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

Abstract

A binder component for a feedstock compound for use in a shaping and sintering process comprises b-i) 3 to 70% by volume of at least one first thermoplastic and/or wax-type material, and b-li) 30 to 97% by volume of at least one second thermoplastic and/or wax-type material, based on the total volume of the binder component. The first thermoplastic and/or wax-type material and the second thermoplastic and/or wax-type material differ in at least one property which property is selected from (1) solubility in a solvent, (2) degradability induced by heat and/or a reactant, and (3) volatility. The first thermoplastic and/or wax-type material is less soluble, less degradable or less volatile than the second thermoplastic and/or wax-type material. T.sub.cross is below 120 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. 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 for a feedstock compound for use in a shaping and sintering process, comprising, based on the total volume of the binder component, b-i) 3 to 70% by volume of at least one first thermoplastic and/or wax-type material, b-ii) 30 to 97% by volume of at least one second thermoplastic and/or wax-type material or a plasticized thermoplastic and/or wax-type material, wherein the first thermoplastic and/or wax-type material and the second thermoplastic and/or wax-type material differ in at least one property which property is selected from (1) solubility in a solvent, (2) degradability induced by heat and/or a reactant, and (3) volatility, wherein the first thermoplastic and/or wax-type material is less soluble, less degradable or less volatile than the second thermoplastic and/or wax-type material, wherein T.sub.cross is below 120 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.

2. The binder component of claim 1, exhibiting a DSC melt peak temperature T.sub.P below 130 C.

3. 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.

4. 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.

5. 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.

6. The binder component of claim 1, wherein the first thermoplastic and/or wax-type material b-i) and/or the second thermoplastic and/or wax-type material b-ii) is selected from vinyl ester polymers; polyolefins; polyamides; polyurethanes; paraffin waxes; ester-type waxes, esters of carboxylic acids, esters of a hydroxybenzoic acid; polyolefin waxes; amide waxes; polycarbonate, poly--methylstyrene; water-soluble or water-dispersible thermoplastic polymers; and mixtures thereof.

7. The binder component of claim 1, wherein the amount of the first thermoplastic and/or wax-type material 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 second thermoplastic and/or wax-type material b-ii) is in the range of about 40 to 95% by volume, based on the total volume of the binder component b).

8. The binder component of claim 1, wherein b-i) is selected from polyesters, polyethers, polyolefins, polyolefin waxes, polyamides and polyacrylates.

9. The binder component of claim 1, wherein b-ii) is selected from polar waxes, or a plasticized thermoplastic and/or wax-type material containing a polar plasticizer.

10. The binder component of claim 9, wherein the binder component b-ii) is a wax-type material selected from aromatic esters and aromatic sulfonamides, or a plasticized thermoplastic and/or wax-type material containing a plasticizer selected from aromatic esters and aromatic sulfonamides.

11. The binder component of claim 1, incorporating a combination of the first thermoplastic and/or wax-type material b-i) and the second thermoplastic and/or wax-type material b-ii) selected from the following table, wherein b-i) and b-ii) differ in solubility in the solvent indicated: TABLE-US-00013 first thermoplastic second thermoplastic and/or wax-type and/or wax-type material (b-i) material (b-ii) polyamide ester-type waxes optionally in combination with stearic acid sulfonamide amide wax optionally in combination with stearic acid polyethylene wax amide wax optionally with optionally in combination propylene-ethylene with stearic acid copolymer polyethylene wax stearic acid higher alcohols esters of organic acids polypropylene wax amide wax optionally in combination with stearic acid polyethylene wax polyalkylene glycol poly(meth)acrylate ester-type waxes optionally in combination with stearic acid sulfonamide optionally in combination with stearic acid polyolefinic copolymer amide wax optionally in combination with polyolefinic copolymers with non-olefinic monomers polyolefinic copolymers ester-type waxes with non-olefinic monomers optionally in combination with stearic acid optionally in combination with polyolefinic copolymers with non-olefinic monomers amide wax optionally in combination with polyolefinic copolymers with non-olefinic monomers copolymeric wax of stearic acid polyolefins amide wax higher alcohols esters of organic acids polyolefinic copolymers amide wax with non-olefinic monomers optionally in combination with polyolefinic copolymers with non-olefinic monomers esters of organic acids polyester ester-type waxes optionally in combination with stearic acid esters of organic acids sulfonamide optionally in combination with stearic acid amide wax optionally in combination with polyolefinic copolymers with non-olefinic monomers higher alcohols polyester optionally in combination with stearic acid polyester-based esters of organic acids thermoplastic elastomer

