven stability tests, DMP gelled in three weeks while KP-140 and MDPP were satisfactory for two months at which time the test was stopped. 6. Industry Test Program Both DMP and MDPP (now called S-117) were sent to selected customers for evaluation. Reports from Johnson, Slmoniz,Franklin Research and UBS all stated that S-117 was comparable to KP-140 in all properties except leveling. This property as we have stated before is 'extremely critical with the wax people. Our contact groups reviewed the formulation we used with Simoniz and were told it was satisfactory. DSW 622168 STLCOPCB4096201 16. Following receipt of these results, additional samples of polish were prepared as given in Section 5 using S-117 and KP-140. These were evaluated on black rubber tile, green asphalt tile, tan vinyl asbestos tile and yellow flexible vinyl tile. Neither formulation would level on the flexible tile. However, on the remaining tile, both polishes looked comparable. In an effort to detemine the reason our results did not correlate with other laboratory samples of the above polishes and the formulations were sent to UBS Chemical for their evaluation. They replied that in the two polishes submltted, leveling and other properties were comparable. However, UBS stated that almost any plasticizer would perform satisfac torily in this formulation and they suggested several formulations for use in evaluating plasticizers. No further work has been done to check out this latest information from UBS. Since the reports from all customers who evaluated S-117 are much the same, we feel certain the cause of the trouble has been explained. - G. Non-Fogging Plasticizer for Automotive Upholstery During the summer of 1958* the vinyl coated fabric indus try received complaints from their customers in the automotive trade that vinyl coatings in the cars were causing "fogging". This fog appears as a condensation or haziness upon the windshields after cars are exposed in a closed condition to the hot summer sun. The condensate has been described as sticky, tacky and difficult to remove. The automotive companies were quick to conclude that vinyl coatings in upholstery and crash pads were at fault. x One of the major reasons for this belief was the simultaneous appearance of the fogging problem and a large increase in the use of vinyl coating for automotive interiors. However, the coaters were not fully convinced that the vinyl coatings were the trouble-makers. Another serious drawback to the investigation of the problem resulted from the random appearance of the fog. As far as could be discovered there was no pattern to the fogging nor could the fogging be connected with any particular auto type or region of the country. 1. Methods Employed in the Industry Various methods were reported from the tra4e as duplicating the heating conditions to cause fogging. The method receiving widest apparent usage was the Chrysler test. Beakers containing the black vinyl specimens are placed on a turntable rotating at 2-3 rpm and covered with plate glass. Infra-red heat lamps are positioned above the beakers to give a temperature of 190 F. as measured by a thermocouple embedded in the vinyl sample. DSW 622169 STLCOPCB4096202 17. After 16 hours the plate glass Is removed and examined for fogging. This basic method was modified by use of flasks or petri dishes in place of beakers but no change of major impor tance was noted. 2. Monsanto Infrared Test The initial laboratory test here used 1-liter Erlenmeyer flasks placed on a Rotosho turntable which was covered with black cardboard. The speed of the turntable was 2-3 revolutions a minute. Watchglass covers were used. The vinyl samples containing carbon black were 3-inch disks cut from 40-mil press polished sheets. A thermocouple was embedded in one sample and connected to a potentiometer for temperature measurement. The flasks were rotated under two 375-watt infra-red lamps for 16 hours maintaining a sample temperature of 19.0-195*1? The amount of fogging on the watch- glass cover was evaluated visually. --: In the early experiments all vinyl specimens were plasticized to equal Shore "A" hardness. To facilitate sample preparation a master batch of the dry ingredients was mixed in the following proportions: Opalon 300 Dyphos DS-207 Kosmos BB - 100 parts - 3 parts - 0.6 parts - 1.5 parts The individual plasticizers and masterbatch were hand mixed, fluxed on the two-roll mill and press polished. 3. Contamination by Glycerine The first results obtained by the above method did not distinguish between various plasticizers. That is, all plasticizers gave equal and heavy fogging. By replacing the flasks with tall Berzelius beakers and using 4-1/2" squares of plate glass, the fog was condensed on the glass. The fog was removed from the glass plate by scraping with a razor blade, for sub sequent I.R. analysis. The fog from various plasticizers and resins was analyzed and in each case the fog was found to be predominately glycerine. The plasticizers per se and the individual dry in gredients were tested but no source for the glycerine contamina tion was found. DSW 622170 STLCOPCB4096203 18. Since the glycerine only appeared from compounded samples, the method of sample preparation was examined. From this study It was concluded that glycerine was being intro duced into the samples from the cellophane which is normally used in the molding operation to prevent sticking of the sample to the molds. Cellophane when subjected to the fogging test produced heavy fogging. Samples of various plasticizers molded without cellophane gave vastly different results from previous samples. 