Document VkRMQYmRgYYXK3wyYjRk4Jv8

pV\ farbrdtf yjj}^ q ^^ /.if.. ji oo fvJl. ^ TT (-<//*'/ i fo'f*t* (c.'ij Jjit CDP-ES-79-5 Issued Sept. 23/ i960 fotmVS. Copy No. CONTAINS CONFIDENTIAL INFORMATION. RESPONSIBILITY OF RECIPIENT. WHEN NO LONGER NEEDED, DESTROY BY BURNING OR SHREDDING. Copy distribution on last page EXPERIMENTAL STATION CHEMICALS, DYES & PIGMENTS DEPARTMENT RESEARCH & DEVELOPMENT DIVISION B. I. DU PONT DE NEMOURS & CO., INC. Ti02 PIGMENTS FOR INDUSTRIAL APPLICATIONS POLYESTER WATERBORNE SYSTEMS PROGRESS REPORT Work Done By: Approved By: Patent Status Approved By Project Codes Type Technical Work: Period Covered: Notebook No.: Personnel: L. J. Matienzo R. J. Bouchard J. W. Heberling 9/18/80 7053-184274 IEB August 31, 1978 - January 31, 17869 L. J. Janvier 1979 ABSTRACT A systematic study of the different steps involved in the formation of the dry film of a water-reducible polyester will allow to determine the factors controlling the deficient hiding of R-900 in this formulation. Techniques to study adsorption of acrylic and polyester water-reducible resins on Ti-Pure surfaces have been developed and conclusions on the nature of the initial adsorption process have been drawn. N40788 1 CDP-ES-79-5 INTRODUCTION Business Objective: Develop understanding of technical requirements for and behavior of Ti02 in new industrial systems (waterborne, high solids, radiation cured, etc.)* Develop pigment to meet specific needs as they are identified {e.g., high hiding Ti02 in waterreducible polyesters). Incentive: To ensure Ti-Pure performance in new systems. Projections are: System Solvent-borne Waterborne High-solids Powder Others % of Industrial Market 1977 (1982) 1987 91 30 5 20 35 1 10 20 35 10 100 100 Ti02 use in industrial coatings has been projected to be 210 MT in 1982 corresponding to -30MT/Y Ti-Pure sales to water borne and high-solids systems. OBJECTIVES A grade of pigment with high gloss and comparable hiding to that developed in an acrylic waterborne system (American Cyanamid XC-4011) is not available from any manu facturer for industrial polyester- systems. The design and selection of such a pigment or a dispersant needed to produce this improvement requires an understanding of surface, dispersant and vehicle interactions in the solvent medium. Fundamental studies in this area of waterborne polyesters are scant, therefore, experimental methods to develop useful information have been investigated* SUMMARY AND CONCLUSIONS Polyester and Acrylic Waterborne Systems Defined system to study adsorption of vehicles . onto Ti-Pure pigments from aqueous solutions. Developed size exclusion chromatography to detect adsorption of polyester from solution. v DUP050059189 * 2 - CDP-ES-79-5 Demonstrated that preferential adsorption of higher molecular weight fractions occurs under similar conditions to those existing in finished paints. Improved size exclusion chromatography to provide quantitative data on polymer adsorption. Developed first Langmuir adsorption isotherm of this type. Showed that polyester adsorption on R-9Q0 is a very fast process and the pigment behaves like alumina. Developed reverse phase liquid chromatography to detect adsorption of molecules from solution and allow direct sampling of slurries. Since a liquid chromatograph was not available in the laboratory, developed a faster technique to detect adsorption using ultraviolet spectroscopy. Showed agreement between data obtained by liquid chromatography and new technique, Determined equilibrium time required for reaction of R-900 (28), R-960 (01), dense silica coated pigment (3% Si02') and clean R-900 base with both acrylic and polyester waterborne Vehicles, obtained adsorption isotherms for r -900 (28), R-960 (01) and R-931 (01) pigments with both acrylic and polyester vehicles. Showed that R-900 C.D, material (Line I, New Johnsonville) behaves like finished product toward adsorption of polyester from solution: alumina is concentrated on base surface. PATENT STATUS r PROGRAM No patent action is contemplated. This program has been dropped, PUBLICATION STATUS time There are no plans to publish this work at the present SPECIAL SAFETY PRECAUTION The only consideration is to have enough ventilation when resins and paints are handled. i DUP050059190 ENVIRONMENTAL CONSIDERATIONS None, CHEMICALS USED R-900 (28), R-960 (01), R-931 (01), Rutile 99.99% Ti02 (SPEX Ind.), Cyplex 1600 polyester solution, American Cyanamid acrylic solution XC-4011, Tetrahydrofuran, Dimethylethanolamine (DMEA), Toluene and Methanol. TOXICITY DATA None, SPECIAL PRECAUTIONS None. ASSISTED BY L. J. Janvier. ACKNOWLEDGEMENT My special thanks to R. E. Johnson, L. Abrams and J. H. Boughton for their interest in this program. DUP050059191  i TABLE QF CONTENTS CDP-ES-79-5 INTRODUCTION............................ . OBJECTIVES . . . . . . . .. . SUMMARY AND CONCLUSIONS . . PATENT STATUS ....... PROGRAM . . , ...... . PUBLICATION STATUS ................... SPECIAL SAFETY PRECAUTION . ENVIRONMENTAL CONSIDERATIONS CHEMICALS USED ....... TOXICITY DATA ............................ SPECIAL PRECAUTIONS . . . . ASSISTED BY . . .... . . . . . . . ACKNOWLEDGEMENT ........... EXPERIMENTAL AND DISCUSSION ................... Polyester and Acrylic Waterborne Resins ..... Experimental slurry Composition ...................................... High Performance Liquid Chromatograph Analysis (HPLC Ultraviolet Analysis of Polyesters and Acrylics From Aqueous Solutions ........... A comparison of Adsorption of Polyester by SEC and UV Methods ................ Interaction of Polyester and Acrylic on Several Oxide Surfaces ............................................................. Kinetic Runs ............................................ .... Adsorption Isotherms .............. Adsorption on R-900 CD Base Material ...... Adsorption on Pure Titanium Dioxide ...... , A Retrospective View on Pigment Surface Chemistry 1 1 1 2 2 2 2 3 3 3 3 3 3 4 4 5 5 7 8 8 8 9 10 10 11 DUP050059192 TABLE OF CONTENTS (CONT'D) TABLES ** ***.* FIGURES ^# # . APPENDIX * INDEXING TERMS #. p*9* 12 22 36 37 DUP050059193 A - 4 CDP-ES-79-5 EXPERIMENTAL AND DISCUSSION The ultimate result on performance of any type of pigments in a paint formulation is a sum of processes that occur since the moment in which the components of the mill base come into contact with each other. In order to develop an acceptable level of hiding and gloss, pigments have to be dispersed in a vehicle until their particle sizes reach the submicron level. The mean diameter of a TiC>2 primary particle is about 0.2 pm but this smallness ensures aggregation since Van Der Waal's forces become important. These short-range forces operate in dispersions of solids in liquids and after the dispersion process stops# the particles may tend to re-aggregate unless a stabilizing mechanism can oppose the forces of attraction. Two stabilizing mechanisms are known and were described in some detail in my previous report (PTD-SA-78-28), Whatever the stabilization mechanism, a dispersion of pigment particles in a liquid is an equilibrium system, if this state is altered at any stage of the paint manufacture and final application, the end result will show some deficiency performance. The adsorption of macrmolecules plays an important role on dispersion of pigment particles in paints, in order to understand the importance of these interactions in a real system# a simplified model of a waterborne paint must be adopted. Since the amount of material adsorbed by the substrate can only be measured indirectly# i.e., by difference in concentration, one must work with dilute solutions. Then# the type of information that can be derived.will answer questions concerning the manner, the energetics and the kinetics of macromolecular attachment# the density of adsorption# the nature of any exchange reactions with solvents or surfactants, and the dependence of these features on the structures of surface, solution and macromolecules. Also, the dependence on such variables like concentration, temperature# pH, zeta potential# electrolytes and cosolutes can be established. Then, one can tie up pigment performance to the type of surface modification required to optimize optical properties in a particular system, in this case polyester waterborne formulations for industrial applications. Polyester and Acrylic Waterborne Resins Acrylic and polyester waterborne paints show different