Document 3QYgjBKDdebBY2m12ZQy78m26

CONTAINS RES WHEN; fSSUUlB .CsS i Distribution on last page CDP-ES-80-11 Issued 3/28/80 Copy No. /*-/ T. C MERCER, JR. C&P DEPT. INFORMATION SERVICES JACKSON lABORATCRY e x p e r ime n t a l s t a t io n RESEARCH AND DEVELOPMENT DIVISION TECHNICAL REPORT CHEMICALS, DYES AND PIGMENTS DEPARTMENT E, I. DU PONT DE NEMOURS & COMPANY TiQ2 MICRONIZING AIDS Work Done By: Report Written By: Approved By: Patent situation Approved By Previous Related Reports: Project Code: Type Technical Work: Period Covered: Notebook No.: Personnel: Paul G. Schmidt Paul G. Schmidt K. K. Bhatia J. W. Heberling Date: 1/7/80 None 7053-184484 IEB Oct. 1978 - Dec. 1979 16096 J. B, Dunson, Jr., G, A. Schurr, J. 0, Hitch, T. B. Ewell ABSTRACT It has been shown that a micronizing aid reduces grinding energy by retaining chemisorbed water and/or hydroxyl on the pigment surface. This water and/or hydroxyl dissipates electro static charge developed during the shearing of the pigment and minimizes re-agglomeration. The effectiveness of micronizing aids has been empirically correlated to their known physical properties, and alternatives to the currently used aid, triethanolamine (TEA), are suggested. N40794 2 CDP-ES-80-11 X. INTRODUCTION Triethanolamine (TEA) is used as a grinding aid to reduce micronizer steam on all plastic grade pigments but is used on only 6% of R-900, R-902 and R-960 production, due to its alleged incompatibility in certain customer formulations. A broadly applicable micronizing aid would not only reduce steam costs but could also reduce inventory costs by eliminating TEA-treated pig ment package codes. Lower micronizer steam/pigment ratios are needed to obtain equivalent gloss and dispersion when TEA is added to the pigment (1). Improvements in product performance due to TEA addition are: Higher gloss in solvent-based paints (1). Better dispersion in plastics (2) (3), solvents and waterborne paints(1). Prevention of yellowing in polyolefin plastics (2). A survey of current literature, compiled by Dave Schussler, Chestnut Run, has Shown many secondary references to TEA-related problems, but with very scanty documentation. He has confirmed, however/ higher millbase viscosity in solution vinyls (4) (5), slight overbake discoloration for TEA codes in polyesters, and Varying effects on the cure rates of acid catalyzed polyesters (6). A large number of organic grinding aids have been tested in our department since "'1965. Reports on the most promising can*didates are listed in the references (7-16). These include amines, polyols, polysiloxanes and azelates. TEA belongs to both the amine and polyol groups. II. OBJECTIVES These studies were initiated to develop a compatible TiOj treatment which will lower the amounts of steam required to micron-' ize R-900, R-902 and R-960 pigments. The approach was to define the mechanism by which TEA improves pigment gloss and dispersion in order to effectively choose new candidates and then select more compatible/ non-amine aids, that would be expected to perform in a similar manner. DUP050059408 - 3 CDP-ES-80-11 III, SUMMARY & CONCLUSIONS Evidence has been accumulated which shows that the role of the micronizing aid is to retain chemisorbed water and/or hydroxyl groups on the pigment surface. This water and/or hydroxyl dissipates electrostatic charge developed during the shearing of the pigment and minimizes re-agglomeration. The effectiveness of a given micronizing aid has been found to be related to its boiling point, molecular weight and its number of functional groups - The functional groups are those which can interact with pigment chemisorbed water or surface hydroxyls and as such can be alcohols, amines, acids or esters. These parameters have been incorporated into an efficiency factor, viz. the micron izing aid efficiency factor (M.A.F.) and related to 30J gloss. The effectiveness of different micronizing aids has been rated and compared to TEA. Sorbitol is one of a series of predicted compounds which might replace TEA and be used to lower the S/P requirements of current production. IV. PATENT SITUATION 1. Filing Action - No patent action is to be initiated at this time. 2. Patent Protection - We have no patents