BINDER COMPONENT FOR A PARTICULATE FEEDSTOCK COMPOUND FOR USE IN A SHAPING AND SINTERING PROCESS, PARTICULATE FEEDSTOCK COMPOUND, AND SHAPING AND SINTERING PROCESS

Abstract

A binder component b) for a particulate feedstock compound for use in a shaping and sintering process contains b-i) 3 to 70% by volume of a polyolefin, a polyolefin wax or an oxidized polyolefin wax, and b-lii) 30 to 97% by volume of a non-polymeric wax or non-polymeric wax-type substance, or a water-soluble or water-dispersible thermoplastic polymer, based on the total volume of the binder component b). The feedstock compound containing the binder component and non-organic sinterable particles is used in an additive manufacturing process, an injection molding process, a pressing process or a casting process.

Claims

1. A binder component b) for a particulate feedstock compound for use in a shaping and sintering process, containing, based on the total volume of the binder component b), b-i) 3 to 65% by volume of a polyolefin, polyolefin wax or an oxidized polyolefin wax, and b-ii) 35 to 97% by volume of a non-polymeric polar wax or non-polymeric polar wax-type substance.

2. The binder component of claim 1, wherein the polyolefin, polyolefin wax or oxidized polyolefin wax b-i) is selected from polyethylene, polypropylene, polyolefinic copolymers, polyolefinic copolymers with non-olefinic monomers, modified polyolefins, polyethylene wax, oxidized polyethylene wax, copolymeric waxes of polyolefins, polypropylene wax, oxidized polypropylene wax, Fischer-Tropsch-wax, oxidized Fischer-Tropsch-wax, and mixtures thereof.

3. The binder component of claim 1, wherein the non-polymeric polar wax or non-polymeric polar wax-type substance b-ii) is selected from amide waxes, wax-type esters, wax-type fatty acids, higher fatty alcohols or polyhydric alcohols and mixtures thereof.

4. The process of claim 3, wherein the non-polymeric wax or non-polymeric wax-type substance b-ii) is a wax-type material selected from aromatic esters and aromatic sulfonamides.

5. The binder component of claim 1, wherein the amount of the polyolefin, polyolefin wax or oxidized polyolefin wax b-i) is in the range of about 5 to 60% by volume, based on the total volume of the binder component b), and/or the amount of the non-polymeric wax or non-polymeric wax-type substance, polyalkylene glycol, or polyvinyl polymer selected from polyvinyl alcohol, polyvinyl lactams, and copolymers thereof b-ii) is in the range of about 40 to 95% by volume, based on the total volume of the binder component b).

6. The binder component of claim 1, wherein the binder component b) further comprises an extraneous dispersant b-iv) selected from organic compound comprising polar and non-polar regions, metal salts of fatty acids, and mixtures thereof, wherein preferably the amount of the extraneous dispersant b-iv) is in the range of about 0 to 10% by volume, based on the total volume of the binder component b).

7. The binder component of claim 1, exhibiting a DSC melt peak temperature T.sub.P below 180? C.

8. The binder component of claim 1, exhibiting a T.sub.cross below 180? C., wherein T.sub.cross is the temperature at the intersection between the storage modulus G curve and the loss modulus G curve in a dynamic viscoelasticity measurement of the binder component.

9. The binder component of claim 1, exhibiting a viscosity, as determined at a temperature of 130? C.; and at a shear rate of 1 s.sup.?1 of below 6 Pa.Math.s.

10. The binder component of claim 1, exhibiting a viscosity, as determined at a temperature of 110? C.; and at a shear rate of 1 s.sup.?1 of below 8 Pa.Math.s.

11. The binder component of claim 1, exhibiting a viscosity, as determined at a temperature of 100? C.; and at a shear rate of 1 s.sup.?1 of below 10 Pa.Math.s.