12. A particulate feedstock compound for use in a shaping and sintering process, 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%0 of the particles have a maximum particle size A.sub.max in the range of 100 nm to 400 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..sub.r 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 particulate feedstock compounds according to claim 12 to obtain a green part, partially debinding the green part by selectively removing the second thermoplastic and/or wax-type material b-ii) to obtain a brown part comprising the sinterable non-organic powder particles a) bound to each other by the first thermoplastic and/or wax-type material b-i), and sintering the brown part to obtain a sintered part.

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

21. A green part obtained by merging a plurality of particulate feedstock compounds according to claim 12.

Description

[0246] The present invention is described in detail below with reference to the attached figures and examples.

[0247] FIG. 1 depicts the storage modulus G curve and the loss modulus G curve of a dynamic viscoelasticity measurement during heating of binder component 1-B for determining the cross-over temperature T.sub.cross of 1-B.

[0248] FIG. 2 depicts the storage modulus G curve and the loss modulus G curve of a dynamic viscoelasticity measurement during heating of binder component 3-B for determining the cross-over temperature T.sub.cross of 3-B.

[0249] FIG. 3 depicts the storage modulus G curve and the loss modulus G curve of a dynamic viscoelasticity measurement of binder component 4-B for determining the cross-over temperature T.sub.cross of 4-B. FIG. 6 was recorded during cooling since a higher value of T.sub.cross was recorded during cooling.

[0250] FIG. 4 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.

[0251] FIG. 5 depicts the second heat ramp of a DSC measurement of binder component 3-B for determining the melt peak temperature T.sub.P of 3-B.

[0252] FIG. 6 depicts the second heat ramp of a DSC measurement of binder component 4-B for determining the melt peak temperature T.sub.P of 4-B.

[0253] FIG. 7 depicts the cylindrical testing specimen (green parts) obtained from feedstock compounds according to table 2, 1-F (FIG. 7 A), 2-F (FIG. 7 B), 3-F (FIG. 7 C) and 4-F (FIG. 7 D).

[0254] FIG. 8 depicts the testing specimen (green parts) obtained by a molding process using feedstock compounds 1-F (FIG. 8 A), 2-F (FIG. 8 B), 3-F (FIG. 8 C), 4-F (FIG. 8 D), 5-F (FIG. 8 E), and 6-F (FIG. 8 E).

[0255] FIG. 9 depicts the notched specimen in side view and top view obtained from the feedstock compound according to table 2, 1-F.

[0256] FIG. 10 depicts the notched specimen in side view and top view obtained from the feedstock compound according to table 2, 2-F.

[0257] FIG. 11 depicts the notched specimen in side view and top view obtained from the feedstock compound according to table 2, 3-F.

[0258] FIG. 12 depicts a 3D-printed oblong first green part in a silicone mold (FIG. 12 A) and an integral part produced by overcasting the oblong first green part with molten feedstock compound (FIG. 12 B).

EXAMPLES

Methods

Dynamic Viscoelasticity Measurements

Determination of Storage Modulus and Loss Modulus

[0259] 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. (in example 2-B of table 3: 160 C., in example 3-B of table 3: 140 C.) and the sample was placed on the hot lower plate. First, it was cooled from 110 C. (140 C., 160 C.) to 60 C., then heated to 110 C. (140 C., 160 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 for the binder, =700 Pa for the feedstock compound). 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, the trigger point was for a deformation =0.1%, except for binder 4-B where the trigger point was 75 C.