in force specific to use of TEA as a micronizer aid. V. PROGRAM The program is to determine micronizer steam reduction with potential alternative aids and to evaluate compatibility with a customer formulation where TEA is believed to cause problems. VI. PUBLICATION STATUS There are no plans to publish any portions of this work. DUP050059409 -4- CDP-ES-80-11 VII. SPECIAL SAFETY PRECAUTIONS The products formed are not toxic. The chemicals used to treat the pigment are handled in accordance with normal practices. However, in situations wherein the pigment gets airborne, dust masks and hoods are used. Gloves are worn for. all chemical handling. VIII. ENVIRONMENTAL CONSIDERATIONS There are no pollution problems associated with this work that would not be considered normal in our pigment processing systems, in the laboratory or plant. IX, ACKNOWLEDGEMENT The writer gratefully acknowledges the assistance of J. B. Dunson, Jr., and G. A. Schurr of the Engineering Department for the experimental work on the ETC micronizer. He is also thankful to C. V. Miller and J. 0, Hitch for analytical assistance, and to T. B. Ewell for his diligence in this work. DUP050059410 5 CBiP-ES -80-11 TABLE OF CONTENTS Page I. INTRODUCTION . ............................................................................. 2 II, OBJECTIVES ................................... ......... 2 III. SUMMARY & CONCLUSIONS.......................................................................... . 3 IV. PATENT SITUATION ............. .......................... 3 V. PROGRAM....................................................... 3 VI.. PUBLICATION STATUS ..............................................................................................3 VII. SPECIAL SAFETY PRECAUTIONS .............. 4 VIII. ENVIRONMENTAL CONSIDERATIONS ............. 4 IX. ACKNOWLEDGEMENT ........................................................ 4 DISCUSSION A. Conductivity Measurements . . . . . , . . . . . . 6 B. Engineering Test Center Mirconizer Tests ..... 7 C. Edge Moor 8 Inch Micronizer Tests ........ 9 D. Thermogravimetric Analysis (desorption) ..... 9 E. Thermogravimetric Analysis (adsorption) ..................... 9 F. Alternatives to TEA ............................................................................10 G. Evaluation of Alternatives ............ 12 APPENDIX .......................... ............ ............................... 13 REFERENCES , . . . .................................................................................. 15 INDEXING TERMS ............................................................................................................ 17 FIGURES I THRU XIV 18-31 TABLES I THRU VIII ............................................................................................ . 32-39 LIST OF CHEMICALS ................................................................... 40 DISTRIBUTION................................................................................................................41 DUP050059411 - 6 CDP-ES-80-11 DISCUSSION Ti02 particles have regions relatively rich in AI2O3 within a matrix relatively poor in AI2O3. These aluminum-rich "islands" will be p-type semiconductors with different values of work func tion, resistivity, and dielectric constant than the n-type semi conductor matrix. As a result, there should be a polarization of charge within the particle which will generate non-uniform external electric fields. The edges of the "islands" will be strongly reactive chemically due to loeal electron density gradients. Par ticles as a result can be held together not only by short range Van der Waal's forces, but also by Coulombic forces capable of relatively long range interactions between "island" edges on adja cent particles. Not only should more work be required to micronize polar ized particles than nonpolarized particles (due to differences in work function and dielectric constant), but due to the high resistivity of the Ti02 matrix the sheared particles will tend to have equal and opposite charges and try to reagglomerate. If the particles are separated more rapidly than electrons (or holes) can move to cancel the polarization, the separated particles will bear equal and