12. A particulate feedstock compound for use in a shaping and sintering process, containing, based on the total volume of the particulate feedstock compound, a) sinterable non-organic particles dispersed throughout the particulate feedstock compound, the sinterable non-organic particles having a particle size distribution such that at least 80% of the particles have a maximum particle size A.sub.max in the range of 100 nm to 200 ?m; and b) the binder component b) of claim 1.

13. The particulate feedstock compound of claim 12, wherein the sinterable non-organic particles are selected from a-i) metal particles selected from iron, stainless steel, steel, copper, bronze, aluminum, tungsten, molybdenum, silver, gold, platinum, titanium, nickel, cobalt, chromium, zinc, niobium, tantalum, yttrium, silicon, magnesium, calcium and combinations thereof, having a particle size distribution such that at least 85% of the particles have a maximum particle size A.sub.max in the range of 500 nm to 400 ?m; a-ii) ceramic particles selected from oxides selected from aluminum oxides, silicon oxides, zirconium oxides, titanium oxides, magnesium oxides, yttrium oxides; carbides selected from silicon carbides, tungsten carbides; nitrides selected from boron nitrides, silicon nitrides, aluminum nitrides; silicates selected from steatite, cordierite, mullite; and combinations thereof, having a particle size distribution such that at least 85% of the particles have a maximum particle size A.sub.max in the range of 200 nm to 25 ?m; a-iii) vitreous particles selected from non-oxide glasses selected from halogenide glasses, chalcogenide glasses; oxide glasses selected from phosphate glasses, borate glasses, silicate glasses selected from aluminosilicate glasses, lead silicate glasses, boron silicate glasses, soda lime silicate glasses, quartz glasses, alkaline silicate glasses; and combinations thereof, having a particle size distribution such that at least 85% of the particles have a maximum particle size A.sub.max in the range of 200 nm to 25 ?m; a-iv) combinations of more than one of the sinterable non-organic particles a-i) to a-iii).

14. The particulate feedstock compound of claim 12 containing the sinterable non-organic particles (a) in an amount of about 0.70 to 0.99.Math.? by volume, wherein ?.sub.r is the critical solids loading by volume.

15. The particulate feedstock compound of claim 12, wherein the amount of the sinterable non-organic particles a) is in the range of about 20 to 90% by volume, and the amount of the binder component b) is in the range of about 10 to 80% by volume.

16. The particulate feedstock compound of claim 12, exhibiting a viscosity, as determined at a temperature of 130? C., and a shear rate of 1 s.sup.?1, of below 600 Pa.Math.s.

17. The particulate feedstock compound of claim 12, exhibiting a viscosity, as determined at a temperature of 110? C., and a shear rate of 1 s.sup.?1, of below 800 Pa.Math.s.

18. The particulate feedstock compound of claim 12, exhibiting a viscosity, as determined at a temperature of 100? C., and a shear rate of 1 s.sup.?1 of below 1000 Pa.Math.s.

19. A process comprising the steps of: merging a plurality of particles of a particulate feedstock compound to obtain a green part, the particulate feedstock compound containing, a) sinterable non-organic particles dispersed throughout the particulate feedstock compound, the sinterable non-organic particles having a particle size distribution such that at least 80% of the particles have a maximum particle size A.sub.max in the range of 100 nm to 200 ?m; and b) a binder component b), the binder component b) containing, based on the total volume of the binder component b), b-i) 3 to 70% by volume of a polyolefin, a polyolefin wax or an oxidized polyolefin wax, and b-ii) 30 to 97% by volume of a non-polymeric wax or non-polymeric wax-type substance partially debinding the green part by selectively removing the non-polymeric wax or non-polymeric wax-type substance, using a solvent to obtain a brown part comprising the sinterable non-organic powder particles a) bound to each other by the polyolefin, polyolefin wax or oxidized polyolefin wax b-i), and sintering the brown part to obtain a sintered part.

20. The process of claim 19, the process being selected from an additive manufacturing process an injection molding process; a pressing process; and a casting process.