Determination of Binder and Feedstock Viscosity

[0260] 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 the following temperatures: T.sub.cross+20 K, 100 C. and at 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

[0261] 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. (in examples 2-B and 3-B of table 3: 180 C.), cooled to 20 C. afterwards and finally heated again in a second heat ramp from 20 C. to 160 C. (180 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

[0262] Binder components 1-B to 6-B were produced according to table 1. Feedstock compounds 1-F to 6-F of binder components 1-B to 6-B were produced according to table 2. Melt peak temperatures T.sub.P, intersection/cross-over-temperatures T.sub.cross are shown in table 3.

TABLE-US-00002 TABLE 1 Binder components 1-B to 6-B; vol.-% relative the total volume of the binder component (b). (b-i) (b-ii) # Material (b-i) [vol.-%] Material (b-ii) [vol.-%] 1-B Griltex 2439 A .sup.[1] 27 Loxiol 2472 .sup.[2] 69 Loxiol G20 .sup.[3] 4 2-B* Griltex 1796A .sup.[4] 27 Loxiol 2472 .sup.[2] 69 Loxiol G20 .sup.[3] 4 3-B* Orgasol 3502 D .sup.[5] 27 Loxiol 2472 .sup.[2] 69 Loxiol G20 .sup.[3] 4 4-B Deurex E 06 K .sup.[6] 30 Deurex A 27 P .sup.[7] 70 5-B Griltex 2439 A .sup.[1] 27 Loxiol 2472 .sup.[2] 73 6-B .sup.[8] Deurex E 06 K .sup.[6] 22 Deurex A 27 P .sup.[7] 70 Vistamaxx 8880 .sup.[9] 5 .sup.[1] copolyamide having a DSC melting range of 115 to 125 C., available from EMS-CHEMIE HOLDING AG .sup.[2] 4-hydroxybenzoic behenylester available from Emery Oleochemicals GmbH .sup.[3] stearic acid available from Emery Oleochemicals GmbH .sup.[4] copolyamide having a DSC melting range of 150 to 160 C., available from EMS-CHEMIE HOLDING AG .sup.[5] copolyamide available from Arkema .sup.[6] polyethylene-wax available from Deurex AG .sup.[7] oleamide available from Deurex AG .sup.[8] additionally containing 3 vol.-% of Licocene PP MA 1332 (maleic anhydride grafted polypropylene available from Clariant) .sup.[9] polyethylene polypropylene copolymer available from Exxon Mobile *comparative example.

TABLE-US-00003 TABLE 2 Feedstock compounds 1-F to 6-F (vol.-% relative the total volume of the particulate feedstock compound). Binder comp. (b) amount (a) (# in amount (b) # metal (a) [vol.-%] table 1) [vol.-%] 1-F stainless steel 316 L .sup.[1] 62 1-B 38 2-F* stainless steel 316 L .sup.[1] 62 2-B* 38 3-F* stainless steel 316 L .sup.[1] 62 3-B* 38 4-F stainless steel 316 L .sup.[1] 65 4-B 35 5-F stainless steel 316 L .sup.[1] 62 5-B 38 6-F stainless steel 316 L .sup.[1] 65 6-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.cross T.sub.P (binder) # [ C.] [ C.] 1-B 56.0 89.0 2-B* 57.1 143.6 3-B* 52.2 127.7 4-B 73.7 84.7 5-B 57.1 90.1 6-B 74.9 91.9 *comparative example.

Manufacture of Green Parts

Laser Additive Manufacturing

[0263] Cylindrical testing specimen were produced by a laser additive manufacturing process using a Formiga P110 (available from EOS GmbH). The feedstock compounds 1-F to 5-F of table 2 were used as starting materials.

[0264] For the feedstock compounds 1-F to 3-F, the laser output was 25 W at a laser speed of 4450 mm/s and the powder bed surface temperature was 60 C. The hatch spacing was varied (0.13 mm vs. 0.07 mm) resulting in a different energy input: A hatch spacing of 0.13 mm resulted in an energy input of 42.3 mJ/mm.sup.2; a hatch spacing of 0.07 mm resulted in an energy input of 78.5 mJ/mm.sup.2.