opposite charges. The pertinent electrical time constant is called the "charge relaxation time constant" and is numerically equal to the product of the permittivity of the material with its resistivity. The role of TEA then could be to reduce the TiC>2 Surface resistivity and its charge relaxation time constant. Amine nitrogen (Lewis base) could react with "island" edges (Lewis acid) . The resulting shift in TEA electron density would permit the ethanolic hydroxyls to function as weak Lewis acids and bond locally with the TiC>2 matrix (n-type semi-conductor = weak Lewis base) . The resulting relatively conductive organic network would permit charge to migrate much more rapidly even with only a fraction of a mono layer coverage. This could be a bulk or localized phenomenon. A. Conductivity Measurements Electrical conductivity measurements showed that TEA treated Ti02 did not permit the more rapid dissipation of charge than non-treated samples. TEA treatment lowered the bulk conductivity of a TiC>2 particle (Pig. I) . The charge relaxation time constants (l.e., the time it takes for an electrostatic charge to migrate across a unit surface)are from 1 to 100 seconds for TEA treated samples; and from 1 to 10 seconds for control R-900.. (The time it takes to shear an agglomerate is estimated to be of the order of 0.1 to 1 millisecond). DUP050059412 -7- CDP-ES-80-11 These results do not preclude, however, that TEA may still be influencing the build-up and dissipation of charge in localized areas of the pigment. Experiments were set up at the Engineering Test Center micronizer to answer this question. B. Engineering Test Center Micronizer Tests The purpose of this investigation was to determine: 1. if electrostatic charge can be detected and measured during the micronization of pigment. 2. if this charge was related to the efficiency of pigment micronization. 3. if the charge can be controlled by an external electric field. 4. the factors which influenced the charge. 5. the effects of TEA, 6. if micronizer parameters can be adjusted to give R-900 dried discharge (D.D.) micronizer efficiencies equivalent to TEA treated R-900 DD. The Engineering Test Center (ETC) micronizer is a single stage, single pass unit with a 0.161 inch sonic nozzle (Fig. II). It is equipped with two spark plugs at the throat of the nozzle. They are connected to a 6000 volt transformer capable of gener ating 0.40 milliamps current. An electron probe (connected to an electrometer) is located at the entrance of a 3 to 5 micron rated cyclone. The probe can detect and measure net electrostatic charge. Micronizer efficiency is determined by the amount of sample pass ing through the cyclone and collected in the second stage Dacron Twill bag filter. Typical 30J gloss values for R-900 collected in the second stage filter are 74 to 76 and for the pigment col lected in the cyclone, 24 to 26, The results of this investigation from over fifty treated and non-treated pigment samples micronized showed; 1. Electrostatic charge was detected and measured during the micronizing of R-900 DD and TEA treated R-900 DD. DUP050059413 8 CDP-ES-80-11 2. This charge was related to the efficiency of the micron!zer. The smaller the net charge measured on the pigment, the greater was its efficiency (Fig. ill). This effect was essentially independent of the presence of TEA, the steam to pigment ratio, the temperature of the stream or the thermal history of the TiC>2 3. The micronizer efficiency could not be significantly altered through the application of external electric fields. The calculated repulsive forces between par ticles as a result of these fields should have been in excess of the attractive forces between the particles (Appendix I). 