behavior associated with the type of pigment# i.e. surface treat ment# used. For example, polyester paints containing R-900 have a hiding power which is about 70% of their value in acrylic resins formulated at the same PVC (ca. 21%). The differences in endresults might be related to the adsorption mechanism of polyester and the type of stabilization which controls flocculation. DUP050059194 5 CDP-ES-79-5 The materials used for this study were two commercial resins. An acrylic, XC-4011, was chosen as a comparison since previous work on this area had used it extensively. Cyplex 1600, a water soluble polyester, was used for adsorption studies. In general, most commercial polyester resins have similar compositions and analogous behavior in this system. Since the structure and composition of the vehicles are important to interpret results, concerning the bonding and nature of the adsorbed layer, the physical and chemical charac terization of these materials was attempted. Table LJM-I shows the results obtained for the chosen polyester and acrylic. The main features of these are: Broad molecular weight distribution Different number of carboxylic groups/molecule Completely different chemical structure and molecular size. Once the approximate dimensions of the average molecule are known and the manner in which it attaches itself to the pigment surface, the thickness of the adsorption layer may be estimated* Experimental Slurry Composition Since the standard paint formulation with Cyplex 1600 contains about eight to ten components, a simplified model system w'as chosen for study. The components which comprise about 90% of the mixture were selected, these were; Cyplex 1600 or Acrylic XC-4011 resin Dimethylethanolamine (DMEA) De-ionized water* Aqueous solutions of resin were made by taking a known amount in a volumetric flask, adding de-ionized water and slowly titrating with DMEA until total dissolution of the resin was detected. The final pH of this solution was adjusted to 8.5-8.6. The slurry samples contained constant limiting ratio of pigment to solution. The slurry concentration was 10.0% PVC, based on R-900. High Performance Liquid Chromatography Analysis (HPLC) Liquid chromatography was considered as the initial experimental technique to give information on adsorption from solution. Since polyesters and acrylics have a broad molecular weight distribution, all of the molecules do not have the same DUP050059195 6 CDP-ES-79-5 bonding ability toward the pigment surface. A special form of HPLC, was chosen for the determination of selective adsorption. Size Exclusion Chromatography (SEC), based on molecular size separation was chosen for this work. The method, of SEC have been described in my previous report (PTD-SA-78-2B). Basic principles would indicate that in the case of macromolecular electrolytes, the larger size molecules will adsorb more easily on a solid surface. Of course both materials, polyesters and acrylics, have different bonding groups. The main adsorption for polyester occurs through ester linkages which hydrogen-bond onto the hydroxylated surface. An average of three ester groups and a carboxylic group exists in the average size molecule. In contrast, xc-4011 interacts with the pigment mostly through carboxylate linkages. In a typical experiment, 20.6g of pigment, were placed in a four-ounce jar and 45.0 ml of a solution of known concentra tion were added. The capped sample was shaken in a Pisher-Kendal1 mixer for a known length of time. Then the supernatant solution was gradually separated from the solid by centrifugation, ini aliquot of the supernatant was evaporated to dryness and the residue was dissolved in THE and then analyzed using a SEC system. Figure LJM-I shows the type of curves obtained from these experiments, in conclusion, as expected, larger size molecules adsorb preferentially on TiOo pigment, and flocculation cannot be caused by cullapse due to low molecular weight materials adsorbed on the coating. Quantification of adsorption results are necessary in order to derive an adsorption isotherm. Preliminary tests showed that area integration of the distributions is directly proportional to concentration and this approach was