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The Role of Catalysts in Low-Gloss Epoxy/Polyester Hybrid Powder Coatings

By John Schmidhauser Cray Valley USA, LLC Exton, Pennsylvania USA Presented at the International Waterborne, High - Solids, and Powder Coatings Symposium Feb 21-23, 2001

Cray Valley USA, LLC Oaklands Corporate Center

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Abstract In this study, the crucial role played by catalysts in the preparation of low-gloss hybrid powder coatings using a reactive additive (styrene maleic anhydride copolymer) is described. First, the reactions that occur during the cure of epoxy/polyester hybrid thermoset powder coatings are reviewed. DSC measurements on model mixtures and fully formulated powder paints revel relative reactivities and the roles of catalysis on the various reaction steps. The gloss properties of the coatings are found to be closely tied to the presence of a catalyst. Several approaches to preparing powder coating formulations that exhibit fast cure kinetics, lowgloss appearance and excellent properties are described. Introduction Gloss is a measure of the amount of light reflected from a surface at a given angle, and is expressed as a value between 0 and 100. Polished plate glass has a value of about 100, and a completely nonreflective surface has a value of 0. Low gloss coatings are typically measured as 60 gloss, although the 85 gloss is also sometimes used. The range of gloss readings are loosely divided into several categories, as shown in Table 1.1
Table 1: Gloss Categories Category High Standard Semi Low Matt

use of certain reactive agents. The choice of gloss control agent depends upon the level of gloss reduction desired and the chemistry of the powder coating. Fillers can give rough surfaces due to the protrusion of the fillers from the surface after baking, which disrupts reflected light. Waxes and other incompatible ingredients tend to segregate on the surface during baking, leaving circular voids or forming a film on the surface. The 60 gloss reduction of both fillers and waxes is limited to about 40. Blends of powders of differing chemistries/reactivities, as well as chemically reactive additives such as polycarboxylic acids or their acid salts are used to achieve low and matt finishes. Low molecular weight styrene-maleic anhydride (SMA) resins are a family of anhydride and partial ester functionalized copolymers which have been widely used as gloss reducing additives in thermoset epoxy powder coatings.2 Earlier studies suggest that a two-stage reaction process leads to the textures observed in low gloss epoxy powder coatings containing SMA.1 In this mechanism, dicyandiamide (Dicy), another epoxy curative traditionally added to epoxy powder coatings, reacts at a different rate than the SMA curing agent, leading to two structural networks within the coating.1 In studies of a similarly reactive low-gloss additive, Lee et al3 observed low gloss epoxy coatings during curing, and saw that the coarse surface morphology formed as the gel point of the coating was reached. After gelation, the surface roughness remained fairly constant even with further curing, although fine structure continued to develop past the gel point. This suggests that the low gloss texture is a consequence of morphology develop-ment during curing, and is not due to stress-induced texture development during the cooling of the powder coated surface. This study explores the use of SMA resins as gloss reducing additives in the more complex epoxypolyester hybrid powder coating system. In these formulations, the reactivities between three components, the epoxy resin, the polyester and the SMA anhydride and/or ester, must be balanced so as to give the different curing rates which create the

Gloss Reading (60) > 85 70 to 85 40 to 70 15 to 40 < 15

The chemical and physical properties of most major classes of powder coatings cure to give a level, glossy surface. However, for aesthetic and functional reasons it is often desirable to have a powder coated surface with a low gloss or matt finish. In such cases, gloss control may be achieved through many different techniques, including the addition of inorganic fillers or organic waxes, the lending of powders of different reactivities or the

low gloss morphology. The curing kinetics of the three possible 2-component combinations are explored first by DSC. Using these results, powder coating formulations are prepared and analyzed. These studies uncover the characteristics of the polyester resin and the SMA resins necessary to obtain low gloss epoxy/polyester hybrid powder coatings.

Experimental Materials Epon 2002 (Shell Chemical) is a standard Type 3 Bisphenol A epoxy resin with EEW 675-760. Albester 2240 (McWhorter Technologies) is a high reactivity carboxyl-terminated 70/30 polyester resin with an acid number range of 35-45 mg KOH/g and a viscosity (at 200C) of 6000-8000 mPa@s.