4. The electrostatic charge was significantly influenced by: a. the water content of the pigment, i.e., temper-* ature of the pigment before micronization - the higher the temperature, the higher the net charge and the lower the efficiency of the micronization (Fig. IV). b. the relative humidity of the steam (steam temp erature) during micronization - the lower the temperature, the smaller the net charge and the higher the efficiency (Fig. V), c. the S/P ratio - higher charge and lower efficiency were observed for feed ratios above and below 200 g/minute, (S/P = 1.7). d. the presence of TEA which decreased the net electrostatic charge and increased efficiency. Table I. Table I shows that at S/P ratios $1.7, R-900 DD can be as efficiently micronized as TEA treated R-900 DD under conditions which maximize the water content of the pigment - no preheat treat ment and low steam temperatures $350F . Under conditions which facilitate dehydration of the pigment - preheat treatment or steam temperature ^350F - the performance of either pigment can be degraded, R-900 DD more so than TEA treated R-900 DD. At S/P ratio >1,7, TEA treated R-900 is micronized more efficiently than R-900 DD. The efficiency at which R-900 DD could be micronized could not be increased to that of TEA treated R-900 DUP050059414 -9- CDP-ES-80-11 by pretreating the R-900 DD, e.g. 90C, 20% relative humidity. Under conditions which facilitate dehydration of the pigments, the performance of both pigments were degraded, R-900 DD more rapidly than TEA treated R-900 DD. C. Edge Moor 8-inch Micronizer Tests Results on the Edge Moor 8 inch micronizer confirm the above effect of pigment moisture on 30 J gloss. Table IX. The effect was smaller for the TEA pigment than for the non-treated pigment. No trends dependent upon steam temperature (relative humidity) could be detected at any pigment moisture level on this equipment. Efforts to improve the gloss of R-900 DD by varying the moisture content of the pigment, e.g,, pre-treatment at 90C, 20% R.H., failed to match the efficiency of the TEA treatment. D. Thermogravimetric Analysis (desorption) Thermogravimetric data were obtained on a series of pigments treated with micronizing aids reported in the literature. The data show that micronizer aids minimize the TGA weight loss (presumably water) of a pigment. The weight loss has been related to the 30J gloss of the pigment. The relationship is independent of the micronizer aid employed. The smaller the weight loss at a given temperature, e.g, 200C, the higher the 30J gloss of the pigment. Pig. VII, Typical TGA curves arc illustrated in Pig, VIII for ethanolamine, diethanolamine and triethanolamine. This result supports the hypothesis that TEA functions by retaining water in the pigment surface which in turn helps to dissipate electrostatic charge. E. Thermogravimetric Analysis (adsorption) Additional evidence was compiled which shows that the amount of TEA adsorbed by the pigment and the effectiveness of TEA as a micronizing aid are proportional to the amount of surface hydroxyl or chemisorbed water on the pigment. The TEA adsorbed by R-900 coated with boehmite, trihydrate or an amorphous alumina at 150C has been measured. Table III. Similar measurements were made on R-960. The boehmite R-900 had a higher affinity for TEA than the corresponding trihydrate or DUP050059415 10 CDP-ES-80-11 amorphous alumina at this temperature. The boehmite alumina R-900 also requires higher temperatures than the trihydrate or amorphous alumina to remove its chemisorbed water. Figure IX. Thus the amount of TEA adsorbed is in proportion to the residual chemisorbed water on the sample. The TEA adsorption by the boehmite alumina coated R-900 was also measured at 100, 150, 200 and 250C, Table III. The amount of TEA adsorbed decreased with increasing temperature. At temperatures above 250C, little or no adsorption was observed. This, however, is probably not only due to the loss of surface hydroxyl but also the result of increasing TEA vapor pressure and lower sticking coefficient. Therefore, the TEA adsorption by boehmite coated R-900 was measured after the sample had been heated to 600G in dry nitrogen, The dehydrated pigment had a significantly smaller amount of TEA adsorbed. Table III. The above results are consistent with the effect observed on the Engineering Test Center and Edge Moor 8-inch micronizers where dehydration of the pigment before the addition of TEA mini mized the effectiveness of the TEA treatment and degraded the 30J gloss of the pigment. This is also shown in Figure X where the TGA weight loss of pigments treated with different amounts of TEA is recorded. The larger the amount of TEA, the smaller the weight loss