4. Infra-red Test Results The following visual results were obtained on new samples molded without cellophane: Degree of Fogging None Slight Moderate Heavy - Harflex 500 DIDP Adipol ODY PlastQLeLn5049-S S-409 Monoplex S-90 G-54 Di-2-ethylhexyl TCP glycolyl phthalate DIDP/S-90 (l/l) TCP/S-90 (l/l) G-62 DIDP-E DOP S-160 S-141 DIDP/S-160 (2/1) S-140 In addition two samples of coated fabric obtained from Textlleather were tested. A-white sample gave slight fogging while a black sample gave heavy fogging. The apparent better performance of the white sample may have resulted from the heat reflective properties of the pigment and consequently lower temperature rather than an improved plasticizer system. 5. Numerical Rating of Fogging The Photovolt Photoelectric Meter with reflectance attachment was used in an attempt to measure the fogging. However, no difference could be detected between a heavily and a slightly fogged surface. The 60* gloss attachment did show a difference in specular reflection of samples which visually appeared to be fogged to different degrees. The following pro cedure was established. The 60* gloss attachment was adjusted to read 100 with a clean plate glass backed by the black carrara glass. The specular reflection of the plate glass cover is taken before and after the fogging test. The difference between the two readings is the "Fog Value". It will be seen that a plate which reads 100 before and after the test has a Fog Value (FV) of 0 indicating no fogging. DSW 622171 STLCOPCB4096204 19. The following table shows the comparison between the visual and Photovolt rating of fogging to indicate the correla tion. Plasticizer DOP DIDP S-90 Fogging Visual Fog Value Heavy Slight None 36 4 0 The infra-red procedure was used to obtain fog values on various Monsanto and competitive plasticizers as shown in Table 8. An experiment was designed to determine the precision of the test method. The experiment consisted of testing two plasticizers, DOP and DIDP, in duplicate In each of four runs. The detailed analysis Is included as Appendix I and will be--' summarized here. The overall precision, that is, variation result ing from between and within experiments, can be represented by a standard deviation (for a single determination) of 6.32 units of specular reflection while the 95# confidence limits for a single test is + 12.64. Within a single experiment the precision Is represented by a standard deviation of 3.71 and 95# confi dence limits of + 7*42. From the detailed analysis It was noted that 65# of the total variation was due to differences between experiments. The major cause of this variation was thought to be lack of temperature control and reproducibility due to use of the heat lamps. The position of the lamps had to be changed from experi ment to experiment to achieve the same temperature in the samples. 6. Oil Immersion Test Procedure In an attempt to improve temperature control, a series of samples in beakers covered with plate glass were placed in an air circulating oven at a 90C. for 16 hours. There was no change in specular reflection for the samples which were DOP, DCP, DNODP, and DIDP. As a result it was concluded that the temperature.differential achieved by only heating the sample while the plate was at room temperature was essential to cause deposition of the fog. DSW 622172 STLCOPCB4096205 20 TABLE 8 Fog Value of Monsanto and Competitive Plasticizers (Formulated to a Shore "A" of ij0-b2~T~ Plasticizer Bis (2-ethylglycolyl) phthalate S-405 S-407 S-402 S-409 (BPA before fil- tering) DIDP DIDP-E S-409 TCP DNODP S-536 (DIDP-E/DOP 1/1) DOP S-606 (DIDP/S-160 2/1) S-141 S-615 (DIDP/S-160 1/2) Ford Special No. 2 S-602 S-160 FV 1 1 1 1 3 61 6a 10 10 16 25 361 43 44 47 46 48 59 Plasticizer FV Paraplex 0-62 1 Monoplex S-90 0 Monoplex S-90 (Opalon 410) 0 Paraplex 0-54 6 Emery 3049-S 6 Eastman NP-10 Flexol 810 13 14 Hercoflex 150 Harflex 300 15 26 Dicapryl phthalate 34 Flexol 580 -- 46 Textileather Coated Fabric White 13 Black 80 Average of 12 determinations 2 Average of 4 determinations Therefore, a Magnl Whirl Utility Oil Bath (Model MW1145) was fitted with a rack and supports to hold six beakers. A liquid level (Dow Corning 550 fluid) was maintained so that the beakers were immersed 2-1/2 inches in the liquid. A cross sectional drawing of the test apparatus is shown in Figure 2. Several runs were completed and a bath temperature of 93*0. was established as giving comparable temperatures to the test using the heat lamps. In addition, since the carbon black was no longer needed to adsorb heat, it was removed from the formulation. DSW 622173 STLCOPCB4096206 21. STLCOPCB4096207 22- A statistical experiment similar to the one pre viously described was performed using the oil bath at 93*C. with 2-1/2 inch immersion of the beakers. The plasticizers, DOP and DXDP, were tested in triplicate in each of four runs. The detailed analysis, given in Appendix II, show that the between experiment standard deviation was 3-1 and 95$ confidence limits +6.48. The within experiment standard deviation was 2*75 while the 95$ confidence limits were 5.84. It will be noted that the between experiment variation was reduced by a factor of two through the use of the new method. In addition the within ex periment precision shows a vast improvement. 7 Temperature, Plasticizer Concentration, and Time Effects Upon Fogging' ' a. Effects of Temperature Upon Fogging The temperature of the oil bath was varied to determine the effect of this variable upon fogging using DIDP, DOP, S-409, G-54 and G-50 as the plasticizers. The results shown in Table 9 indicate a fogging dependence upon the test temperature. The DOP data appears to change rapidly in the ' range of 75-90C. and may be leveling off at each end. DIDP levels off at 75-80C. The polymeries are approaching a FV - of 0 at 70C. This work Indicates the temperature to be very critical and as a result a test temperature for the oil immersion method was established at 85C. At this temperature the values for the various plasticizers correlate well with results obtained by the infra-red heating methods. Temp., C. 93 88 82 76 71 TABLE 9 Temperature Dependence of Fogging Fog Value DOP DIDP 