21. The process of claim 19, wherein the step of merging a plurality of the particulate feedstock compounds comprises the steps of: providing a first layer of feedstock compound particles; selectively densifying the first layer of feedstock compound particles to bind the compound particles to each other in a predefined manner so to produce a first shaped part layer; providing at least one further layer of feedstock compound particles on the first shaped part layer; and selectively densifying the further layer feedstock compound particles to bind the feedstock compound particles to each other in a predefined manner so to produce at least one further shaped part layer, the first shaped part layer and the further shaped part layers forming a green part.

22. A green part obtained by merging a plurality of particles of a particulate feedstock compound, the particulate feedstock compound containing, a) sinterable non-organic particles dispersed throughout the particulate feedstock compound, the sinterable non-organic particles having a particle size distribution such that at least 80% of the particles have a maximum particle size A.sub.max in the range of 100 nm to 200 ?m; and b) a binder component b), the binder component b) containing, based on the total volume of the binder component b), b-i) 3 to 70% by volume of a polyolefin, a polyolefin wax or an oxidized polyolefin wax, and b-ii) 30 to 97% by volume of a non-polymeric wax or non-polymeric wax-type substance.

Description

[0189] The present invention is described in detail below with reference to the attached figures and examples.

[0190] FIG. 1 depicts the second heat ramp of a DSC measurement of binder component 1-B for determining the melt peak temperature T.sub.P of 1-B.

[0191] FIG. 2 depicts the cylindrical testing specimen (green part) obtained from feedstock compound 1-F.

[0192] FIG. 3 depicts the testing specimen made from feedstock compounds 1-F (FIG. 3A), 2-F (FIG. 3B), 3-F (FIG. 3C), 4-F (FIG. 3D), 5-F (FIG. 3E), and 6-F (FIG. 3F).

EXAMPLES

Methods

Dynamic Viscoelasticity Measurements

Determination of Storage Modulus and Loss Modulus

[0193] The dynamic viscoelasticity measurements to determine storage modulus and loss modulus were performed in accordance with DIN 53019-4:2016-10 using a NETZSCH Kinexus Pro+ device with a Peltier temperature-controlled measuring system. The measurements were performed with a plate-plate geometry with a diameter of 40 mm and a frequency of 1 Hz in oscillation mode. The measuring gap was 0.15 mm. For carrying out the measurement, the geometry was heated up to 110? C. for examples 1-B and 2-B and the sample was placed on the hot lower plate. First, it was cooled from 110? C. to 60? C., then heated to 110? C., each with a cooling and heating rate of 1 K/min. In the cooling ramp, the measurement was started in deformation controlled mode with a constant deformation ?=0.1%. After reaching a trigger point, the measurement was switched to shear stress controlled mode with a constant shear stress ?=100 Pa. In the heating ramp, the measurement was started in shear stress controlled mode with a constant shear stress of ?=300 Pa. After reaching a trigger point, the measurement was switched to deformation controlled mode with a constant deformation ?=0.1%. In the heating ramp, for example 1-B, the trigger point was 75? C., for example 2-B, the trigger point was a deformation ?=0.1%.

Determination of Binder and Feedstock Viscosity

[0194] The dynamic viscoelasticity measurements to determine the viscosity were performed in accordance with EN ISO 3219:1994 using a NETZSCH Kinexus Pro+ device with a Peltier temperature-controlled measuring system. The measurements were performed with a plate-plate geometry with a diameter of 40 mm. The measuring gap was 0.15 mm. The measurements were performed isothermal at 100? C. and 130? C. Different shear rates between 0.01 and 100 s.sup.?1 were applied to determine the viscosity at different shear rates. The measurements were carried out in the range of the steady state flow. The steady state is an indicator for a time-independent flow. A purely viscous flow leads to a steady state of 1. Viscosity values determined outside the time-independent flow are not reliable. Values at a steady state below 0.90 or above 1.10, preferably below 0.95 or above 1.05, more preferably below 0.97 or above 1.03 is assumed to be not fully reliable anymore. In case of doubt, the measurement has to be repeated or another suitable measuring setup like different plate diameter, plate-cone geometry or concentrical cylinder geometry has to be selected, which are known per se.