[0265] For the feedstock compound 4-F, the hatch spacing was 0.13 mm at a laser speed of 3000 mm/s and the powder bed surface temperature was 60 C. The laser output was varied (20 W vs. 25 W) resulting in a different energy input: A laser output of 25 W resulted in an energy input of 64.1 mJ/mm.sup.2; a laser output of 20 W resulted in an energy input of 51.3 mJ/mm.sup.2.

[0266] The feedstock compounds 1-F to 3-F of table 2 were used as starting materials for producing notched specimen by a laser additive manufacturing process using a Formiga P110 as described above (see cylindrical testing specimen). Herein, the term notched specimen denotes a rectangular solid which comprises one or more notches, wherein the notches may have different widths. Such notched specimen are depicted in side view and top view in FIGS. 9 to 11.

[0267] In FIG. 9, feedstock compound 1-F was used as starting material at a laser output of 25 W, a laser speed of 4450 mm/s and a hatch spacing of 0.13 mm resulting in an energy input of 42.3 mJ/mm.sup.2.

[0268] In FIG. 10, feedstock compound 2-F was used as starting material at a laser output of 25 W, a laser speed of 4450 mm/s and a hatch spacing of 0.07 mm resulting in an energy input of 78.5 mJ/mm.sup.2.

[0269] In FIG. 11, feedstock compound 3-F was used as starting material at a laser output of 25 W, a laser speed of 4450 mm/s and a hatch spacing of 0.07 mm resulting in an energy input of 78.5 mJ/mm.sup.2.

[0270] The production of such notched specimen aimed at obtaining specimen, i.e. parts, of high density with, at the same time, high representation of the geometry of the aimed part and little caking of the particulate feedstock compound, preferably at low laser energy input. The results are depicted in FIGS. 9 to 11: Solely the notched specimen depicted in FIG. 9 provides high density, high representation of the geometry and little caking at low laser energy input of 42.3 mJ/mm.sup.2. Contrarily, the notched specimens in FIGS. 10 and 11 are less dense and/or the notches are less properly shaped due to caking at an energy input of 78.5 mJ/mm.sup.2.

Molding Process

[0271] Further testing specimen were prepared by a molding and casting process using feedstock compounds 1-F to 6-F. For performing the molding and casting process, a silicone mold having a cuboid cavity of 80105 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 (4-F); or at a temperature of 210 C. (2-F, 3-F, 5-F) or 170 C. (1-F) or 130 C. (6-F) using a hot glue gun from REKA Klebetechnik and introduced into the cuboid cavity of the pre-heated mold by casting (4-F) or applying a pressure of 3 to 6 bar for pressing the feedstock compound (1-F to 3-F, 5-F, 6-F) out of the hot glue gun via an open nozzle having a diameter of 4 mm.

[0272] 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.

[0273] The testing specimen made from feedstock compound 1-F is depicted in FIG. 8 A; the testing specimen made from feedstock compound 2-F is depicted in FIG. 8 B; the testing specimen made from feedstock compound 3-F is depicted in FIG. 8 C; the testing specimen made from feedstock compound 4-F is depicted in FIG. 8 D; the testing specimen made from feedstock compound 5-F is depicted in FIG. 8 E; the testing specimen made from feedstock compound 6-F is depicted in FIG. 8 F. Except for feedstock compound 4-F (only front view), in each case, front view and back view of the testing specimen are shown.

Overcasting Process

[0274] Feedstock compound 1-F was used to produce an oblong first green part which was then overcast with molten feedstock compound 1-F. The oblong first green part was produced via 3D-printing using feedstock compound 1-F as described above and placed in a silicone mold having a cuboid cavity of 80105 mm, see FIG. 12 A. The mold containing the oblong first green part was pre-heated to a temperature of 60 C. in an oven. Then, feedstock compound 1-F was molten at a temperature of 170 C. using a hot glue gun from REKA Klebetechnik and introduced into the cuboid cavity of the pre-heated mold by applying a pressure of 6 bar for pressing the feedstock compound out of the hot glue gun via an open nozzle having a diameter of 4 mm. After solidification, the resulting integral part was taken out of the mold. A picture of the integral part is depicted in FIG. 12 B; the sintered integral part is depicted in FIG. 12 C.