Bisphenol A Epoxy Resin

Albester 2250 (McWhorter Technologies) is an uncatalyzed version of Albester 2240. Crylcoat 7401 (UCB Chemical) is a high reactivity carboxylfunctionalized 70/30 polyester resin with an acid number range of 32-40 mg KOH/g and a melt viscosity (at 160C) of 25-42 Pa@s. Crylcoat 7402 (UCB Chemical) is the uncatalyzed version of Crylcoat 7401. Resiflow P-67 (Estron Chemical) is a flow-control agent. Huberbrite #1 (J. M. Huber) is a grade of powdered barium sulfate suitable for use in powder coatings.

SMA 3000 (Cray Valley Company) is a low molecular weight copolymer of styrene and maleic anhydride in a 3:1 ratio, available in powder (P) and ultrafine powder (UFP) grades, with an acid number of 265305. SMA 10840 (Cray Valley Company) is a copolymer of styrene and maleic anhydride esterified about 65% with iso-octanol, having an acid number of about 240.


C H C H2

3 O





CH 2


C H C H 0.35 C H C H 0.65 O C C O OR O H

] 10

SMA 3000

SMA 10840 ( R = iso-octyl)

DSC Studies Resin mixtures for DSC analysis were dry blended by grinding in a coffee mill for 5 minutes. The powders were analyzed on a TA Instruments DSC 2920 instrument, using a heating profile of 10 C/ min. Powder Coating Formulations All formulations are given in phr (parts-per-hundred resin), where the mass of resin (epoxy + polyester) totals 100 and all other ingredients are given as a fraction of this mass. Formulations were prepared on a 1 kg scale, with pre-mixing via a bag-shake, where the ingredients were simply shaken together in a bag. After pre-mixing, the blend was passed through a lab-scale 50mm twin-screw APV extruder. Unless stated otherwise, all formulations were prepared under high-shear conditions, at 400 rpm with a rear-zone temperature of 175F and a front-zone temperature of 100F. After cooling, the resin blends were ground in a hammermill and passed through a 140 mesh (105 mm) screen. Test panels were sprayed using an electrostatic spraygun to a dry film thickness of 2.0 0.2 mils and cured in an oven at 350, 375 or 400F for 10 minutes, at 375F for 10 minutes or at 300F for 20 minutes. Physical Testing Panels were evaluated for 60 gloss, forward impact resistance, reverse impact resistance, crosshatch adhesion and solvent resistance. Gloss values were measured using a BYK Micro-Gloss 60 meter with a statistics feature; all reported values are the average of ten readings. Impact resistance was measured using a Gardner impact tester and reported values are the highest level of impact at which the coatings showed no cracking. Solvent resistance was evaluated by rubbing a cotton ball soaked in methyl ethyl ketone (MEK) back and forth over the surface 50 times. After drying, the coating was inspected for any changes in appearance. A pass rating indicates no visible change, while a fail indicates that the film was completely removed. A rating of slight softening was given when the coating

became softer with a visible change in appearance. Softened indicates more severe swelling, where a significant amount of the coating came off onto the cotton ball. Chemistry Of Polyester-Epoxy Hybrid Formulations Polyester-epoxy hybrid powder coatings contain both epoxy resins and carboxyl-terminated polyester resins, and may also contain a catalyst to drive the curing reactions. Polyester producers market high reactivity, active or low temperature curing polyester resins which have been admixed with catalysts during production.4 These catalysts are intended to speed the cure rate or to lower the cure temperature of high-gloss hybrid coatings. In this study they are investigated to find if they aide in the cure of gloss reducing additives. To understand the effect of catalyst addition on low gloss hybrid formulations, we chose to concentrate on two SMA Resins (SMA 3000 and 10840), one epoxy resin (Epon 2002) and two families of 70/30 carboxyl-terminated polyester resins (Albester 2240/2250 from McWhorter and Crylcoat 7401/ 7402 from UCB). These polyester resins are catalyzed and uncatalyzed versions of the same materials, allowing us to examine the use of precatalyzed polyesters, to add external catalysts to uncatalyzed formulations, and to perform control experiments. Individual reaction steps in the curing of the epoxy/ polyester/SMA formulations are illustrated in Figure 1. The initial reaction between SMA 3000 and the epoxy resin involves the reaction between anhydride and alcohol functionality (A), between SMA 10840 and epoxy resin involves epoxy and acid functionality (B), between polyester resin and epoxy involves acid and epoxy functionality (C) and between epoxy resin and the product of reaction A involves epoxy and acid functionality (D).5 It is these reactions which are first investigated by DSC.