651 56, 54, 38, 35, 31, 33, 20, 22, 55 38 25 22 241 17, 12, 14 6, 4, 6 6, 4, 3 4, 2, 2 S-409 G-50 G-54 93 36, 35 25, 32 29, 26 86 24, 17 20, 17 14, 19 8l 15, 16 17, 14 5, 7 76 4, 6 1, 1 0, 5 x- average of 12 determination from statistical study. DSW 622175 STLCOPCB4096208 23 b. Effect of Plasticizer Concentration Upon Fogging Polyvinyl chloride samples plasticized with three plasticizers at three levels of plasticizer concentration were evaluated for fogging in the oil bath method at 93C. The re sults given In Table 10 show little difference in fog value between 40 and 50# concentrations. At low concentrations, the fog value was higher. As a result, future tests were run at 40# plasticizer concentration. TABLE 10 Plasticizer Concentration vs. Fogging Plasticizer Plasticizer Concentration, # 25-b 40 50 DIDP Santiclzer 409 Paraplex G-54 Fog Value * 39 26 47 39 37 35 27 36 --1 39 - Average of two determinations c. Continued Testing of Same Specimens A series of polymeric plasticizers, Santiclzer 409, Paraplex G-50 and G-54, were tested three times using the same samples to determine the effect upon fogging of repeated heating. The samples were then heated in open beakers at the test temperature in an effort to drive off volatile constituents. The results shown in Table 11 indicate very little change in the samples as a result of continued and repeated testing or preheating of the samples in open containers. ....... TABLE 11 Repeated Testing of Samples (Oil Immersion at 93 for lb hours) Plasticizer System Specular Reflection1 Test No. 1 3 42 S-409 G-50 G-54 ` ' 64 63 63 60 71 6l 70 66 72 76 78 74 1- Average of two determinations. 2- Samples heated 16 hours at 93C. in open beakers between Test No. 3 and Test No. 4. ' STLCOPCB4096209 24 . 8. Test Results on Monsanto and Competitive Plasticizers Table 12 gives the fog values obtained on Mon santo and competitive plasticizers when tested at 40# concentra tion in Opalon 300 using theoil immersion procedure at 85C. It will be noted that range of fog values from 0 to 50 repre senting no fogging to heavy fogging are given. TABLE 12 Fog Values by the Oil Immersion Method (40# Plasticizer Concentration in Opalon 300) (Test Temperature 85C.) Plasticizer Fog Value Paraplex G-62 Emery 3049-S Decyl tridecyl phthalate Santicizer 405 Monoplex S-90 Elastex 37-H S-407 Harflex 375 Harflex 300 DIDP DIDP-E Admex 761 Harflex 305 S-403 Paraplex G-54 S-409 DN0DP D0P 0 2 4 4 5 6 6 9 9 12 12 15 14 14 16 24 34 50 9 Testing of Plasticizers and Resin per se Following receipt of a call report in which a customer stated that plasticizers per se would not fog by the Chrysler test, it was believed that the oil immersion methods would prove useful due to an external heat source. Samples of D0P and DIDP tested per se at 85C gave comparable results with those obtained on plasticized PVC samples. The test was extended to cover a number of additional plasticizers and resins as shown in Tables 13 and 14. It will be noted that the only serious cross oven is Paraplex G-54 which gave a fog value of 16 when tested in PVC while the per se fog value was 3* DSW 622177 STLCOPCB4096210 25. TABLE 13 Fog Values of Plasticizers Per Se (d5C. in oil Immersion test) Plasticizer Fog Value Paraplex G-62 Paraplex G-25 Admex 747 Paraplex G-40 Harflex 375 Harflex 305 Elastex 37-R S-405 Monoplex S-90 Emery 3049-S Ditridecyl phthalate Paraplex G-54 Harflex 350 S-407 S-403 Paraplex G-53 DIDP, DIDP-E Admex 770 Admex 761 Monoplex S-73 DOS Paraplex G-50 Admex 746 TCP Admex CL 748 DIDA NP-10 DN0DP Plastoleln 9058 (DOZ) DNODA DOP DCP Isohexyl benzyl phthalate (TEA) DOA Harflex 300-X Isohexyl benzyl phthalate (carbonate) Benzoflex 9-80M S-141 S-160 0 0 0 1 1 1 1 1 2 2 2 3 3 4 7 10 12 12 16 17 17 18 19 20 20 27 36 37 47 52 56 57 58 59 62 68 72 73 78 DSW 622178 STLCOPCB4096211 TABLE 14 Fog Values of Resina Per Se (ti5"C. Inoil bathj 26- Plasticizers Opalon 300(Rerun of sample 7) Opalon 410(Rerun of sample 10) Opalon 505 Opalon 300 FM Geon 101 Geon 203 Geon 121 Geon103 EP Marvinol VR-50 Pliovlc VO PlJovic AO Vygen 105 Escambia PVC Pearls Exon 654 Fog Value 18 23 8 30 25 1 77 0 0 61 0 4 26 79 A series of plasticizers and resins were tested per se by the oil immersion method at a bath temperature of 100C. and the results are given in Table 15 The conclusion reached upon examination of the data show that testing at 100C. tends to resolve and separate those plasticizers which were grouped in the fog value range of 0-5 by testing at 85C. TABLE 15 Fog Value of Plasticizers and Resins Per Se at 100"C. Plasticizers Fog Value G-62 Dltridecyl Phthalate G-50 DOP DIDP-E S-403 S-405 3-407 S-409 Plaskon 37- R 3049 S Harflex 375 G-54 S-90 Opalon 330 FM Geon 103-EP 0 25 60 69 43 32 12 16 35 9 1 I 34 II 53 11 DSW 622179 STLCOPCB4096212 27. Since In the test on the plasticizer per se no allowance is made for losses of plasticizer due to milling and other processing, several polymeric plasticizers were heated for various times at 195C. in open dishes in an effort to reduce the fog value. As shown in Table 16, some reduction in fog value is evident but the change is so low in magnitude that processing conditions would have little or no effect upon fog value. This work does not help explain the vast difference encountered in G-54 when tested in a compound versus per se testing. TABLE 16 Effect of Preheating on Fog Values Plasticizers S-409 Paraplex G-54 S-409 + 10# 0-62 Precondition, hrs. at 0 172 1 Fog Values 21 lb ~T3------ 59 10 - 16 16 195*C. 2 10-- 7 10 . 10. Fog Value of POP From Several Manufacturers The oil immersion method was used to test DOP from various manufacturers for fogging characteristics. The results of two runs on the same samples are given in Table 17, which shows no appreciable difference among the suppliers. TABLE 17 Fog Value of DOP from Several Manufacturers (Per se measurements at ti5*C. by oil immersion) Manufacturer Fog Value 1st Test 2nd Test Carbide Eastman Goodrich Monsanto 63 62 62 63 58 54 61 60 DSW 622180 STLCOPCB4096213 28. 