adopted for quantitative analysis. Then, the amount of material adsorbed by the surface can be measured by area differences of the polyester or acrylic solution before and after contact. Figure LJM-II presents the changes on molecular size distribution before, at and after a monolayer coverage of polyester on R-900 as measured by SEC on several samples after contact of solution and pigment. Table II gives the results obtained for Cyplex 1600 and R-900 used to determine the Langmuir adsorption isotherm for the process at room temperature. The method above described has a drawback since samples have to be evaporated to dryness and then carefully diluted with THF before analysis. As an improvement, another HPLC method was designed to allow direct handling of aqueous samples. The technique adopted was Reverse Phase Liquid Chromatography which allows to program solvent polarity and thus separation of molecules at different and controllable rates. Figure LJM-III shows the marked difference after adsorption, although, it is necessary to note that in this case the smaller and more polar molecules elute Out of the column first. DUP050059196 -7- CDP-ES-79-5 The above results conclude that# as predicted, lower molecular weight species remain in solution and in equilibrium with higher size macromolecules adsorbed on the pigment surface. IntermoieCular rearrangements, at least with an alumina-only surface, do not occur. Intramolecular re-distributions are expected to continue for some time as detected in organic solvent systems containing simple polyesters (K, Hamman and G. Joppien, 1977). It is expected that after a few hours, about 40 to 70% of the ester-hydroxyl linkages remain undisturbed. About two out of three ester groups remain in contact with the surface and the thickness of the adsorbed layer increases slightly but does not provide enough of a distance to produce steric stabilization. Electrostatic effects then become important at the operating pH, since the macromolecules are ionized. Ultraviolet Analysis of Polyesters and Acrylics From Aqueous Solutions As explained above, the adsorption process can be followed by HPLC but sample preparation is rather involved and data handling consumes a relatively large portion of time. Since aromatic acids or anhydrides are used in the synthesis of commercial polyesters, they absorb strongly in the ultraviolet region of the electromagnetic spectrum. Infrared work has shown that' even the nonadsorbing fractions contain these aromatic groups and polyester molecules of all sizes adsorb in the UV. Figure LJM-IV shows the spectrum of a methanolic solution of polyester after contact with R-900. The methanol vs. methanol reference spectrum is added for comparison. The peaks appearing at X 279 and 288 nm are assigned to n * t t * transitions. These maxima do not shift on adsorption and their absorbance readings can be used to determine concentrations in the range in which the Beer-Larobert law is obeyed. Likewise, acrylic resins containing unsaturated bonds which show appreciable UV absorption below 270 nm. Methanolic solutions of XC-4011 have a UV band at 268 nm and this maximum can be used to follow concentration changes. In both cases, methanol solutions are used since this solvent allows the un coiling of the macromolecules present in aqueous solutions which if not considered, will induce scattering losses in the measure ments . If the concentration range is kept below micelle formation, good linear correlations are possible for both materials. Figure LJM-V prevents typical calibration curves. DUP050059197 A Comparison of Adsorption of Polyester bv SEC and UV Methods ------ -------------- Some samples of Cyplex 1600 and R-900 were prepared and the concentration of adsorbed polyester was measured by peak area integration (SEC) or by direct determination of resin in the supernatant solution (UV). The adsorption isotherms for both sets of data are shown in Figure LJM-VI and show that: The saturation point or monolayer coverage for Cyplex 1600 on R-900 (28) is 52.5 ma/a by SEC and 49.1 mg/g by UV analysis. ,, UJA 0 The differences on the above results/ although small, are attributed to: - Inherent experimental error