and, referring to Fig. VII, the greater the 30J gloss. The above hypothesis can be summarized as such: The amount of TEA adsorbed by the pigment is proportional to the resi dual surface hydroxyl on the pigment. The effectiveness of TEA as a micronizing aid is a result of it minimizing the loss of the surface hydroxyl during micronization. It was also noted that TEA does not significantly adsorb onto R-960 pigment or pigment coated with amorphous alumina such as R-931. It utility as a micronizing aid for these pigments is therefore questionable. This has been reported by other investi gators . In these experimental runs, the TEA was heated to 9DC and passed over the Ti02 samples through dry nitrogen. F. ALTERNATES TO TEA Other high boiling, low molecular weight compounds which could adhere to the pigment chemisorbed water or hydroxyl func tionality were evaluated. DUP050059416 - 11 CDP-ES-80-11 A brief review of the literature revealed that the monoand di-carboxylic acid hydrocarbons met many of the requirements. The TGA adsorption at 150 C for these and other aids. Pig- VII, was determined for boehmite alumina coated R-900. Table IV shows the materials. Fig. XI shows that the amounts adsorbed were directly related to the boiling point of the material independent of alco holic, amine or carboxylic acid functionality. There was no adsorp tion of a high boiling compound with only hydrocarbon functionality, viz. nona-decane (B.P. 330C) . It appeared, therefore, that the effectiveness of a micronizing aid should be related to its boiling point, inversely related to its molecular weight, and directly related to its number of functional groups, High boiling point compounds are required in order to permit condensation - sticking - of the compounds to the surface water or hydroxyl group. Low molecular weight com pounds are required to maximize the number of moles of the aid and multi-functionality to interact with the maximum number of hydroxyl groups. The functionality could therefore be an amine, ester, acid or polyol, etc. Table V is the result of an effort to rate the efficiencies of micronizing aids evaluated based on the above criteria. The efficiency of each aid is estimated as its boiling point or decom position temperature divided by molecular weight times the number of functional group and is represented as M.A.F., Micronizer Aid Efficiency Factor. The only micronizer aid illustrated with an M.A.F. greater than TEA (M.A.F. = 7.21) is pentaerythritol (M.A.F. = 8.40) . After TEA is trimethylol propane (M.A.F. =* 6.2). The next six micronizing aids has M.A.F.'s closely grouped between 4,0 and 5.0, The remaining aids have M.A.F.'s below 3.50. From this table only pentaerythritol and trimethylol propane should be suitable replacements for TEA. There are, however, problems in coating pigment with pentaerythritol because of its high meiting point, 262C, and limited solubility in common solvents. Fig. XII is a plot of 30J gloss versus the M.A.F. for many of the micronizing aids evaluated. The pooled standard deviation of the 30J gloss measurement is 2.3. The 30J standard deviation for this correlation is 2.8. The correlation coefficient is 0.92. These results indicate that the best micronizing aids would be those with the largest number of functional groups and the lowest total molecular weight for a given boiling point. Ideally this corresponds to a compound composed solely of functional groups. The functional group number - molecular weight ratio could then be expressed as n over n times "F" where n is the number of functional groups and "F" is the formula weight of each group. This ratio would be a constant for each functional group. The M.A.F. could then be expressed as the boiling point times the constant. DUP050059417 - 12 CDP-ES-80-ll Table VI lists the reciprocal formula weights of the basic units containing the functional groups which make up the molecular weight of a micronizing aid. Also listed are the boiling point ranges required by compounds to have an M.A.F. greater than TEA assuming that all the functional groups indicated can interact with pigment surface hydroxyl. Table PGS-I explains why alcohols and amines have been the preferred micronizing aids - their