DSC Measurements

[0195] The DSC measurements were performed using a NETZSCH DSC 214 Polyma device. The sample was prepared in an aluminum Concavus pan (crucible) from NETZSCH with perforated lid. For this purpose, a sample is heated in a first heat ramp from ?20? C. to 160? C. cooled to ?20? C. afterwards and finally heated again in a second heat ramp from ?20? C. to 160? C., each with a heating and cooling rate of 10 K/min. Measurement were performed with nitrogen in quality 5.0 as purging gas with a gas flow of 40 mL/min.

Production Examples

[0196] Binder components 1-B to 7-B were produced according to table 1. Feedstock compounds 1-F to 7-F of binder components 1-B to 7-B were produced according to table 2. The melt peak temperatures and intersection temperatures of binder components 1-B and 2-B are depicted in table 3.

TABLE-US-00002 TABLE 1 Binder components 1-B to 7-B; vol.-% relative the total volume of the binder component (b). material (b-i) material (b-ii) material (b-iii) material (b-iv) # (b-i) [vol.-%] (b-ii) [vol.-%] (b-iii) [vol.-%] (b-iv) [vol.-%] 1-B Deurex 30 Deurex 70 E 06 K .sup.[1] A 27 P .sup.[2] 2-B Deurex 22 Deurex 70 Vistamaxx 5 Licocene? PP 3 E 06 K .sup.[1] A 27 P .sup.[2] 8880 .sup.[3] MA 1332 .sup.[4] 3-B Deurex 22 Deurex 70 Escorene 5 Licocene? PP 3 E 06 K .sup.[1] A 27 P .sup.[2] AD2528 .sup.[5] MA 1332 .sup.[4] 4-B Deurex 22 Deurex 70 ENBA 5 Licocene? PP 3 E 06 K .sup.[1] A 27 P .sup.[2] 33901 .sup.[6] MA 1332 .sup.[4] 5-B Deurex 30 PEG 67 stearic acid 3 E 06 K .sup.[1] 8000 .sup.[7] 6-B* Deurex 30 Paraffin 67 stearic acid 3 E 06 K .sup.[1] 6062 .sup.[8] 7-B Deurex 30 Deurex 70 P 36 K .sup.[9] A 28 .sup.[10] .sup.[1] polyethylene-wax available from Deurex AG .sup.[2] oleamide available from Deurex AG .sup.[3] polyethylene polypropylene copolymer available from Exxon Mobile .sup.[4] maleic anhydride grafted polypropylene available from Clariant .sup.[5] ethylene vinyl acetate copolymer available from Exxon Mobile .sup.[6] ethylene n-butyl acrylate copolymer available from Exxon Mobile .sup.[7] polyethylene glycole 8000 available from Carl Roth GmbH + Co. KG .sup.[8] paraffin 6062 available from chemiekontor.de GmbH .sup.[9] polypropylene wax available from Deurex AG .sup.[10] stearamide available from Deurex AG *comparative example

TABLE-US-00003 TABLE 2 Feedstock compounds 1-F to 7-F; vol.-% relative the total volume of the particulate feedstock compound). binder amount (a) comp. (b) amount (b) # metal (a) [vol.-%] (# in table 1) [vol.-%] 1-F stainless steel 316 L .sup.[1] 65 1-B 35 2-F stainless steel 316 L .sup.[1] 65 2-B 35 3-F stainless steel 316 L .sup.[1] 65 3-B 35 4-F stainless steel 316 L .sup.[1] 65 4-B 35 5-F stainless steel 316 L .sup.[1] 65 5-B 35 6-F* stainless steel 316 L .sup.[1] 65 6-B* 35 7-F stainless steel 316 L .sup.[1] 65 7-B 35 .sup.[1] gas atomized, particle size 90%: 22 ?m, available from Sandvik Osprey Ltd. *comparative example

TABLE-US-00004 TABLE 3 Melt peak temperatures T.sub.P and intersection temperatures T.sub.cross. # T.sub.P [? C.] T.sub.cross [? C.] 1-B 73.7 84.7 2-B 74.9 91.9 * comparative example.