Manufacture of Sintered Parts

[0275] The green part was then subjected to a solvent debinding step and a sintering step. For solvent debinding, the green parts made of feedstock compounds 4-F and 6-F were dipped into acetone or ethanol in a way that it was fully immersed in the respective solvent at a temperature of 45 C. for 16 h.

[0276] 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 had a uniform shape but showed cracks after debinding.

TABLE-US-00005 TABLE 4 Debinding results of feedstock compounds 4-F and 6-F in different solvents. Feedstock compound (# in table 2) acetone ethanol 4-F + + 6-F c +

[0277] 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.

[0278] The rheometer measurements were performed for determination of viscosity in accordance with EN ISO 3219:1994 using a Kinexus rheometer (available from NETZSCH).

[0279] Table 5 shows the viscosity values of binder components 1-B to 4-B and 6-B and feedstock compounds 1-F to 4-F and 6-F determined at a temperature of 130 C.

[0280] Table 6 shows the viscosity values of binder components 1-B to 4-B and feedstock compounds 1-F to 4-F determined at a temperature of T.sub.cross+20 K.

[0281] Table 7 shows the viscosity values of binder components 1-B to 4-B and 6-B and feedstock compounds 1-F to 4-F and 6-F determined at a temperature of 100 C.

TABLE-US-00006 TABLE 5 Viscosity values of binder components 1-B to 4-B and 6-B and feedstock compounds 1-F to 4-F and 6-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 n.d. .sup.[0] 2.369 2.241 2.132 2-B* n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] 3-B* n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] 4-B 0.040 0.008 0.004 0.004 5-B n.d. .sup.[2] n.d. .sup.[2] n.d. .sup.[2] n.d. .sup.[2] 6-B 0.008 0.004 0.006 0.006 1-F 333.6 102.7 65.93 n.d. .sup.[0] 2-F* n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] 3-F* n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] 4-F 0.416 0.488 1.155 1.055 5-F n.d. .sup.[2] n.d. .sup.[2] n.d. .sup.[2] n.d. .sup.[2] 6-F 224.1 31.52 13.95 5.564 .sup.[0] not determined; measured viscosity value outside steady state flow. .sup.[1] not determined; melting point higher than 130 C. .sup.[2] not determined. *comparative example.

TABLE-US-00007 TABLE 6 Viscosity values of binder components 1-B to 4-B and feedstock compounds 1-F to 4-F at T.sub.cross + 20 K. T.sub.cross + viscosity viscosity viscosity viscosity 20 K at 0.1 s.sup.1 at 1 s.sup.1 at 10 s.sup.1 at 100 s.sup.1 # [ C.] [Pa .Math. s] [Pa .Math. s] [Pa .Math. s] [Pa .Math. s] 1-B 110 3.762 3.463 3.203 3.095 2-B* 160 2.195 1.658 1.272 1.124 3-B* 148 27.96 18.80 10.43 9.027 4-B 100 0.298 0.126 0.042 0.015 5-B 110 n.d. .sup.[0] n.d. .sup.[0] n.d. .sup.[0] n.d. .sup.[0] 1-F 110 n.d. .sup.[1] 179.2 116.7 15.80 2-F* 160 237.2 43.53 8.684 0.095 3-F* 148 1210 252.5 2.618 0.009 4-F 100 9.088 8.679 5.474 2.945 5-F 116 n.d. .sup.[0] n.d. .sup.[0] n.d. .sup.[0] n.d. .sup.[0] *comparative example. .sup.[0] not determined. .sup.[1] not determined; measured viscosity value outside steady state flow.