reciprocal formula weights are the highest. Also, the literature boiling points of compounds associated with the other functional groups are well below those required - with the exception of the silicones. A review of the literature shows that some of the best non-nitrogen containing candidates for a new micronizing aid are the polyols: d-glucose, meso-erythritol, sorbitol and galactitol (Table VII). These compounds are water soluble and melt below the temperatures associated with micronization. G. EVALUATION OF AtTERNATIVES The 30J gloss of R-900 pigment treated with the above aids and their costs are shown in Table VIII. All 30j glosses were equivalent to or better than the gloss of the TEA treated sample with the possible exception of d-glucose where some decomposition was noted. Overall, sorbitol is the lowest in cost of this series and would be the best alternative to TEA. TGA data also confirms these findings. Previous tests showed that the weight-loss of a treated pigment at 200C is inversely related to the 30J gloss of the pigment. The weight losses at 200C for the experimental pigments were almost identical, Fig. XIII, and smaller than for the TEA treated pigment, Fig. XIV. DUP050059418 13 CDP-ES-80-11 APPENDIX REPULSIVE AND ATTRACTICE FORCES BETWEEN PIGMENT PARTICLES The estimated number of 1 micron Ti02 particles at a feed rate to the micronizer of 200 grams per minute is 1.5 X 10^2 particles per sec. With a corona current from both spark plugs of 0.45 milliamperes, the electron flow per second is calculated to be 2.8 X 1015 electrons/sec. The number of electrons generated per 1 micron particle is thus approximately 2 X 10% The repulsive force between two particles, each with an electri cal charge of 100 electrons, (100 is the maximum number possible on a 1/2 micron diameter particle without establishing corona) is 2 X 103 dynes/cm^. x ql q2 F = . ,, h2 F force in Newtons q = charge in coulombs e = absolute dielectric constant of media in farads/meter h = separation between particles - meters (assume 1/2 p) DUP050059419 - 14 CDP-ES-80-11 F- (100 x 1.6 x 10~19)2 4tr x 8.85 x lO"12 x (0.5 x 10-5)2 -12 5 F - 9/3 x 10 Newtons x 10 dynes/Newton 9.3 x 10 dynes The area of l/2u particle * 2 . J X (.25)2 y2 X 10~8 cm2/y2 = 4.68 x 10 -10 cm2 cross section area Force per unit area - 9.3 x 10 --7 dynes - 2 x 10 3 dynes/cm7 4.68 x 10-10 The attractive forces between particles as Lifshity* calculates as 0.093 dynes/cm/ _ he H4 2it 240 V1/ * <0> calculated for a particle l/2y apart h = Planck's const.-erg-sec. c = Velocity of light-cm/sec H Particle separation dist.- ems e - Static dielectric const. 4> - Const, (value from Tables) 6.62 x IQ"27 x 3.0 X (3.14)2 F (5)4 x 240 x 0.77 . 2 F = .093 dynes/cm Less than 5 electrons per particle would have been required to make the repulsive forces smaller than the attractive forces. electrons) 2 x 10' (5)2 (100)2 049 dynes/cm2 Soviet Physics, Vol. 2, No. 1, January 1956, "The Theory of Molecular Attractive Forces Between Solids", DUP050059420 - 15 * CDP-ES-80-11 REFERENCES 1. J. B, Hill, New Johnsonville, Semiannual Plant Tech. Report/ PTJ-SA-76-2, June, 1976, p. 227d. 2. J. T. Looby, Edgemoor, Semiannual Plant Tech. Report, PTE-SA-75-2, p. 143. 3. J. T. Looby, Edgemoor, Semiannual Plant Tech. Report, PTE-SA-76-2, p. 106. 4. Fed. Series on Coating Tech., Unit 19, 5. H. E. Casseday, Pigments Marketing Report No, 108, 9/2/77. 6. B. H. Garth, Chestnut Run Work Request, WG-21-76. 7. R. C. Smith, Edgemoor, Semiannual Plant Tech. Report, PTE-SA-55-6. (A review of work done on organic treatments before 1955.) 8. G. E. Watkins, New Johnsonville Triannual Plant Tech. Report, PTJ-TA-66-3, p.. 96d. 9. G. E. Watkins, New Johnsonville Triannual Plant Tech. Report, PTJ-TA-67-1, p. 30d. 10. G, E. Watkins, New Johnsonville Triannual Plant Tech, Report, PTJ-TA-67-2, p. 59d. 11. M. R. Baloga and G. E, Watkins, New Johnsonville Triannual Plant Tech. Report, PTJ-TA-68-1, p. 14d. 12. G. E. Watkins, New Johnsonville Triannual Plant Tech. Report, PTJ-TA-68-2, p. 35d. 13. A. B. Canfield, New Johnsonville Report, PTJ-18-69. 