Figure 1. Idealized reactions involved in curing of epoxy resin/polyester resin/SMA resin formulations.











SMA Ester


CO2H Polyester







DSC Curing Studies Of Epoxy/Polyester/SMA Formulations Differential scanning calorimetry (DSC) is a powerful tool for studying the kinetics of curing reactions.6 A variety of kinetic data may be garnered from DSC traces acquired in isothermal or dynamic mode, including the enthalpy of curing, the length of time to cure at specific temperatures, the temperatures at which curing begins or exhibits a maximum in the curing exotherm under specific heating rates, and the extent of cure at certain conditions. When similar systems are examined under identical heating rates, the temperature at which curing begins can be utilized as a comparative measure of cure rates. Powder coating or other crosslinking formulations that cure at lower temperatures on the DSC will probably be found to cure more quickly or at lower temperatures under application conditions. Samples of the mixtures of two of the three resin components (catalyzed and un-catalyzed) and fully formulated hybrid powders were analyzed via DSC

at 10C/min. The curing onset temperature (To) and temperature of the maximum exotherm (Tmax) were measured for each sample (see Figure 2 for a typical trace). This onset temperature data is compiled in Table 2. Figure 2. Typical DSC trace of epoxy/polyester/SMA resin formulation showing To and Tmax.









o Up






Universal V2.6D TA Instruments

Temperature (C)

Table 2. Onset temperatures of resin reactions determined by DCS.

Tg Onset (C) With Catalyst* >210 147 175 >210 147 148 149 146

Composition SMA 3000 + Albester 2250 EPON 2002 + Albester 2250 SMA 3000 + EPON 2002 SMA 10840 + Albester 2250 EPON 2002 + Albester 2250 SMA 10840 + EPON 2002 SMA 3000 + Albester 2250 + EPON 2002 SMA 10840 + Albester 2250 + EPON 2002 * 0.5 Wt. % Tetrabutylphosphonium bromide added.

No Catalyst >210 193 >210 >210 193 180 195 190

These DSC studies indicate that all reactions are slow in the absence of an esterification catalyst, although the reactions of the carboxylic acid functionalized SMA resin (10840) occur at a lower temperature compared to reactions of the anhydride functionalized SMA resin (3000). The catalyst has the most pronounced effect on the reaction between the SMA resins and the epoxy resin. Based on these results we looked at powder coating formulations based on pre-catalyzed polyester resins. SMA 3000 Hybrid Formulations with Pre-Catalyzed Polyesters Two families of carboxyl-terminated polyester resins were chosen for this study: Crylcoat 7401 and 7402; and Albester 2240 and 2250. All resins are of the 70/30-type, with Crylcoat 7401 and Albester 2240

containing catalysts. Pre-catalyzed formulations containing SMA 3000P are outlined in Table 3. All formulations were prepared as outlined in Section 2. The results from formulations H1-H4 are summarized in Table 4. All coatings were found to exhibit poorer solvent resistance than comparable epoxy formulations, which is typical of hybrids in general, probably due to a lower crosslink density. Curing at 400F or higher is recommended, as higher glosses and reduced physical properties are obtained at lower curing temperatures. It appears that these high temperatures are required to allow curing to be as complete as possible. The lowest glosses were obtained using the Crylcoat resin with 10 parts of SMA 3000.

Table 3: Formulations - Hybrids containing SMA 3000 and Pre-catalyzed Polyesters

Material Epon 2002 Crylcoat 7401 Albester 2240 SMA 3000P Carbon Black Resiflow P-67 Barium sulfate Benzoin Total parts 5 2.0 1.2 40 0.5 148.7