obtained by any method based on the measurement of concen tration differences. - Size exclusion chromatography use tetrahydrofuran as the carrier solvent while UV analysis used absolute methanol. - The detection by SEC is made at 254 nm while the second technique uses the peak maximum at 288 nm. In summary, UV spectrophotometrie analysis for commercial polyester and acrylic vehicles yields adsorption data as good as any obtained using a more elaborate analytical technique. Interaction of Polyester and Acrylic on Several Oxide Surfaces ' ' The control on adsorption is governed by the nature of the outermost layer of the pigment present at the solid-liquid interface, and, it is possible to anticipate different behavior as the composition of the coating changes. Ultimately, this will contribute to the performance of the pigment in a waterborne paint composition. Several commercial and experimental pigments were selected to study these effects. The composition of the surface was varied from silica only through silica-alumina mixtures and finally alumina-only coatings. Two types of experiments were performed and these are discussed below. Kinetic Runs Since the intention of the present study was to compare macromolecular adsorption with pigment surface composition, the equilibrium time for the process was measured in each case. A sample of polyester or acrylic of known concentration was con tacted with pigment and the decay of absorbance of the supernatant DUP050059198 9 - CDP-ES-79-5 solution was followed as a function of time. The concentration of the solutions was carefully chosen to maintain sub-monolayer coverage. In other words, preliminary runs were made to determine the concentration range in which the pigment surface remained active and showed absorbance changes. Figures LJM-VII and vm present the curves obtained'with four different pigments in polyester and acrylic solutions respectively. Table LJM-III summarizes the equilibrium times for both sets of experiments. Conclusions: An alumina-only surface reaches equilibrium faster than any other pigment, More macromolecular adsorption is achieved with an alumina coating. The adsorption of polyester and acrylic is minimal for dense silica coated pigments within 100 hours of contact. Adsorption isotherms The adsorption isotherm for any system under investigation was derived by measuring the change in concentration in the liquid phase after equilibrium was attained. In each study, the amount of pigment and the volume of solution were kept constant. The concentration of polyester or acrylic varied gradually from sample to sample and, normally, ten samples were used for each isotherm. Also a calibration curve at the specified wavelength was obtained for the initial solutions and used to measure the unknown concen trations. The isolation of the supernatant solution follows the procedure described in my previous report (PTD-SA-78-2B). The experimental results for R-900 (28), R-931 (01) and R-960 (01) in polyester and acrylic solutions are listed in Tables LJM-IV-IX. Figures LJM-IX and X show the adsorption isotherms for these pigments in both vehicles. The following observations are noted: The adsorption process is relatively fast for polyester solutions. In both cases, stronger interaction is obtained with an alumina-only surface, The approximate monolayer coverages for the pigments ares Pigment R-900 (28) R-931(01) R-960 (01) Cyplex 1600 45 rog/g 40 22 XC-4011 13 mg/g 10 3 jr DUP050059199 - 10 CDP-ES-79-5 Monolayer coverage for polyester extends to a relatively high concentration range (60-70 g/1) of the supernatant solution. Multilayer buildup is noticed above 30 g/1 for supernatant solutions containing acrylic resin* Adsorption on R-900 CD Base Material In order to determine the adsorption differences between the base and the finished material, a representative sample of R-900 CD (New Johnsonvilie. Line I) was cleaned according to the procedure developed by l . Abrams (PTD-SA-78-2B, p. 16). The base material usually contains less than 1% co-oxidized alumina. It was hoped that the systematic leaching of the base would produce more of a rutile surface to observe its behavior. The experimental results