11. Evaluation of Various Samples of S-409 from Plant Production :: A testing program was undertaken In an effort to help the plant reduce the fog value of S-409 by correlating fogging with a controllable property. The relationship of viscosity and fogging was determined as shown in Table 18. There appears to be no direct relationship of viscosity and fogging. The evaluation of S-409 containing 0.2# charcoal at various stages of the finishing operation is shown in Table 19. In this case the steaming operation reduces the fog value a slight amount while addition of Bisphenol A had no further effect. The results on several composite lots of S-409 are given in Table 20 along with a representative value for Paraplex G-54. It should be noted that S-409 appears to be improving slightly but still does not approach the low fogging of G-54. TABLE 18 Comparison of Fog Value with Viscosity of S-409 (Plant Produced) S-409 Viscosity (centistokes) Fog Value (Per se at 85C Batch 64 Batch 65 Batch 67 Batch 76 Batch 77 Batch 79 175 15 164 9 144 8 125 21, 20, 19 121 10, 14 129 14, 15 TABLE 19 Fog Values of S-409 at Various Stages of Production S-409 Batch No. Fog Value (Per se at 85C.) Before After After Steaming Steaming BPA Addition Filtered 87 15, 15 95 12 98 14 98 (lab filtered) 9 9, 10 10 8, 141 8 9, 9 11 9 14 - 10 - j_- Double steaming time DSW 622181 STLCOPCB4096214 29. TABLE 20 Fogging Results on Tank Cars of S-409 Lot No. Fog Values (Per se test at 85C.) C-9 C-ll C-12 CQ -15 C-73 (W-Bldg.) 15 11 18, 21 10, 10, 10, 6 13, 14, 17, 18, 19 9, 10, 14 G-54 5, 6 12. Evaluation of Chrysler and Ford Specimens The Development Department obtained several samples of fogging and non-fogging films from both Ford and Chrysler.. These were tested by the oil Immersion method at 85C. for two consecutive runs with results as shown in Table 21. It will be noted that excellent spread is obtained on the Ford samples while on the Chrysler sample the difference between fogging and non-fogging is not so great. TABLE 21 Evaluation of Chrysler and Ford Specimens Chrysler, Thermocouple Standard Chrysler, non-fogging Chrysler, fogging Ford, non-fogging Ford, fogging Ford, fogging Fog Value at 85C. 1st Run 2nd Run 19 13 62 36 72 72 34 28 70 41 71 59 DSW 622182 STLCOPCB4096215 30. 13 Fords Fade-Ometer Test Ford Motor Company developed a test method for determination of fogging using the Fade-Ometer as the source of ultra violet light and heat. The samples are placed in glass dishes with the coated side down and held in place with a wire gauze rack. The dish is sealed with a clean glass plate and the assembly is supported on a Fade-Ometer holder. The unit is placed in the Fade-Ometer, coated fabric side toward the light source for 20 hours at a black panel temperature of ltV5F. (maximum 150F.). The fog on the glass plate is measured with a Weston Foot Candle, taking four readings of light transmittance on each plate and reporting the average. The minimum light transmission for an acceptable sample is 75 14. Ford Program -- A cooperative program was started with Ford to pre- _ pare samples here for testing by their Fade-Ometer test for possible acceptance by Ford. Acceptance by Ford of a plasti cizer system would be of great benefit in attempting to sell Ford's suppliers. a. Laboratory Prepared Samples A series of nine formulations were milled and molded for fogging studies. These Included Ford's standard plus others which would duplicate the standard in performance as shown in Table 22. It is interesting to note that the fog values of the various formulations also given in Table 22 can be related almost directly to the per se fog values of the plasticizers. Also that the fog value from plasticized PVC using a mixed plasticizer system is slightly more than the per se value of the highest fogging plasticizer. The differences obtained on per se measurements of the resins can be further shown in compounded sheets. DSW 622183 STLCOPCB4096216 31 TABLE 22 Ford Formulations for Fogging Geon 103 EP Std. 2 3 4 5 6 7 8 103" 100 100 1(50" 100 100 100 100 9 ---- Opalon 300 - - - - - - - - 100 Dlcapryl phthalate 36.7 - - - - - - -- - DIDP-E - 40 40 40 40 40 40 40 40 Admex 7^6 7.8 7*8 7*8 7*8 - - -- -- -- Paraplex G-62 - - - -66666 DOZ DNODA DIDA DOS 12.5 12.3 - - - - - 12.5 - 14 -- - - - 12.5 - 14 ------- 14 -- - -- --_ - . 14 -- -- _ 14 Duranite 25 25 25 25 25 25 25 25 25 Mark M 3333 33 3 3 3 Mark PL 0.25 0.25 0.25 0.25 0.25 0.25 0.25 O.25 Q-r25 Stearic Acid 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Fog Value 72 58 66 35 64 31 --*40 27 34 b. Samples Prepared by Springfield for Fogging Analysis' Six samples of calendered film were prepared by Springfield for submission to Ford for testing by their test for possible acceptance. The plasticizer systems were a compari son of the Ford standard plasticizer system of dlcapryl phthalate and dioctyl azelate with DIDP-E plus other flexlbalizlng plas ticizers as shown in Table 23. The test results by the oil immersion and FadeOmeter test conducted here plus the results obtained by Ford using their Fade-Ometer test are also given in Table 23- The results by the oil immersion show more fogging than anticipated. Monsanto's results by the Fade-Ometer are very erratic while Ford's results agree somewhat with the oil immersion values. Due to the additional work done on stabilizers and lubricants since the above formulations had been requested, it was felt that Formulation F could be compounded to meet Ford's Specification of 75* DSW 622184 STLCOPCB4096217 32. TABLE 2J> Formulations and Test Results on Calendered ' Film Prepared by Springfield Opalon 330-FM Geon 103-EP DCP DIDP-E Monoplex S-73 Paraplex G-62 DOZ(azelate) DNODA DIDA DOS (sebacate) Atomite Mark M Mark PL Stearic Acid Carbon Black Monsanto Fog Value i Monsanto Result using Ford TM1 Ford Results2 A 100 - 36.7 - 7-8 - 12.5 - 25 3 0.25 0.50 1.0 B lM 40 7-8 - 12.5 - 25 3 0.25 0.50 1.0 c 100 -.