H1 50 50

H2 50 50

H3 50 50

H4 50

50 10 2.0 1.2 40 0.5 153.7 20 2.0 1.2 40 0.5 163.7 10 2.0 1.2 40 0.5 153.7

Table 4: Results - SMA 3000 with Pre-catalyzed Polyester Hybrids

Formulation - Cure Temp(F)/Time(min) H1 - 400/10 H1 - 375/10 H2 - 400/10 H2 - 350/10 H3 - 400/10 H3 - 375/10 H4 - 400/10 H4 - 350/10 Gloss (60) 22.3 54.5 11.0 58.2 15.6 31.0 48.3 81.0 Forward Impact (in-lb) 60 40 20 20 20 20 20 < 20 Reverse Impact (in-lb) 40 40 < 20 20 < 20 < 20 < 20 < 20 Crosshatch Adhesion pass pass pass pass pass pass pass pass MEK 50 Double Rubs sl. softening softened sl. softening fail sl. softening softened sl. softening softened

Inductively coupled plasma (ICP) analysis was used to determine the type and amount of catalyst present in some commercially-available polyester resins. Due to the nature of the production of pre-catalyzed polyesters, a high thermal stability catalyst is required. All four polyester resins contained from 120 to 140 ppm tin. While tin compounds are commonly used as an esterification catalyst between alcohols and carboxylic acids, they are less effective

for acid-epoxy reactions. However, it was also found that the active forms of the polyester resins contained phosphorus (Crylcoat 7401 = 362 ppm P, Albester 2240 = 139 ppm P), while the uncatalyzed resins did not (Crylcoat 7402 = 6 ppm P, Albester 2250 = 6 ppm P). Therefore, the effect of gloss reduction by adding phosphorus catalysts to otherwise high gloss formulations was investigated.

Table 5: Formulations - External Catalysts in SMA 3000 Hybrids

Material Epon 2002 Albester 2250 Crylcoat 7402 SMA 3000P Methyltriphenyl phosphonium bromide Triphenylphosphine Tetrabutyl phosphonium bromide Carbon Black Resiflow P-67 Barium sulfate Benzoin Total parts 2.0 1.2 40 0.5 153.7 10 10 0.25 10 0.75 0.25 0.75 0.25 2.0 1.2 40 0.5 154.0 2.0 1.2 40 0.5 154.5 2.0 1.2 40 0.5 154.0 2.0 1.2 40 0.5 154.5 2.0 1.2 40 0.5 154.0 0.75 2.0 1.2 40 0.5 154.5 0.75 2.0 1.2 40 0.5 149.5 0.25 2.0 1.2 40 0.5 154.0 0.75 2.0 1.2 40 0.5 154.5 10 10 10 10 5 H5 50 50 H6 50 50 H7 50 50 H8 50 50 H9 50 50 H10 50 50 H11 50 50 H12 50 50 50 10 50 10 H13 50 H14 50

SMA 3000 in Hybrids - Addition of External Catalysts In addition to using pre-catalyzed polyester resins, it is possible to add catalyst independently. This should give the formulator greater control over the properties and cost of their coating, although a little more development work is required to optimize the formulation. Three different catalysts were tried at different levels in hybrid formulations containing Crylcoat 7402 and Albester 2250. Formulations shown in Table 9 were prepared as described in Section 2.

The results from formulations H5-H14 are summarized in Table 10. The control experiment (H5) containing no catalyst had a very high gloss with no solvent resistance, indicating that no cure took place. Formulations H6-H11 compare the effectiveness of three different phosphorus-containing catalysts at low and high levels in an Albester 2250 formulation. From these results, it is apparent that tetrabutylphosphonium bromide (TBPBr) is the best catalyst on an equivalent weight basis giving a gloss as low as 18.5 when incorporated at 0.75 phr.

Table 6: Results - Hybrids Containing Externally Added Catalysts

Formulation - Cure Temp(F)/Time(min) H5 - 400/10 H5 - 350/10 H6 - 400/10 H7 - 400/10 H8 - 400/10 H8 - 375/10 H9 - 400/10 H9 - 375/10 H10 - 400/10 H10 - 375/10 H11 - 400/10 H11 - 375/10 H12 - 400/10 H12 - 375/10 H13 - 400/10 H13 - 375/10 H14 - 400/10 H14 - 375/10 Gloss (60) 92.0 88.3 55.8 23.6 50.5 70.1 23.7 48.2 44.3 48.7 18.5 39.9 33.3 57.9 17.1 47.9 14.5 47.3 Forward Impact (in-lb) 160 20 20 40 20 20 40 40 20 20 20 20 40 20 60 20 20 20 Reverse Impact (in-lb) 140 < 20 < 20 < 20 < 20 < 20 20 < 20 < 20 < 20 < 20 < 20 20 < 20 40 < 20 < 20 < 20 Crosshatch Adhesion pass pass pass pass pass pass pass pass pass pass pass pass pass pass pass pass pass pass MEK 50 Double Rubs removed removed sl. softening sl. softening sl. softening softened sl. softening sl. softening sl. softening softened sl. softening softened sl. softening sl. softening sl. softening fail sl. softening fail