TABLE-US-00008 TABLE 7 Viscosity values of binder components 1-B to 4-B and 6-B and feedstock compounds 1-F to 4-F and 6-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 6.247 5.654 5.312 5.121 2-B* n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] 3-B* n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] 4-B 0.298 0.126 0.042 0.015 5-B n.d. .sup.[2] n.d. .sup.[2] n.d. .sup.[2] n.d. .sup.[2] 6-B 1.752 0.231 0.050 0.021 1-F 448.2 257.6 159.0 n.d. .sup.[3] 2-F* n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] 3-F* n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] 4-F 9.088 8.679 5.474 2.945 5-F n.d. .sup.[2] n.d. .sup.[2] n.d. .sup.[2] n.d. .sup.[2] 6-F 559.9 168.6 23.46 7.081 .sup.[1] not determined; melting point higher than 100 C. .sup.[2] not determined. .sup.[3] not determined; measured viscosity value outside steady state flow. *comparative example.

Further Examples

[0282]

TABLE-US-00009 TABLE 8 Binder components 7-B to 28-B; vol.-% relative the total volume of the binder component (b). (b-i) (b-ii) # material (b-i) [vol.-%] material (b-ii) [vol.-%] 7-B Technovit 9100 PMMA 20 Loxiol 2472 .sup.[2] 65 powder .sup.[1] Loxiol G20 .sup.[3] 15 8-B Jowat 256.10 .sup.[4] 30 Deurex A 27 P .sup.[7] 67 Licocene 1332 TP .sup.[5] 3 9-B Jowat 280.10 .sup.[8] 20 Loxiol 2472 .sup.[2] 57 Loxiol G20 .sup.[3] 20 Licocene 1332 TP .sup.[5] 3 10-B Jowat 280.10 .sup.[8] 20 Deurex A 27 P .sup.[7] 77 Licocene 1332 TP .sup.[5] 3 11-B Deurex E 06 K .sup.[6] 30 Loxiol G20 .sup.[3] 70 12-B VISCOWAX 353 .sup.[9] 30 Loxiol G20 .sup.[3] 70 13-B VISCOWAX 353 .sup.[9] 30 Deurex A 27 P .sup.[7] 70 14-B Deurex E 06 K .sup.[6] 30 1-octadecanol .sup.[10] 70 15-B Deurex E 06 K .sup.[6] 30 monostearin .sup.[11] 70 16-B Griltex 2439 A .sup.[12] 30 N-ethyltoluene-4- 55 sulfonamide .sup.[13] Deurex A 27 P .sup.[7] 10 Loxiol G20 .sup.[3] 5 17-B polycaprolactone .sup.[14] 20 Loxiol 2472 .sup.[2] 60 Loxiol G20 .sup.[3] 20 18-B polycaprolactone .sup.[14] 20 monostearin .sup.[11] 80 19-B polycaprolactone .sup.[14] 20 N-ethyltoluene-4- 75 sulfonamide .sup.[13] Loxiol G20 .sup.[3] 5 20-B polycaprolactone .sup.[14] 20 Deurex A 27 P .sup.[7] 77 Licocene 1332 TP .sup.[5] 3 21-B polycaprolactone .sup.[14] 20 1-octadecanol .sup.[10] 80 22-B VISCOWAX 353 .sup.[9] 30 1-octadecanol .sup.[10] 70 23-B VISCOWAX 353 .sup.[9] 30 monostearin .sup.[11] 70 24-B Technovit 9100 20 N-ethyltoluene-4- 75 PMMA powder .sup.[1] sulfonamide .sup.[13] 5 Loxiol G20 .sup.[3] 25-B EnBA EN 33901 .sup.[15] 20 Deurex A 27 P .sup.[7] 77 Licocene 1332 TP .sup.[5] 3 26-B EnBA EN 33901 .sup.[15] 20 monostearin .sup.[11] 80 27-B polycaprolactone .sup.[14] 20 diphenyl phthalate .sup.[17] 75 Loxiol G20 .sup.[3] 5 28-B Riteflex 425 .sup.[16] 20 monostearin .sup.[11] 80 .sup.[1] polymethylmethacrylat available at MORPHISTO GmbH .sup.[2] 4-hydroxybenzoic behenylester available from Emery Oleochemicals GmbH .sup.[3] stearic acid available from Emery Oleochemicals GmbH .sup.[4] copolymer based on different polyolefins available from Jowat AG .sup.[5] propylene-ethylene-maleic anhydride copolymer available from Clariant International Ltd .sup.[6] polyethylene-wax available from Deurex AG .sup.[7] oleamide available from Deurex AG .sup.[8] copolymer based on ethylene and vinyl acetate available from Jowat AG .sup.[9] wax based on ethylene and vinyl acetate available from Innospec Leuna GmbH .sup.[10] 1-octadecanol available from Sigma-Aldrich .sup.[11] monostearin (glycerol 2-stearate) available TCI Deutschland GmbH .sup.[12] copolyamide having a DSC melting range of 115 to 125 C., available from EMS-CHEMIE HOLDING AG .sup.[13] N-ethyltoluene-4-sulfonamide available from Sigma-Aldrich .sup.[14] polycaprolactone available from Materialix .sup.[15] copolymer based on ethylene and n-butyl acrylate available from ExxonMobil .sup.[16] polyester-based thermoplastic elastomer available from Celanese GmbH .sup.[17] diphenyl phthalate available from Sigma-Aldrich