Manufacturing of Green Parts

Laser Additive Manufacturing

[0197] A cylindrical testing specimen was produced by a laser additive manufacturing process using a Formiga P110 (available from EOS GmbH). The feedstock compound 1-F of table 2 was used as starting material, the hatch spacing was 0.13 mm at a laser speed of 3000 mm/s and a laser output of 23 W. The powder bed surface temperature was 60? C. The resulting cylindrical testing specimen is depicted in FIG. 2.

Molding Process

Molding and Casting Process

[0198] Further testing specimen have been prepared by a molding and casting process using feedstock compounds 1-F to 7-F. For performing the molding and casting process, a silicone mold having a cuboid cavity of 80?10?5 mm was prepared and pre-heated to a temperature of 60? C. in an oven. The feedstock compound to be investigated was molten at a temperature of 130? C. in a pot (1-F) or using a hot glue gun from REKA Klebetechnik (2-F to 7-F) and introduced into the cuboid cavity of the pre-heated mold by casting (1-F) or applying a pressure of 3 to 6 bar for pressing the feedstock compound (2-F to 7-F) out of the hot glue gun via an open nozzle having a diameter of 4 mm.

[0199] After solidification of the molten feedstock compound, the resulting testing specimen was taken out of the mold. In order to obtain testing specimen having uniform surface properties, protruding feedstock material was grinded off using sanding paper.

[0200] The testing specimen made from feedstock compound 1-F is depicted in FIG. 3A; the testing specimen made from feedstock compound 2-F is depicted in FIG. 3B; the testing specimen made from feedstock compound 3-F is depicted in FIG. 3C; the testing specimen made from feedstock compound 4-F is depicted in FIG. 3D; the testing specimen made from feedstock compound 5-F is depicted in FIG. 3E; the testing specimen made from feedstock compound 6-F* is depicted in FIG. 3F. Except for feedstock compound 1-F (only front view), in each case, front view and back view of the testing specimen are shown.

Manufacture of Sintered Parts

[0201] The green part was then subjected to a solvent debinding step and a sintering step. For solvent debinding, the green part was dipped into the solvent as shown in table 4 in a way that it was fully immersed in the solvent at a temperature of 45? C. for 16 h. Feedstock compounds 1-F and 7-F were dipped into acetone and ethanol; feedstock compounds 2-F, 3F and 4-F were dipped into ethanol; feedstock compound 5-F was dipped into water; feedstock compound 6-F* was dipped into hexane.

[0202] Debinding was successful for feedstock compounds 1-F to 5-F and 7-F; feedstock compound 6-F* softened and disintegrated during debinding in hexane and thus could not be taken out of the solvent.

[0203] The debinding results are summarized in table 4; + denotes that debinding worked, i.e. that the specimen was taken out of the solvent without damage or destruction of the specimen: c denotes that the debound parts did not have a uniform shape but showed cracks after debinding; ? denotes that debinding was not possible as e.g. the green part disintegrated in the solvent during debinding and could not be taken out of the solvent.