showed that: Equilibrium with CD material is reached in less * than an hour in polyester solutions and the amount adsorbed is comparable to that of R-900. The adsorption isotherm for the CD base/polyester material is very close to that of R-900 (28) and actually both sets of data can be plotted on a common isotherm as shown in Figure LJM-XI. v If the monolayer coverages of R-900 (28) are expressed as equivalents of carboxylic group/ gram of pigment, they become; 39 x 10~ (for Cyplex 1600) and x 10" (for XC-40I1) equi valents/gram. The monolayer coverages agree well with adsorption concentrations of simple ions on clean R-900 base. For example, the measured concentration of F" ion on R-900 base is between ZtS-40^equivalents x 10"/g. Although -- we are dealing in our investigation with polyelectrolytes, the adsorption sizes are those available to simple ions. (N-*-** ..-V^1 W il**' These observations lead to a reasonable hypothesis; the alumina in the base pigment is highly concentrated on the surface and controls its adsorption behavior. Adsorption on Pure Titanium Dioxide To test the hypothesis above described, TiOj of 99.99% purity was obtained from SPEX Industries. The analytical charac terization of this material is given in Table LJM-X. DUP050059200 - 11 CDP-ES-79-5 Kinetic runs on this material with both polyester acrylic reveal that no adsorption is observed within 100 hours of contact. One can imagine that if surface contamination by silica occurred, the results could be explained rather easily. For example, if during the synthesis of the titanium dioxide, there is some Sio? diffusion.to the surface the zeta potential of the solid would tend to approximate that of pure silica. The isoelectric*point of pure Si02 is below pH 2.0. The sample under investigation has an isoelectric point of about 3.6 to 3.8 pH units. The nonadsorption results may be explained solely on zeta potential values in the neighborhood of the operating pH. For example, at pH 6.4, the particles have a charge Of -58 mV and repulsion between polyelectrolyte and pigment will increase. The possible contamination of silica on the rutile surface can be elucidated by Secondary Ion Mass Spectroscopy (SIMS). Figure LJM-xil is a typical spectrum of the composition of the first monolayers of the 'rutile sample. The peaks that appear around m/e 47.00 belong to the titanium isotopes and thdse around m/e 65.00, to their corresponding TiOH+ counter parts, The peak around m/e 28.0 corresponds to silicon. Figure LJM-XIII is an expansion of the region between m/e 22.0 and 33.0. Note the presence of two silicon isotopes in the region of m/e 28.0-29.0 The etching profile of the rutile surface is presented in Figure LJM-XIV and it is clear that there is not that much Si02 present. In view of these results, I can safely conclude that: The amount of co-oxidized alumina on the base is enough to provide comparable behavior to a fully coated pigment such as R-900. Careful control during alumina deposition may provide equal performance to R-900 for pigments containing less than 3% Al20g. A Retrospective View on Pigment Surface Chemistry A combination of analytical techniques and physical measurements enables us to produce a new approach to the under standing of pigment behavior in new industrial systems. The end-point performance is the sum of many complex processes in which adsorption, competition reactions and electrokinetic properties play an interlocking role. The solution of current deficiencies, unusual pigment behavior in well known systems and dispersion behavior must be achieved only by a systematic approach and the understanding of fundamental principles. DUP050059201 - 12 TABLE LJM-I Characterization of Begins CDP-ES-79-5 $6. w XC-4011 Acrylic "".."...... .........'