- 40 - 6 - 14 -- 25 3 0.25 O.50 1.0 D 1M -- 40 - 6 16 -- 25 3 O.25 0.50 1.0 E Totf -- F _ 100 40 40 -- '_ 66 -- 14 25 3 0.25 0.50 1.0 __ 16 25 3 0T25 0.50 1.0 60 51 64 41 38 36 57 67 70 71 64 68 54 50 50 52 62 70 1- Fog Value where 0 indicates no fogging. 2- Transmission where 100 indicates no fogging. c. Additional Films Prepared by Springfield Four additional calendered film formulations were suggested to Springfield incorporating the low-fogging stabilizer and lubricant systems. Springfield added three other formulations giving a total of seven as outlined in Table 24. These seven films were tested by the oil immersion method at 85C. with the results shown in Table 24 as was predicted. Five of these films were submitted to Ford for evaluation by their Fade-Ometer method. Ford's results were very discouraging since they would hardly distinguish between the fogging and non-fogging plasticizer systems. Actually sample No. 3 in this series was almost Identical with a previous sample which had been rated at 'JO. The major difference was the change in stabilizer system. DSW 622185 STLCOPCB4096218 33. Ford was informed of this discrepancy and agreed to rerun sample No. 3* This was done with the following results: 54, 56, 56 and 59* Thus, it appeared that S-169 would not be approved by Ford. However, during isolated runs in the past the tre mendous difference between white and black samples or pig mented and clear samples when tested with heat lamps or the Fade-Ometer had been noted. It was hoped that possibly this difference could also be detected with various colors and, thus, avoid a flat rejection of S-169 by Ford (see Section 18). The physical properties of several films were obtained to compare the performance of the DIDP-E/DIDA mix ture with Fordrs standard. The relationship was excellent. A portion of each film sample submitted to Ford was returned and the fog value redetermined by the oil immersion method. The results were in close agreement with those previously obtained. -- TABLE 24 Formulations and Test Results on Springfield Film Opalon 330-FM Geon 103-EP 1 23 4567 - TOO- TOO- TOO- 'TOO- TOO- 100 - 100 - -- DCP DIDP-E Monoplex S-73 Paraplex G-62 DOZ (Azelate) DIDA Santicizer 409 36.7 36.7 __ - - 40 40 40 45 23 7-8 7.8 - - - - - - -- 6 6 5- - 12.5 12.5 - - - -- - 16 16 16 16 16 - - - - - - 22 Atomite Mark WS Dyphos Calcium Stearate Kosmos BB(carbon black) 25 2 - 0.25 1.0 25 2 - 0.23 1.0 25 2 - 0.25 1.0 25 2 - 0.23 1.0 25 - 4 0.25 1.0 25 - 4 0.25 1.0 25 - 4 0.25 1.0 Oil Immersion Fog Value 65 63 15 24 18 18 24 Ford Results 50 50 64 68 - - 72 Ford Results 42 52 58 54 - - 64 Ford Results 42 55 52 70 70 Tf -43.4 -48.3 -41.3 -41.2 Shore Hardness 75 73 80 80 Loop Compatibility OK OK OK OK DSW 622186 STLCOPCB4096219 34. 15 Evaluation of Stabilizers and Lubricants The stabilizers and lubricants used in the standard Ford test plus others were tested for fogging as Indicated in Table 25- It appears that proper choice of stabilizer and lubricant can produce low fogging systems. To check this in a complete formulation, Mark WS and Mark XI each were substituted in formulation No. 6, Table 22 with calcium stearate as a lub ricant. The fog value was reduced from 51 to 21 with WS and 20 with XI. These results indicate the tremendous influence that small amounts of high fogging ingredients have upon the fogging characteristics of a finished formulation. TABLE 25 Fog Value of Stabilizers and Lubricants (Tested in Oil Immersion at &5UC. for lb Hours) DIDP-E Mark M Mark PL Stearic Acid Calcium Stearate (Harshaw's 5-V-l) Mark WS Mark XI Fog Value 33 0.2 0.2 4 drops 0.1 0.1 - 63 - 43* 3 - 0.1 - 23 33 --- -- -- 0.1 - 14 - '- 12 3 --- -- -- 0.1 - 17 3 0.1 14 Fog condensed as large clear droplets. This condition although representing heavy fogging gives low readings. 16. Composition of Santiclzer 169 (X-6060) During a visit to Ford, they were informed of an experimental product, X-6060,which would pass the fogging requirements and still give satisfactory performance at a reasonable price. It was known that X-6060 would contain 40 parts* DIDP-E and 16 parts DIDA. In order to confuse any possible analysis it was felt that a small percentage of S-409 would be advantageous. Therefore, three mixtures were prepared containing the above proportions of DIDP-E and DIDA with 0, 5 and 10# S-409* DSW 622187 STLCOPCB4096220 55- X-6060 was stored in the freezing compartment of a refrigerator for two weeks without visual change with regard to cloudiness or further haze formation. X-6060 X-6060 + 5# S-409 X-6060 + 10# S-409 TABLE 26 Fog Values of X-6060 Fog Value per se at 85C. 20 17-1/2 24-1/2 17. ADM*s Admex 747 Ford tested and approved Admex 747 as a non^_ . fogging plasticizer for automotive uses. The fog value of Admex 747 is 0 and its only drawback is cost (46 cents a pound). As it later developed the cost factor was sufficient to prevent its wholesale adoption in automotive fabrics. Based on Fordrs approval, Admex 747 was inves tigated thoroughly by the oil immersion test alone and combined with various other plasticizers and lubricants. The results are given in Table 27. The performance of Admex 747 is excellent in fogging. However, at 40# concentration, the material is incom patible in the loop test. TABLE 27 Fog Values of Admex 747 and Combinations Containing Admex 7^7 Fog Value (Oil Immersion, 85C., 16 hrs.) Admex 747 Admex 747/S-169 (l/l) Admex 747/DIDP-E (l/l) Admex 747/DIDA (l/l) Admex 747/Mark WS1 Admex 747/Mark PI1 Admex 747/Calcium stearate1 Admex 747/Mark M1 Admex 747/Stearlc Acid1 1- 1/4 gram additive to 3 grams Admex 747* 0 16 10 24 5 70 0 46 18 DSW 622188 STLCOPCB4096221 36. 