TABLE-US-00005 TABLE 4 Debinding results of feedstock compounds 1-F to 7-F in different solvents. feedstock compound (# in table 2) acetone ethanol water hexane 1-F + + n.d. n.d. 2-F c + n.d. n.d. 3-F c + n.d. n.d. 4-F c + n.d. n.d. 5-F n.d. n.d. + n.d. 6-F* n.d. n.d. n.d. ? 7-F ? + n.d. n.d. n.d. = not determined *comparative example

[0204] Sintering of the debound parts to obtain the sintered parts was carried out in a cycle with a heating and cooling rate of 5 K/min, holding times of 2 h at 380? C., of 1 h at 600? C., of 30 min at 1100? C. and of 2 h at a final sintering temperature of 1380? C.

[0205] The rheometer measurement was performed for determination of viscosity in accordance with EN ISO 3219:1994 using a Kinexus rheometer (available from NETZSCH).

[0206] Tables 5 and 6 show the viscosity values of binder components 1-B and 2-B and feedstock compounds 1-F and 2-F, determined at 130? C. and 100? C.

TABLE-US-00006 TABLE 5 Viscosity values of binder components 1-B and 2-B and feedstock compounds 1-F and 2-F at 130? C. viscosity viscosity viscosity viscosity at 0.1 s.sup.?1 at 1 s.sup.?1 at 10 s.sup.?1 at 100 s.sup.?1 # [Pa .Math. s] [Pa .Math. s] [Pa .Math. s] [Pa .Math. s] 1-B 0.040 0.008 0.004 0.004 1-F 0.416 0.488 1.155 1.055 2-B 0.008 0.004 0.006 0.006 2-F 224.1 31.52 13.95 5.564

TABLE-US-00007 TABLE 6 Viscosity values of binder components 1-B and 2-B and feedstock compounds 1-F and 2-F at 100? C. viscosity viscosity viscosity viscosity at 0.1 s.sup.?1 at 1 s.sup.?1 at 10 s.sup.?1 at 100 s.sup.?1 # [Pa .Math. s] [Pa .Math. s] [Pa .Math. s] [Pa .Math. s] 1-B 0.298 0.126 0.042 0.015 1-F 9.088 8.679 5.474 2.945 2-B 1.752 0.231 0.050 0.021 2-F 559.9 168.6 23.46 7.081

Further Examples

[0207]

TABLE-US-00008 TABLE 7 Binder components 8-B to 19-B; vol.-% relative the total volume of the binder component (b). (b-i) (b-ii) # material (b-i) [vol.-%] material (b-ii) [vol.-%] 8-B Jowat 256.10 .sup.[1] 27 Deurex A 27 P .sup.[2] 67 Licocene 1332 TP .sup.[3] 3 9-B Jowat 280.10 .sup.[4] 20 Loxiol 2472 .sup.[5] 57 Loxiol G20 .sup.[6] 20 Licocene 1332 TP .sup.[3] 3 10-B Jowat 280.10 .sup.[4] 20 Deurex A 27 P .sup.[2] 77 Licocene 1332 TP .sup.[3] 3 11-B Deurex E 06 K .sup.[7] 30 Loxiol G20 .sup.[6] 70 12-B VISCOWAX 353 .sup.[8] 30 Loxiol G20 .sup.[6] 70 13-B VISCOWAX 353 .sup.[8] 30 Deurex A 27 P .sup.[4] 70 14-B Deurex E 06 K .sup.[7] 30 1-octadecanol .sup.[9] 70 15-B Deurex E 06 K .sup.[7] 30 monostearin .sup.[10] 70 16-B VISCOWAX 353 .sup.[8] 30 1-octadecanol .sup.[9] 70 17-B VISCOWAX 353 .sup.[8] 30 monostearin .sup.[10] 70 18-B EnBA EN 33901 .sup.[11] 20 Deurex A 27 P .sup.[2] 77 Licocene 1332 TP .sup.[3] 3 19-B EnBA EN 33901 .sup.[11] 20 monostearin .sup.[10] 80 .sup.[1] copolymer based on different polyolefins available from Jowat AG .sup.[2] oleamide available from Deurex AG .sup.[3] propylene-ethylene-maleic anhydride copolymer available from Clariant International Ltd .sup.[4] copolymer based on ethylene and vinyl acetate available from Jowat AG .sup.[5] 4-hydroxybenzoic behenylester available from Emery Oleochemicals GmbH .sup.[6] stearic acid available from Emery Oleochemicals GmbH .sup.[7] polyethylene-wax available from Deurex AG .sup.[8] wax based on ethylene and vinyl acetate available from Innospec Leuna GmbH .sup.[9] 1-octadecanol available from Sigma-Aldrich .sup.[10] monostearin (glycerol 2-stearate) available TCI Deutschland GmbH .sup.[11] copolymer based on ethylene and n-butyl acrylate available from ExxonMobil