Effect of Phosphorus Content on SMA 3000Containing Hybrids Powder Coatings A direct comparison of H11 with H14 indicates that the most significant factor on gloss reduction is actually the choice of polyester resin. In both these externally catalyzed formulations and in the precatalyzed formulations (H1-H4), Crylcoat resins outperform the Albester resins. Calculation of the amount of phosphorus in all hybrid formulations (H1-H14) allows us to examine the effect of phosphorus content on the gloss (Figure 3). It is apparent from Figure 3 that Albester formulations are quite sensitive to the level of catalysis, while Crylcoat formulations do not show much dependence on catalyst levels. The reason for this difference is not known, although the two polyesters do have different viscosities.

The DCS cure properties of formulations H1-H14 were measured as described in Section 4, and they are summarized in Table 7. For these formulations based on SMA 3000, fast cure kinetics, as measured by either low onset temperatures or low curing maxima, correlates with lower gloss properties. This data highlights the differing cure behaviors of formulations prepared from Crylcoat and Albester resins (Figures 4 and 5). The gloss of Albester formulations decreases with increasing reactivity (lower To and Tmax), while the gloss of Crylcoat-based formulations seems to be relatively independent.

Figure 3. Effect of phosphorus content on the gloss of Albester () and Crylcoat ( ) hybrid formulations.

Gloss of Hybrid Formulations



Albester 60 Gloss




0 -0.005








Phosphorus (wt. %)


Table 7: DSC Analysis of Hybrid Formulations

Formulation H1 H2 H4 H5 H6 H7 H8 H9 H10 H11 H12 H13 H14 60 Gloss * 22.3 11.0 48.3 92.0 55.8 23.6 50.5 23.7 44.3 18.5 33.3 17.1 14.5 Cure Onset** (C) 124.8 128.3 134.8 166.6 132.6 119.1 134.7 93.1 130.7 119.4 116.3 133.2 112.7 Cure Maxima** (C) 166.5, 176.8 173.1 176.5 288.9 194.7 157.7 168.8 154.1, 169.6 153.7, 195.9 164.1 165.7 188.6 161.6

*When cured at 400F for 10min. ** Measured via DSC at 10C/min.

Figure 4: Effect of powder coating reactivity, as shown by the temperature at the maximum in the curing exotherm measured via DSC, on gloss reduction in both Albester () and Crylcoat ( ) formulations.

Effect of Reactivity on Gloss - Cure Maximum



60 Gloss



Albester Crylcoat

0 140









Temp. at Cure Maximum (C)


Figure 5: Effect of powder coating reactivity, as shown by the temperature at the onset of curing measured via DSC, on gloss reduction in both Albester () and Crylcoat ( ) formulations.

Effect of Reactivity on Gloss - Cure Onset



60 Gloss



Albester Crylcoat

0 80






Cure Onset (C)

Hybrid Powder Coatings Formulations WithAcid Functionalized SMA Resin (10840) A number of formulations containing an acid functionalized reactive additive, SMA 10840, were

prepared. The same resins and catalysts were used as in the SMA 3000 formulations, substituting SMA 10840 for 3000. These formulations are shown in Table 8.

Table 8. Formulations - SMA 10840 in Hybrid formulations

Material Epon 2002 Crylcoat 7401 Albester 2250 SMA 10840 Tetrabutyl phosphonium bromide Carbon Black Resiflow P-67 Barium sulfate Benzoin Total parts 2.0 1.2 40 0.5 148.7 2.0 1.2 40 0.5 153.7 2.0 1.2 40 0.5 155.7 2.0 1.2 40 0.5 163.7 5 10 12 20 I 50 50 II 50 50 III 50 50 IV 50 50 50 5 0.75 2.0 1.2 40 0.5 149.5 V 50


Table 9. Characterization of hybrid powder coatings containing SMA 10840.