18. Study of the Ford Test a. Temperature Effect The Ford Fade-Ometer Test was studied In an attempt to explain the lack of correlation between the two laboratories. Sample dishes of the same dimensions as the Ford dishes were obtained. However, standard Fade-Ometer holders were used in place of the Ford holders. In addition, readings of the fog were taken on the Photovolt meter. Due to the type of measurement used by Ford where high transmission indicates low fogging, our results by the Ford test were reported as specular reflection to have results in the same order of magnitude. A previous study at a black panel temperature of 135F. had indicated rather good correlation with the ___ oil immersion method as shown in Table 28. ~ Tests conducted on three of the Springfield ' film samples at the low temperature gave fair agreement with the oil immersion test and showed a difference between high and low fogging samples. These results are given in Table 29. As the black panel temperature was increased to the range of l40-l45F. as recommended by Ford, difficulty was encountered in reading the panels. It appeared that a gradation occurred in the fog from the top to bottom of the panel. This could not be eliminated and, thus, four readings of the fog value were obtained on each panel and the results averaged for the final value. The temperature of the specimen was also obtained by means of a thermocouple embedded in a black specimen. It was found that the specimen temperature was related to the black panel temperature as follows: Black Panel Temperature Specimen Temperature 140-150F. 135-140 120-125 182F. 175 165 Another problem encountered was temperature variation and range from Fade-Ometer to Fade-Ometer. No method was discovered to effectively control this condition and the solution was the use of one Fade-Ometer for the study. DSW 622189 STLCOPCB4096222 37- TABLE 28 Correlation between Oil Immersion and Fade-Ometer Results Sample Temp, F. WS Formulation XI Formulation 40# DOP 40# DIDP Ford F 135 13If 5 rt if Fog Value Fade-Oneter Oil Immersion 16 21 15 20 6l 50 12 12 33 38 TABLE: 29 Fade-Ometer Tests on Springfield Film Film No. Fog Value (Fad-Ometer at 155-*F. _________ for 20 hours) 2 74,75 3 59,41 4 34,44 Six of the Springfield films were tested by the Fade-Ometer method with results shown In Table 50. In this case the reported values are specular reflection so that the com parison with Ford's results is simpler. The results show some agreement with Ford's but the variation on each plate is high. TABLE 30 Fade-Ometer Results on Springfield Film Film No. ------ 1-------- 2 3 4 5 6 , -Ford's Results1 42742 53=45 50,52,55=52 64,58,52=58 68,54,70=64 Fade-Ometer Specular Reflection2 24.27.25.24 = 25 24.25.24.25 = 24 61.48.57.76 = 6l 57.49.59.66 = 58 66.46.65.67 = 60 69.68.65.77 = 70 . iResult of three tests. 2Four readings from one plate from one test. DSW 622190 STLCOPCB4096223 38. b. Specimen Color Effect Upon several occasions the vast difference In fogging between white and black samples when tested in the Fade-Ometer has been noted. If this difference can also be noted between various colors, S-I69 could still conceivably find a market. A series of S-l69 plasticized compositions in various colors (Table 31) were prepared and when tested by the Fade-Ometer test most of the colors seemed to pass the Ford Specification. . Samples were submitted to Ford and the white, blue, red and yellow passed their specification by a good margin in all cases except yellow (Table 31) The effect of color was tested upon two series of compounds in white, yellow and blue with two plasticizer systems; the Ford standard and S-169- The results shown in Table 32 indicate with the Ford standard plasjti-Cjizer system that the fogging is still great and apparently not influenced by the color of the sample while with S-I69 these colors show little fogging, except for the phthalacyanine green and blue. It appears that these pigments act much like carbon black In their adsorption and heat build-up. The phthalacyanine green pigmented sample showed no difference in fogging when the pigment concentration was reduced to one-fourth the original concentration. Under these same conditions, the blue showed some improvement but the fogging was still heavier than the ultramarine blue. The sample temperature inside the cell was determined by placing a thermocouple between two specimens and taking a reading after equilibrium had been reached. The differences between the various colored specimens was not as great as expected but the correlation with fogging character istics appears to be good as indicated in Table 33. 19- Fogging Characteristics of Mixtures of S-I69 and Admex 747 ~ : In an effort to determine if small amounts of Admex 7^7 added to S-169 would produce formulations which would meet the Ford test, a series with varying mixtures were tested by both test methods. The formulations and results given in Table 3^, indicate little improvement In fogging is noted when a black specimen is tested in the Fade-Ometer until most of the S-I69 is replaced. In the oil immersion method, the fogging decreases gradually as the concentration of Admex 7^7 is increased. DSW 622191 STLCOPCB4096224 39- TABLE.31 Effect of Color Upon Fogging Georf; 101 S-169 Mark WS - Calcium Stearate (5-V-l) Atomite Bon Dark Red (RL-586-D) Chrome Yellow (Y-433-D) Ultra Marine Blue Phthalocyanlne Green Carbon Black Monsanto Fade-Ometer Test Ford Pade-Ometer Test 18 12 0.3 0.1 5 - - 92 91 18 12 0.3 0.1 5 l/l6 - - - -. 18 12 0.3 0.1 3 1/8 - - 88 90 92 82-5 18 18 18 12 12 12 0.3 0.3 0. 0.1 0.1 0. 555 1/16 - - -- 1/16 - _ _ 0. 