TABLE-US-00009 TABLE 8 Melt peak temperatures Tp and intersection temperatures Tcross. T.sub.P T.sub.cross [T.sub.cross ? T.sub.P] # [? C.] (binder) [? C.] (binder) [? C.] 8-B 76.0 114.6 38.6 9-B 62.0 60.9 ?1.1 10-B 76.9 72.0 ?4.9 11-B 57.2 76.0 18.8 12-B 58.1 54.1 ?4.0 13-B 77.0 71.8 ?5.2 14-B 58.7 75.4 16.7 15-B 64.1 67.3 3.2 16-B 59.8 72.9 13.1 17-B 68.8 65.5 ?3.3 18-B 76.9 73.9 ?3.0 19-B 69.3 64.6 ?4.7

TABLE-US-00010 TABLE 9 Viscosity values of binder components 8-B to 19-B at 130? C. viscosity viscosity viscosity viscosity at 0.1 s.sup.?1 at 1 s.sup.?1 at 10 s.sup.?1 at 100 s.sup.?1 # [Pa .Math. s] [Pa .Math. s] [Pa .Math. s] [Pa .Math. s] 8-B n.d. .sup.[1] n.d. .sup.[1] 0.006 0.005 9-B n.d. .sup.[1] 0.426 0.362 0.314 10-B n.d. .sup.[1] 0.149 0.158 0.146 11-B n.d. .sup.[1] n.d. .sup.[1] 0.002 0.002 12-B n.d. .sup.[1] 0.032 0.030 0.030 13-B n.d. .sup.[1] 0.029 0.028 0.028 14-B n.d. .sup.[1] n.d. .sup.[1] 0.002 0.002 15-B 0.016 0.006 0.005 0.005 16-B n.d. .sup.[1] 0.018 0.019 0.020 17-B n.d. .sup.[1] 0.036 0.037 0.038 18-B 0.076 0.082 0.083 0.085 19-B 0.053 0.065 0.067 0.072 .sup.[1] not determined; measured viscosity value outside steady state flow.

TABLE-US-00011 TABLE 10 Viscosity values of binder components 8-B to 19-B at 100? C. viscosity viscosity viscosity viscosity at 0.1 s.sup.?1 at 1 s.sup.?1 at 10 s.sup.?1 at 100 s.sup.?1 # [Pa .Math. s] [Pa .Math. s] [Pa .Math. s] [Pa .Math. s] 8-B n.d. .sup.[1] 1.441 0.370 0.113 9-B 0.901 0.941 1.231 0.963 10-B n.d. .sup.[1] 0.395 0.418 0.378 11-B n.d. .sup.[1] n.d. .sup.[1] 0.009 0.006 12-B n.d. .sup.[1] 0.061 0.058 0.058 13-B n.d. .sup.[1] 0.060 0.060 0.060 14-B n.d. .sup.[1] n.d. .sup.[1] 0.005 0.004 15-B 0.106 0.049 0.021 0.013 16-B n.d. .sup.[1] 0.036 0.037 0.038 17-B n.d. .sup.[1] 0.082 0.082 0.083 18-B 0.191 0.189 0.190 0.193 19-B 0.103 0.063 0.061 n.d. .sup.[1] .sup.[1] not determined; measured viscosity value outside steady state flow.