Formulation - Cure Temp(F)/Time(min) I - 400/10 I - 375/10 II - 400/10 II - 300/20 III - 400/10 III - 375/10 IV - 400/10 IV - 375/10 V - 400/10 V - 375/10 Gloss (60) 81.2 89.8 83.5 95.1 80.1 88.6 85.4 88.6 83.5 86.0 Forward Impact (in-lb) 20 20 80 20 40 20 40 20 40 20 Reverse Impact (in-lb) < 20 < 20 40 < 20 40 < 20 40 < 20 40 < 20 Crosshatch Adhesion pass pass pass pass pass pass pass pass pass pass MEK 50 Double Rubs sl. Softening sl. Softening sl. Softening sl. Softening sl. Softening sl. Softening sl. Softening sl. Softening sl. Softening sl. Softening

Characterization of formulations I-V is summarized in Table 9. Surprisingly, all powder coatings prepared with SMA 10840 exhibited high gloss. However, the coatings exhibited good solvent resistance indicating that the coatings were fully cured. From the DSC studies in Section 4, it is clear that SMA 10840 reacts more readily with EPON 2002 than does SMA 3000. This is probably due to there being two reactive pathways available for the 10840 resin: reaction of the 10840 carboxylic acid groups with the EPON epoxy groups, and reaction of the 10840 anhydride groups with the EPON alcohol groups. Therefore, the overall reactivity of 10840 with EPON is similar to that of the polyester resin with EPON. This could explain the difference in matting behavior exhibited by SMA 3000 and 10840, since it is believed that different cure rates are needed to set up the two-network morphology needed for a low gloss finish. As such, SMA 3000 and EPON cure at a different rate than the polyester and EPON, giving a low gloss finish, while 10840 and the polyester cure at similar rates with EPON, giving a uniform, single phase high gloss surface to those powder coatings.

Conclusions SMA Resins work as reactive gloss reducing agents in epoxy/polyester hybrid powder coatings through formation of a two-phase micro-texture morphology. Models studies indicated that catalysis of the SMA resin anhydride epoxy resin alcohol reaction is necessary to develop the proper morphology during curing to give a low gloss surface. The catalyst can be present is a component of the polyester resin, or can be added separately to the powder paint formulation. Phosphonium salts were found to highly effective in giving low gloss powder coatings, and tetrabutylphosphonium bromide is particularly recommended as a catalyst for use at 0.25-1 phr in these types of formulations. Acknowledgments Thanks to Doug Richart of D. S. Richart Associates for preparing and coating the formulations outlined in this report, and thanks also for many helpful suggestions and discussions. The assistance of Reta Tanjala, Jeanine Willcox and Wes Robinson of the ATOFINA Chemicals, Inc. King of Prussia Analytical Department are much appreciated.


References 1. Richart, D. S. The surface topography of powder coatings and its relation to gloss, Powder Coating 1999, 2, 25-35. 2. Salitros, J. J.; Patarcity, R. Gloss modification of thermoset powder coatings with styrene, maleic anhydride copolymers, Proceedings of the Int. Waterborne, High-Solids and Powder Coatings Symp. 1992. 3. Lee, S. S.; Han, H. Z. Y.; Hilborn, J. G.; Mnson, J.-A. E. Surface structure build-up in thermosetting powder coatings during curing, Prog. Org. Coat. 1999, 36, 79-88. 4. Panandiker, K. P.; Wiedow, T. Low Temperature Cure Carboxyl Terminated Polyesters US Patent 5,637,654, 1997.

5. May, C. A. Epoxy Resins, Chemistry and Technology, 2nd Ed., Marcel Dekker, New York, 1988, p. 501. 6. a) Pielichowski, K.; Czub, P.; Pielichowski, J. Characterization of the cure of some epoxides and their sulphur-containing analogs with hexahydrophthalic anhydride by DSC and TGA, J. Appl. Poly. Sci. 1998, 69, 451-460. b) Vora, R. A.; Trivedi, H. C.; Patel, C. P.; Kazlauciunas, A.; Guthrie, J. T.; Trivedi, M. C. Cure kinetics of epoxy resin with styrene maleic anhydride copolymer by DSC technique, Polymers & Polymer Composites 1995, 4(1), 6167.

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