14. G. E. Watkins, New Johnsonville Triannual Plant Tech, Report, PTJ-TA-70-1, p. 14d. 15. G. E. Watkins, New Johnsonville Triannual Plant Tech. Report, PTJ-TA-70-2, p. 20d. 16. G. E, Watkins, New Johnsonville Triannual Plant Tech. Report, PTJ-TA-70-3, p, 44d, 17. G* E. Watkins, New Johnsonville Triannual Plant Tech. Report, PTJ-TA-71-3, p. 47d. 18. H. A. Wildt, Edgemoor Triannual Plant Tech. Report, PTE-TA-72-2, p. 107 19. J. T. Looby, Edgemoor Triannual Plant Tech, Report, PTE-TA-72-2, p. 129. 20. J. T. Looby, Edgemoor Semiannual Plant Tech. Report, PTE-SA-74-1, p, 65 DUP050059421 16 CDP-ES-80-11 21. G. E. Watkins, New Johnsonville Semiannual Plant Tech. Report, PTJ-SA-76-1, p. 98d. 22. G. Ferris, Chestnut Run Work Request, WG-32-76 (PTS-3781). DUP050059422 INDEXING TERMS TEA Mieronizing Aid Electrostatic Charge Effect of Moisture New Mieronizing Aids Ti02 Grinding R-900 17 CDP-ES-80-11 DUP050059423 - 18 CDP-ES-80-11 Figure I Resistivity vs. Reciprocal Degrees Kelvin For R-900 Pigment RESIST WITY<OHM-METERS) I017 30-JUL-79 H DUP050059424 - 19 figure II Engineering Test Center Micronizer CDP-ES-80-11 6. Access for charge or mass sampling* 7. ' Coarse fraction from primary cyclone. 8. Fine fraction from secondary cyclone. 9. Access for charge or mass sampling, 10. Scrub water feed. 11. Pipeline scrubber/condenser. 12. Air vent to vacuum system through meter. 13. Whitewater from hotwell. 14. 2 Champion spark plugs 0.050 gap 0.40 milliamps 15. 1/4" stainless steel probe in Teflon jacket. Electrically isolatable components (>10 meg ohms to ground when analyzer circuit is open) corona charger steam nozzle venturi throat charge analyzer cyclones charge analyzer DUP050059425 20 - CDP-ES-80-11 Figure III ETC % Efficiency vs, Microamps in Shear 2one For R-900 DD % EFFICIENCY 095I 30-JUL-79 DUP050059426 MICRO AMPS 21 Figure IV ETC: Microamps and % Efficiency vs. Pigment Preheat Temp. F For R-900 DD Pigment CDP-ES-80-11 10*05 3S-JUL-79 DUP050059427 MICROAMPS 22 - Figure V ETC .Miqroamps and % Efficiency vs* Steam Temp. F 0 For R-900 DD Pigment CDP-ES-80-11 10112 30-JUL-79 HmhH* o Hn>* o Relative Humidity DUP050059428 itBTlClfflCY - 23 - Figure VI ETC Microamps and % Efficiency vs. Feed,Hate steam to Pigment Ratio For R-900 pigment CDP-ES-80-11 3**JULr79 M icro a m p s DUP050059429 - 24 FIGURE VII 30J Gloss vs. TGA Weight Loss 200C For R-900 Pigment and Micron!zer Aids (0.5%) CDP-ES-80-11 30J GLOSS 30J GLOSS US TGft 10*13 17-JUL-79 30J G loss MZR Aid (0.5% weight) 1) Ethanol Amine 2) Diethanol Amine 3) Triethanol'Amine b) Trimethanol propane 5) Pentacrythritol 6) AMP 7) Nitrilo triacetic acid 8) Dioctyl azelate 9) Control 10) TEA (.25% weight) DUP050059430 MASS tOSS(MCG) - 25 Figure VIII TGA Mass Loss vs. Temperature MZR. Tri-Di-Mono-Ethanol Amines n R"900 Plgment CDP-ES-80-11 09'47 6-AUG-79 T(C) DUP050059431 200. 300. 400. 500. 600. 11'38 30-MAV-79 26 CDP-ES-80-11 ,i 11 i I n i i Ll l l i .I i i .i.L-I. i i ! i 1 < i m I . i . 1 . , i | i i , , | , f tot 4 Vi /!/ * FIGURE I X d (Mass L o s s ) /d (T em p.) v s . Temp, f o r R -900 DERIVATIVE CURVES, TI02, MZR DHASS/DT Xie -3 - rrn'-prn ; i i i i 11111 11 i i ip II]IIII 9 TT 9 in 9 u> 9 to 9 in in T i* pi cj cu cu ^ in* 9 99 DUP050059432 DUP050059433 - 28 - FIGURE XI M1CR0NIZER AID BOILING POINT G .............VS ' % WT. ADSORBED OHTQ R-900 - 15QPC XUT ADSORBED ONTO R900 ISO C CDP-ES-80-11 1) Ethanol Amine 2) Methanol Amine 3) Triethanol Amine h) AMP 5) Oleic Acid 6) Palmitic Acid 7) Trimethylol Propane Q) Glutsric Acid 9) Trimethylol Propane 10) Nona-decane DUP050059434 - 29 CDP-ES-80-11 Figure XII 30J Gloss vs. Micronizer Aid Efficiency Factor 30J GLOSS 1. Tri-ethanol Amine 2. Di-ethanol Amine 3. Ethanol Amine 4. Trimethylol propane 6. Oleic acid 7. Adipic acid 8. Palmitic acid 9. Pimelic acid 10. Glutaric Acid 11. Nona-decane 12. Control (water) 13, Control (alcohol) 14, Control (hexane) 15. Amino-methyl propanol 16. Nitrilotriacetic acid 17, Di-octyl azelate DUP050059435 -30 - CDP-ES~80-ll O JC o fr- DUP050059436 31 CDP-BS-80-11 C* o i-- DUP050059437 32 CDP-ES-80-11 Table I Effect of TEA and S/P ETC % Efficiency vs. TEA and S/P % EFFICIENCY Pigment Temp. 75 F S/P 0.4 R-900 D.D. R-900 D.D. (TEA) 20.4 20.0 0.7 23.9 25.8 1.7 29.0 34.4 2.5 15.2 32.0 4.2 11.0 30.0 25DF R-900 D.D. R-900 D.D. (TEA) 24.0 to o\ o 10.0 28.0 450F R-900 D.D. R-900 D.D. (TEA) 15.0 26.0 194F 20 %RH R-900 D.D. R-900 D.D.