95 72 54 96 - -- TABLE 32 Effect of Color on Fogging., of Two Different Plasticizer Systems Color Plasticizer System Specular Reflection Fade-Ometer Oil Immersion White White Ultra Marine Blue Ultra Marine Blue Yellow Yellow Phthalacyanine Green Phthalacyanine Green Phthalacyanine Blue Phthalacyanine Blue DCP and S-73 S-169 DCP and S-73 S-169 DCP and S-73 S-169 DCP and S-73 S-169 DCP and S-73 S-I69 50 93 45 90 42 92 - 45 69 31 74 36 80 40 80 38 75 36 80 35 77 DSW 622192 STLCOPCB4096225 40 TABLE 33 Specimen Temperature of Various Colored St^ecimens in Pade-Ometer (Black Panel Temperature 14frFT) ^ Color White Yellow Ultra Marine Blue Phthalacyanine Green Phthalacyanine Green Phthalacyanine Blue Phthalacyanine Blue Black Concentration,$ 0.1 0.1 0.05 0.05 0.01 0.05 0.01 0.05 Specimen Temp.,P. 170 170 175 180 178 178 175 185 i TABLE 34 Study of Mixtures of Admex 747 and S-I69 (55 phr plasticizer in Geon 103 EP) % Admex 747 in S-I69 Specular Reflection Fade -Ometer --------err immersion White Black White Black 0 94 74 87 89 18 96 67 85 86 36 96 71 86 88 54 95 68 91 89 73 97 74 93 91 100 97 92 99 98 20. Fogging as a Function of Resin A series of compositions in both white and black containing different resins were evaluated in the Pade-Ometer test. The formulations as shown in Table 35 was run with Geon 101 , Opalon 300 and Geon 103 EP. These resins were tested since they represented a range of fog values when tested per se. DSW 622193 STLCOPCB4096226 41 It was found (Table 35) in black that the fogging characteristics of the plasticized composition can be related to the per se fog value of the resins. In white formulations this is not so evident although in this case the fogging of all samples was low. In another experiment, three plastisol grade resins: Opalon 410, Geon 121 and Marvinol VR-50, were for mulated with S-I69 and Admex 747 at two concentrations to determine if the resin fogging characteristics influenced the fogging of the plasticized composition. The formulation contained plasticizer at 65 or 100 phr: G-62, 5 phr; Mark WS, 1.5 phr; and Atomite, 25 phr. TABLE 35 Fogging Characteristics Based on Resin Type (56 phr Admex 747, 6 phr G-62, stearate, 25 phr Atomite) Resin Type ' ' 2 phr Mark WS, 0.:2 phr calcium' Specular Reflection Fade-Ometer - White Black Geon 101 Geon 103 EP Opalon 300 . 97 87 97 94 95 89 The results, shown In Table 36, give a direct correlation between per se resin fogging characteristics and composition fogging. That is, Geon 121 is high fogging when tested both ways, Opalon 410 Is next while Marvinol VR-50 fogs the least. It was also found that plasticizer concentration has little or no effect upon fogging characteristics. TABLE 36 Effect of Plasticizer Concentration and Resin Type on Fogging Resin Color Plasticizer Specular Reflection Fadeometer Oil Bath PHR 6^5 100 b5 TOO Opalon 410 Black Geon 121 Black Marvinol VR-50 Black VR-50 Black 410 White 121 White S-I69 S-169 S-I69 Admex 747 S-I69 'S-I69 44 48 69 69 24 24 30 24 55 48 66 70 82 92 97 97 79 73 68 71 28 23 37 32 DSW 622194 STLCOPCB4096227 42- A number of per se samples of Opalon 330 FM were fogged by the oil Immersion method to obtain sufficient fog to be scrapped from the plate glass and analyzed by Infra-red. The majority of the samples of scrapplngs was found to be a fatty acid similar to but not stearic acid. A second minor component was Identified as mo3t likely ammonium chloride. 21. Fogging Tests on Toscony Fabrics1 Samples Thirteen samples of film and coated fabric were received from Toscony Fabrics for evaluation of fogging character istics. The samples represented components of a coated fabric such as film, cotton, sheeting, adhesive layer and top coating. The results are given in Table 37 It is Interesting to note that the difference between DOP and DIDP is washed out when the films are laminated to fabric with S-624 a3 the adhesive (No. 3 and No. 4). Top coating does not help this condition. When TCP/DIDP are used in the adhesive formulation, the low fogging characteristics of DIDP again are shown. Top coating again apparently has only a slight effect upon fogging. The only apparent cross-over appears with No. 12 and No. 13 where the two adhesive formulations are coated on cotton sheeting. Since Geon 121 is a high fogger (fog value of 77)j we felt the resin could be overshadowing the plasticizer differences. Therefore, a plastisol similar to the adhesive formulations in No. 12 and No. 13 was prepared using Marvinol VR-50 (fog value of 0). The plastisols were coated on glass and fused 10 minutes at 175C. Fog values were determined: 68 for S-624 and 16 for TCP/DIDP. Thus, we feel the resin accounts for the similar results between No. 13 and No. 13* Samples No. 1 and No. 2 were also tested by the Ford Fade-Ometer test with very little fogging. This is due to the white color of the samples wherein insufficient heat was generated to cause fogging since DOP gave a fog value of only 20 and DIDP gave a reading of zero. DSW 622195 STLCOPCB4096228 43. Sample 1 2 3 4 5 6 7 8 9 10 11 12 13 TABLE 37 Fogging Results on Toscony Fabrics Samples Film Plasticizer DOP DIDP DOP DIDP DOP DIDP DOP DIDP DOP DIDP Cotton Sheeting Cotton Sheeting Cotton Sheeting Adhesive Plasticizer __ .--S-624 S-624 S-624 S-624 TCP/DIDP tcp/didp TCP/DIDP TCP/DIDP --- S-624 TCP/DIDP Top Coat No No No No Yes Yes No No Yes Yes - No No Fog Value 62 25 77 62 69 66 60 32 60 27 34 81 77 -- 22. Fog Value on Decyl Trldecyl Phthalate Several laboratory prepared samples of decyl trldecyl phthalate were evaluated by the oil immersion method . Each run yielded results difficult to interpret due to the presence of a crescent shaped pattern of heavy fogging. This heavily fogged area covered approximately one-quarter of the exposed glass and was generally toward the outer or cool side of the beaker, leaving the impression that a highly volatile component was condensing. A retest of the same plasticizer sample gave a fog value of 5 with a normal appearance. The test was repeated with several different samples and the same result was obtained each time. A sample of decyl trldecyl phthalate was heated in an open container in the air circulating oven at 173C. for 30 minutes. Following this treatment the sample was tested for fogging by the oil immersion method at 85C. The fog value was 2. An equal molar mixture of DIDP and ditridecyl phthalate was tested in the oil immersion test and found to have a fog value of 6. This result is surprising since generally the fog value of mixtures approached that of the most highly fogging component. A sample of decyl trldecyl phthalate which had been sent to Springfield was returned and a portion was given additional steaming by M. W. Farrar in which a small amount of volatile material was taken off. Three samples of each material were tested DSW 622196 STLCOPCB4096229 44. with the specular reflection values of 94, 94 and 94 for the returned sample and 94, 95 and 95 for the old steamed sample. The uniform fogging and lack of a crescent shaped curve on the returned material leads us to believe it must be from a different lot than previously tested. 