----- ----- *------ -- Acid Number 96 % Solids = 78 Molecular Weight: Mn * 6060 * 20800 wv W/% \S\ t $ 4^ Composition (molar percent) ; acrylic acid = 33.0/49.5/6.6/10.9 Cyplex 1600 Polyester .Acid Number 49 % Solids *74 Molecular Weight; .7*b Mn - 1670 MW = 4370 l, 46 * < i*4 jvy, (acid molar ratio) Neopentylglycol/trimethylolpropane/dipropylene glycol 72/12/21 (molar ratio of acetates) DUP050059202 13 - CDP-ES-79-5 TABLE LJM-II Adsorption of Cyplex 1600 Polyester on R-900(28) as Measured by SEC Sample 1 2 3 4 5 6 7 8 9 10 AO 20.41 42.29 74.00 102.5 126.4 176.1 255.8 421.1 624.6 919.5 Ax 1.327 2.742 5.816 7.098 10.10 13.39 14.50 184.0 364.2 632.8 CO (g/1) 1.85 3.70 6.66 8.88 11.1 14.8 22.2 37.0 52.2 82.1 ce (g/1) 0.120 0.240 0.523 0,615 0.886 1.12 1.26 16.2 30.4 56,5 Ca (mg/g R-900) 3.77 7.57 13.4 18.1 22.3 29.9 45,8 45.5 47.5 55.9 Ao Area of initial polyester. Ax - Area of polyester after adsorption. Co = Initial concentration of polyester. Ce = Concentration of polyester in supernatant. Ca - Concentration of polyester adsorbed on pigment. DUP050059203 - 14 - CDP-ES-79-5 TABLE LJM-III Equilibrium Time for Adsorption of Water-Reducible Vehicles on Several Pigment Surfaces Pigment R-900 (28) R-931 (01) R-960 (01) SSL-4981 Resin Cyplex 1600 Cyplex 1600 Cyplex 1600 Cyplex 1600 Surface Type a i2o 3 ax23/si02 sio2 Time (hrs.) <1 15 30 >>100 R-900(28) R-931(01) R-960(01) SSL-4981 XC-4011 XC-4011 XC-4011 XC-4011 m203 ai2o3/sio2 A123^ S:'l02 sio2 10 5 5 >>100 DUP050059204 Sample 68-1 68-2 68-3 68-6 68-7 68-8 68.9 68-10 15 - CDP-ES-79-5 TABLE LJM-IV Adsorption of Cyplex 1600 on R-900(28) * Co (g/1)*** 1.85 3.70 6.66 14.8 22.2 37.0 52.2 82.1 Ce (g/1)** 0.54 0.62 0.84 1.78 3.12 17.4 32.1 60.5 Ca (g/1) 1.31 3.08 5.82 13.0 19,1 19.6 20.1 21.6 A (mg/g R2.86 6,73 12,7 28.4 41.7 42.8 43.9 47,2 Co - Initial concentration Ce = Supernatant concentration Ca = Concentration of adsorbed polyester A - Concentration of adsorbed polyester in mg/g of pigment. *Samples contained 20.6 g. of R-900 and 45.0 ml of polyester solution. **Measured by UV analysis. DUP050059205 16 CDP-ES-79-5 TABLE LJM-V Adsorption of Cyplex 1600 on R-931(01) Sample 150-1 150-2 150-3 150-4 150-5 150-6 150-7 150-8 150-9 Co (g/l) 3.53 5.89 11.8 23.6 29 .4 35.3 41.2 58.8 88.4 Ce (g/l) 0.656 0.778 1.39 8.80 13.3 18.0 22.2 38.3 67.5 Ca (g/l) 2.87 5.11 10.4 14.8 16.1 17.3 19.0 20.5 20.9 A (mg/g R-931) 6.27 11.2 22.7 32.3 35.2 37.8 41,5 44.8 45,6 DUP050059206 - 17 - CDP-ES-79-5 T'P AB*LE LJ. " M-VI Adsorption of Cyplex 1600 on R-960(01) Sample 114-1 114-2 114-3 114-4 114-5 114-6 114-7 114-8 Co (g/1) 3.29 5.48 11.0 21.9 27.4 32.9 38.4 54.8 Ce (g/1) 0.68 1,35 4.74 15.1 18.5 21.6 28.0 45.2 Ca (g/1) 2.61 4.13 6.26 6.80 8.90 11.3 10*4 9.6 A (mg/g R-960) 5.70 9,02 13.7 14.8 19.4 24.7 22.7 21.0 DUP050059207 Sample 117-1 117-2 117-3 117-4 117-5 117-6 117-7 117-8 117-9 117-10 18 TABLE LJM-VII CDP-ES-79-5 Adsorption of XC-4011 on R-900(28) Co (g/1) 3.87 6,45 12.9 25.8 32.2 38.7 45,1 64.5 96.8 129.0 Ce (g/1) 0,34 1.58 7.54 19.8 26.3 32.1 38.0 55.6 84.3 117,8 Ca (g/1) 3.53 4.87 5.36 6.00 5.90 6.63 7.07 8.90 12.4 11.2 A (mg/g R-900) 7.71 10.6 11,7 13.1 12.9 14.5 15.4 19.4 27,1 24.5 Co - Initial Concentration Ce = Supernatant concentration Ca * Concentration of adsorbed acrylic A = Concentration of adsorbed acrylic in mg/g pigment* DUP050059208 TABLE LJM-VIII Adsorption of XC-4Q11 on R-931(01) sample 153-1 153-2 153-3 153-4 153-5 153-6 153-7 153-8 153-9 CO (q/1) 4.08 6.80 13.6 27.2 3,4.0 40.8 47,6 68.0 102.0 * ' Ce (g/1) 1.90 4,37 10.7 24,0 30,3 35.7 42.8 62.0 85.5 Ca (g/1) 2.18 2.43 2.90 3.20 3.66 5.10 4.80 6.00 16*5 A (mg/g R-931) 4,76 5.31 6.33 6.99 7.99 11.1 10.5 13,5 36,0 DUP050059209 - 20 CDP-ES-79-5 Sample 115-1 115-2 115-3 115-4 115-5 115-6 115-7 115-8 115-9 115-10 TABLE LJM-IX Adsorption of XC-4Q11 op B-960(01) Co (g/1) 3.87 6.45 12.9 25.8 32.2 38.7 45.1 64.5 96.8 129.0 Ce (g/1) 3.16 5.43 11.5 24,3 30.4 36.9 40.1 56.8 86.6 106.1 ca (g/1) 0.71 1.02 1.40 1.50 1.80 1.80 5.00 7.70 10,2 22.9 A (mg/g R-960) 1.55 2.23 3,06 3.28 3.93 3.93 10.9 16.8 22.3 50,0 DUP050059210 - 21 - CDP-ES-79-5 TABLE LJM-X Analytical Characterization of 99.99% TiOo (SPEX Ind. Lot No. 10731) Crystal Structure: 99% rutile Surface Area: o 0.83 m /g Semiquantitative Analysis SPEX Industries Fe 30-60 ppm Si 0.5-2.0 ppm A1 <1 ppm Mg Pb <1 ppm Cr 5-20 ppm CDP Jackson Lab ^ ^(*) 20 ppm 10 ppm 20 ppm 5 ppm 5 ppm 1 ppm (*) It includes matrix correction for Ti02 DUP050059211 & 8 w I Pm DUP050059212 OF POLYESTER R E S IN AS DETECTED BY SEC 23 CDP-ES-79-5 FIGURE LJM-IIt MOLECULAR HEIGHT DISTRIBUTIONS ON SUPERNATANT SOLUTIONS OR POLYESTER BEFORE, AT AND AFTER MONOLAYER COVERAGE ON R-900. DUP050059213 - 24 - . mmii in* ). ; 4si iut* in (> *.i * irv'ti ;n c i< !