TABLE-US-00010 TABLE 9 Melt peak temperatures T.sub.P and intersection temperatures T.sub.cross. T.sub.cross T.sub.P (binder) # [ C.] [ C.] 7-B 63.6 74.4 8-B 76.0 114.6 9-B 62.0 60.9 10-B 76.9 72.0 11-B 57.2 76.0 12-B 58.1 54.1 13-B 77.0 71.8 14-B 58.7 75.4 15-B 64.1 67.3 16-B 30.6 62.5 17-B 51.2 52.9 18-B 69.5 61.6 19-B 50.4 48.1 20-B 77.6 73.5 21-B 61.7 58.9 22-B 59.8 72.9 23-B 68.8 65.5 24-B 53.6 36.9 25-B 76.9 73.9 26-B 69.3 64.6 27-B 52.1 35.1 28-B 68.8 67.5

TABLE-US-00011 TABLE 10 Viscosity values of binder components 7-B to 28-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] 7-B 5.601 4.142 3.762 n.d. .sup.[1] 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] 0.306 0.309 0.311 17-B 1.682 1.538 1.412 1.295 18-B n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] 19-B 2.315 2.360 2.371 2.349 20-B 0.521 0.433 n.d. .sup.[1] n.d. .sup.[1] 21-B 1.763 1.371 1.156 0.728 22-B n.d. .sup.[1] 0.018 0.019 0.020 23-B n.d. .sup.[1] 0.036 0.037 0.038 24-B 2.262 2.242 2.282 2.168 25-B 0.076 0.082 0.083 0.085 26-B 0.053 0.065 0.067 0.072 27-B 5.513 5.600 5.575 5.359 28-B 4.491 4.123 3.569 2.895 .sup.[1] not determined; measured viscosity value outside steady state flow.

TABLE-US-00012 TABLE 11 Viscosity values of binder components 7-B to 28-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] 7-B 28.89 27.63 25.98 n.d. .sup.[1] 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 0.965 0.962 0.966 0.972 17-B 6.378 5.754 5.424 5.181 18-B 1.858 0.400 0.073 n.d. .sup.[1] 19-B 6.795 4.887 5.139 5.143 20-B n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] 21-B 8.538 2.907 1.922 n.d. .sup.[1] 22-B n.d. .sup.[1] 0.036 0.037 0.038 23-B n.d. .sup.[1] 0.082 0.082 0.083 24-B n.d. .sup.[1] 7.592 6.210 5.580 25-B 0.191 0.189 0.190 0.193 26-B 0.103 0.063 0.061 n.d. .sup.[1] 27-B 15.890 13.330 13.160 12.240 28-B n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] n.d. .sup.[1] .sup.[1] not determined; measured viscosity value outside steady state flow.