25 Fogging as Related to Carbon Black, Blsphenol A, HB-40 and Volatility : : a. Effect of Carbon Black on Fogging Carbon black was removed from the formulation when it was no longer needed to give good heat absorbing qualities to the plasticized sheet. The question of possible stabilizing action of the carbon black was answered by an experiment comparing white and black samples in the oil immersion method. The results tabulated in Table 38 indicate that no stabilizing action is obtained from the carbon black. TABLE 38 Carbon Black Effect Upon Fogging Plasticizer Fog Value S-409 Black S-409 White 63, 67 = 65 68 G-54 Black G-54 White 77, 76 = 76.5 77 b. Effect of Blsphenol A Upon Fogging The fogging characteristics of Blsphenol A per se and slight amounts added to Admex 747 were determined in the oil immersion method. This work was necessary due to the widespread usage of BPA in vinyl compounding as an antioxidant. BPA per se fogs excessively (FV =88). However, when 1^ BPA is added to Admex 747 and tested per se the fog value is 3 and when the con centrate of BPA is reduced to 0.25$, no fog can be measured. Therefore, at the normal concentrations BPA has little or no effect upon fogging. DSW 622197 STLCOPCB4096230 45. c. Fog Value of Combinations of POP and HB-40 J. K. Sears found that HB-40 exerted an anti oxidant effect upon DOP. Therefore DOP containing 5$ HB-40 was tested in the oil immersion test to see if this effect was notice able in fogging. The results indicated it was not since the mix ture had a FV of 74 and DOP alone has a FV of 56. d. Relationship of Fogging to Volatility Two samples of the Springfield film (Table 23) were run in duplicate in the activated carbon test with cages for 24 hours at 87*0. The results, tabulated in Table 39, indicate small differences between the two samples. However, it was believed that experimental error would tend to overshadow this difference. TABLE 39 Volatility Versus Fogging (Springfield Samples, Table 23) Volatility, # Sample Fog Value loss of Total Wt. A 60 0.81,0.77 = 0.79 F 56 0.72,0.63 = 0.68 VIII. ACKNOWLEDGMENT The excellent cooperation of the Sales and Development Departments is gratefully acknowledged. We particularly appreciate the help of D. H. Bechtold, J. Glenn Hicks and Springfield personnel on the problem of fogging. W. W. Paris is to be thanked for his statistical help. IX. APPENDIX Notebook Pages SL 6866 13459-60, 65, 67-75, 77, 87-88 20169-79, 81, 96-98, 200 24372, 80, 84 25703, 5, 7, 9=10, 15-17, 26-8, 30-4, 36, 41, 44-5, 48-9 31751-2, 54-8, 63, 65, 67-8, 70, 75-8, 81-7, 91-2, 95,98-800. 39252-3,56-61, 64-70, 72-3, 75, 78, 82, 84-7, 89-94, 96,98, 300. - J. R. Darby hhm DSW 622198 N. W. Touchette STLCOPCB4096231 46. APPENDIX I Windshield Fogging Test Precision I. Experimental Data The following replicated 2x4 factorial experiment was per formed to determine the precision of the windshield fogging test using black samples and infra-red heat source. Experiment 1 2 3 4 Experimental Data Plasticizer DOP DIDP DOP DIDP DOP DIDP DOP DIDP Specular Reflection 57, 64 88, 86 49, 48 81, 79 65, 6l 89, 92 52, 47 82, 91 II. Analysis of Data The above experiment was analyzed by a standard analysis of variance with the following results. Source Plasticizer Experiments Residual Total Sums of Squares 5,815.0625 555.6875 151.1875 4,519.9575 ANOVA Table D.F. 1 5 11 Mean Square 5,815.0625 118.5625 15.7445 15 F 277.4*** 8.65** E(MS)^1^ 8(5p|; (i) = Variances which the mean squares estimate *** Significant at the 99*9$' level ** Significant at the 99*0 level The mean squares obtained in the analysis of variance can be separated into the components of the total variance which they estimate as follows: Thus if. = variance due to experimental error = variance due to experiments <nT variance due to plasticizers DSW 622199 STLCOPCB4096232 47 APPENDIX II Windshield Fogging Test Precision I. Experimental Data The following experiment was performed to determine the preclsion of the windshield fogging test using white vinyl discs and heated in an oil bath at 93*0. Experiment Plasticizer Specular Reflection 1 DOP 40, 33, 33 DIDP 78, 73, 78 2 DOP 35, 35, 42 DIDP 81, 74, 78 3 DOP 32, 32, 35 DIDP 76, 73, 73 4 DOP 37, 38, 37 DIDP 76, 77, 78 -- II. Analysis of Data The above data was analyzed by a standard analysis of variance with the following results. ANOVA Table Source DF Plasticizer 1 Experiment 3 Residual Total 19 23 Sums of Squares 9,841.5 59.33333 123.16669 10,024.0 Mean Squares 9,841.5 19.77777 6,48246 F E(MS) *** <^8+ 12^ 3-051 *** Significant at 99-9# Significant at 90# level of significance DSW 622200 STLCOPCB4096233 48. For One Sample In Each Experiment: Within experiment standard deviation = Sw =y^^="*2.54607 Within experiment 95$ confidence limits = + 5*52 Between experiment standard deviation = Sb2= 6.48246 + 2.2159 =8.69856 sb = 2.9495 Between experiment 95$ confidence limits = + 6.15 When Duplicate Samples are run: _S_ S- =NfrT" sw x = 1.800 95$ limits = + 5.76 Sb x - 2.0855 95$ limits = + 4.35 When Triplicate Samples are Run: swx =1.470 = I.705 95$ limits = + 5.07 95$ limits = + 5.56 DSW 622201 STLCOPCB4096234 r_ Cl CJ h DSW 622202 STLCOPCB4096235