< no CDP-J3S-79-5 tt/f W*.*- f .u - FIGURE LJM-IIIs REVERSE PHASE CHROMATOGRAMS' FOR POLYESTER SOLUTIONS BEFORE (MOVE) AND AFTER (BELOW) CONTACT WITH R-900. SOLVENT MIXTURE USED A 10% EXPONENTIAL GRADIENT. DUP050059214 25 CDP-ES-79-5 FIGURE LJM-IV: ULTRAVIOLET SPECTRA OF CYPLBX 1600 SOLUTIONS IN METHANOL (ABOVE) AND REFERENCE SOLVENT (BELOW). DUP050059215 - 26 CDP-ES-79-5 ttSGRBMKT CALIBRATION CURVE I4*9 22 V--78 ABSORBANCE 16'2 2 Jrt.v-79 FIGURE LJM-V: TYPICAL CALIBRATION CURVES FOR CYPLEX 1600 (ABOVE) AND XC-4011 (BELOW) METHANOL SOLUTIONS OBTAINED BY ULTRAVIOLET SPECTROSCOPY. DUP050059216 - 27 CDP-ES-79-5 MG POLYESTER/ GM R-908 ummnk abs o r pt io n is o t h er m 16*09 r.-0Ci-78 FIGOEE LJM-VI: COMPARISON OF ADSORPTION ISOTHERMS OBTAINED BY SEC (LC DATA) AND UV ANALYSIS (UV DATA) FOR THE ADSORPTION OP CYPLEX 1600 ON R-900(28). DUP050059217 - 28 CDP-ES-79-5 OQ 10 20 30 40 SO 60 70 80 TIME (Hrs) FIGURE UM-VIIs REACTION OF CYPLEX 1600 WATER REDUCIBLE POLYESTER AT SIMILAR INITIAL CONCENTRATIONS WITH: A) DENSE SILICA COATED PIGMENT (SSL-4981) B) R-960 (01) C) R-931 (01) D) R-900 (28) 90 DUP050059218 29 CDP-ES-79-5 TIME (Hrs) FIGURE UM-VIIIi Reaction of XC-4011 Water Reducible Acrylic At Similar Initial Concentrations With; A) Dons Silica Coated Pigment (SSL-49R1) B) R-960 (01) C) R-931 (01) 1 R-900 (28) DUP050059219 M illig ra m s o f p o ly e s te r/g o f p ig m e n t ISOTHERMS FOR CYPLEX 1600 POLYESTER ADSORPTION FROM AQUEOUS SLURRY FIGURE WM-IXs ADSORPTION ISOTHERMS FOR CYPLEX 1600 WITH SEVERAL TYPES OF TI-PURE PIGMENTS. DUP050059220 - 31 - CDP-ES-79-5 ISOTHERMS FOR XC-4011 ACRYLIC ADSORPTION FROM AQUEOUS SLURRY M illig ra m s o f a c r y lic /g o f pigm ent Equilibrium Concentration <g/L) FIGURE UM-Xs ADSORPTION ISOTHERMS FOR XC-4011 WITH SEVERAL TOPES OF TI-PURE PIGMENTS. DUP050059221 M illig ra m s o f P o ly e s te r/g o f Pigm ent 32 CDP-ES-79-5 ADSORPTION OF CYPLEX 1600 POLYESTER PROM AQUEOUS SOLUTION ONTO R-900 (28) AND R-900 BASE* 60 50 40 30 20 10 10 20 30 40 50 60 70 80 EQUILIBRIUM CONCENTRATION (g/L) Legend Data Obtained for R-900 (28) Data obtained for R-900 Base (*) Material cleaned according to L. Abrams' description. FIGURE LJM-XI DUP050059222 - 33 - CDP-ES-79-5 <$> <s> m SAMPLE-TIGS SPEX S 9 . 99X FIGURE L J M -X IIs EXPANDED SIMS SPECTRUM OF T iO g (SFEX 99.99%) BETWEEN m /e 2 2 .0 a n d 3 0 .0 0 am u. o XU Ttl> + li*nJ <fi 1*1 _! CO -c U<nl Q 71 o M ra m H * cn to ru m M\ Iar-. > (A * N f~ UJ -I fU a iu o -a U) wzi-iijr lL > DUP050059223 SAMPLETIC S SPEX 9 9 . 9SX FIGUKE LJM -X III: SIM S SPECTRUM OP T iO p (SPEX 99.99$) BETWEEN m /e 2 1 .0 0 and 7 3 .0 0 I U. > DUP050059224 35 - CDP-ES-79-5 o SAMPLE'TICS SPEX S9.S9X H10 5 s dP ON <03>> XPIWQ*! f & s H I Pi 055 H 1 W HZf-WZ(OHH> *, f ... lu > .... .................. DUP050059225 - 36 - CDP-ES-79-5 APPENDIX I PIGMENTS USED IN ADSORPTION STUDIES Sample R-900 (28) Lot 4730*** R-960 (01) lot 6079(*()**) R-931 (01) Lot 6639 ^ SPEX ind. Ti02 99.99% SSL-4981 CD Base1 ; % Alo0, 3.6 2.7 N.A. 0.001 0.7 0.1 % Si02 0.1 5.8 N.A. <0.002 1.3 0.1 % T102 95.2 91.4 N.A. 99.9 97.8 98.2 Surface Area (m2/g) 12.9 12.3 14.6 0.87 6.70 5.62 (*) Shipping standard (**) Cleaned Dine I NJ Base N.A.-Not Available DUP050059226 - 37 INDEXING TERMS Acrylic Adsorption Alumina CD Base Cyplex 1600 Isotherm Macromolecules Monolayer Polyelectrolytes Polyester R-900 R-931 R-961 Reverse Phase Liquid Chromatography Rutile Silica SIMS Sites Size Exclusion Chromatography Surface Chemistry XC-4011 Waterborne CDP-ES-79-5 DUP050059227 38 CDP-ES-79-5 DISTRIBUTION 1. L. J. Matienzo 2. D, Nguyen 3. b. H. Eastham 4. G* E. Lynskey 5. w. L. Kreroer 6. K. L. Uhland 7, R, J. Bouchard 8. R. L. Hall 9, G. A. Ganley 10. P. Z. Larson/R. W. Hess/R. A. Fenoglio 11. A. MacLachlan/A. S. Bjornson/L. T. Frick/J G. Ishikawa 12. E. C. Broge/J. Blackwell/J. A. Bluiriberg/J. R. Webster 13. R. J. Mattson 14. L. N. Fisher, Legal 16. Central Report Index, ISD, Centre Rd. Bldg 3211 20. L. A. Wierzbowski, EM 21. D. M. Glenn, F&F, Marshall Lab. 22. R. D. Vest, F&F, E174 23. A. Baidins 24. W. H. Morrison 25. J. H. Boughton 26. J. G. Dickinson, C.R. DUP050059228