(TEA) 26.0 26.8 14.0 29.0 DUP050059438 33 CDP-ES-80-11 TABLE II EDGE MOOR 8" MICRONIZER 303 GLOSS VS PIGMENT PRE-TREATMENT Pigment Pretreatment Temp. S/P 1.5 2.3 75P R-900 DD R-900 DD (TEA) 78 80 78 84 250 F R-900 DD R-900 DD (TEA) 77 78 78 815 450E R-900 DD R-900 DD (TEA) 73 76 78 815 200F 20% RH R-900 DD R-900 DD (TEA) 78 80 DUP050059439 34 CDP-ES-80-11 CO On -C=Ot 0 o o O o ON ON UON oO CO o MICRONIZER AID ADSORPTION BY TiCU PIGMENT in Nitrogen 0o & 1 (*H4 *oH iHOr\ o IA H O IA H Q LA H <D EH Q OO o O 1a O LA rH H CVI OJ O IA H o oO O On o J o 1 On On P5 1 mi 1 1 CO FH4 OCO CVI C\J 0) D C\J VoO IAj .. 3 CO ON 4 I * ff <D *H S& O o On l Ph CO o OJ > <u A rtf H aa> <y 5 <aV fi <L> 4 a0 2O 1 i SHJ aipH>* <ID ai> DUP050059440 35 r& < CO o H CM H NO On H o ON CO O Pt CO ITS o o o o 0 O OH O6Oo o o f CDP-ES-80-11 TGA MICRONIZER AID ADSORPTION BY T iO . PIGMENT M <M 3 && H p. & :HO I cad 1 0HP) o ri a oaH S' ap; I3 *6Hd <D 0 0 $ S *8d I aJ o 5> 1 oop DUP050059441 - 36 - CDP-ES-80-'ll ^ <o a o oo CO O -3* -=r CVI &3 $ <S $ $ oCO 0o0 cy CO 00 CO b" CM o Q o Q vo CO CM *s o l B o -H 8p CVI CO CO S'CO CO CVI CM CO CM CM CM CM po OH ii vo OS .3* LA CVI VO .l/S CM O CO rH CM VO CM CO -3* CO 3t O OS -3" in CO vo O VO rH m CO VO in H H H H CM H H H H H ..-st CM CM CM CM ci> Jo ro 8ft rH VH o d oo o os o CO CM o o vo 3b o o CO vo 00 oo -3* o b-- b- in vo 00 8CO CO CM CM 00 00 CM CO 00 H H OO oo CO a0) & ft Ho QH III $1 1 H (V, a d rl O p p H s jj d H *d H 3 H 3 P HO O pH | 1S H H J 3 H H 0* p 5 8o 1 fd H i p S *P P p P H 3 p P +> P p o H s P H HP CD H 1l aoa) P 4> P 04 O 125 O to S4T MU SS HHP^ P f CQ (=-i * {^2? {25 H CM 00-3* DUP050059442 - 37 < * I P. CO Oon Cm OcOn SHot O Scnt --a=*r tory IfocA- o CinO o -a* cCCMMn -COaM- CmCVOJ j-at- cn CM ITS cn VoO cn vIAo -it -avo -a* CiOnMn CDP-ES-80-11 RECIPROCAL FORMULA WEIGHTS FOR COMMON FUNCTIONAL GROUPS' . X On oj O r-i cn -acn st st * St in St in CO in i*- >S. *>+. > * "N* H H H H H H H ri o < Is oo CO I Is w1-3 -S o CM ts oca <? ^ / > ,x a jn t i 01 01I 1 ? IOO o2 aww <? 8 i i CM &T a <? .Hs o g oa % J0ooC 3 oOS3 t 0n36H 55 I? 0r4s0OH3) a<OU CrH4O 4wu0W3 a a 8 CQ d o Hd 3 DUP050059443 Compound d-glucqse meso-erythritol sorbitol galactitol TEA 38 TABLE VII CDP-ES-80-11 MEW MICRQNIZING AID CANDIDATES Mail. Wt. 180 122 183 183 ll9 B.P 310d 329 360d 360s 360 f' No. of Funct. Grouns 6 5* U 5* 4* 4 3* M.A.F 10.3 8.6 10.8 9.8 T.8 7.8 7.2 assuming one group not functional ** " two groups " M d, decomposes s, sublimes DUP050059444 39 CDP-ES-80-11 TABLE VIII 30 J GLOSS ALTERNATIVES TO TEA CANDIDATE d-glucose***** m-erythritol sorbitol galactitol TMP TEA Control 30J GLOSS* 75.7 77.0 77.3 76.0 77.7 76.7 73 COST CENTS/LB, 13.0 *** 24.2 *** 27,5 16.0 * S/P a* 2.5, average of 3 measurements ** some decomposition during micrOnization *** available only in small quantities DUP050059445 LIST OF CHEMICALS Chemical Manufacturer/Distributor d-Sorbitol me so-Erythrito1 Dulcitol TMP Dextrose Carbowax 200 " 300 Palmetic Acid Ethanol Amine Calcium Nitrate Sodium Silicate TEA Boric Acid Glutaric Acid Dioctyl Azelate Nona-Decane Sodium Borate 1,2,4 Butanetrol Adipic Acid Nitrilo Acetic Acid Pimelic Acid Pentaerythritol Oleic Acid Sodium Pyro Phosphate " Metaborate TEA UPLA 713 774 801 734 803 2-Amino-2 Methyl-/Propanol TKPP Fisher Aldrich Eastman Aldrich Fisher Union Carbide II If Fisher Eastman MCB Du Pont . Fisher Fisher Eastman Reichhold Aldr.ich Fisher Aldriqh Fisher Eastman ll Fisher II II II Henkle ll II ii ii Aldrich Alfa DUP050059446 - 41 - CDP-ES-80-11 DISTRIBUTION 1. Paul G. Schmidt .2 K. K. Bhatia 3. W. J. Marshall, EM 4. H. B. Clark/R. W. Hess 5. R. A. Darby/A. S. Bjornson/L. T. Frick/J. G. Ishikawa 6. E. C.' Broge/J. Blackwell/J. A. Blumberg 7. J, M. Hustler .8 W. L. Kremer/G. H, Senkler, EM 9. L. N. Fisher/G. A. Hapka 10-11. Central Report index. Information Systems Department, c Rd. 3211 12-13. L, A. Wierzbowski, EM 14-19. .20 .21 22. CD&P Information Center, Experimental Station, Building 336 J. B, Dunson, Jr., Engineering Dept., Louviers D. H. Eastham/T. B. Scarfe/D. P. Schussler, DeLisle G. E. Lynskey/D. U. Gwost/M. Baloga, Johnsonville 23. J. G, Dickinson/W. J. McGinnis, Chestnut Run DUP050059447