COMPOSITION FOR USE IN AN ADDITIVE MANUFACTURING PROCESS

Abstract

The present invention concerns a composition comprising at least one polymer, wherein the polymer is in the form of polymer particles, and wherein the composition contains at least one additive, wherein the additive is in a proportion of at most 2% by weight of the composition. Furthermore, the present invention concerns a method for the production of the composition in accordance with the invention, as well as a method for the production of an article comprising the composition in accordance with the invention. Finally, the present invention concerns the use of the composition in accordance with the invention.

Claims

1. A composition comprising (a) at least one polymer, wherein the polymer is in the form of polymer particles and wherein the polymer is selected from at least one thermoplastic polymer, and (b) at least one additive, wherein the at least one additive is in a proportion of at least 0.005% by weight of the composition, and/or wherein the additive is in a proportion of at most 2% by weight of the composition.

2. The composition as claimed in claim 1, wherein the additive is selected from at least one semicrystalline polymer, a semicrystalline polyol, a semicrystalline surfactant and/or a semicrystalline protective colloid.

3. The composition as claimed in claim 1, wherein the additive is selected from at least one polyol and/or from at least one polyethylene oxide and/or from at least one polyvinyl alcohol and/or from poloxamers and/or from sodium dodecyl sulphate, wherein the polyol is selected from at least one polyethylene glycol.

4. The composition as claimed in claim 1, wherein the crystallization temperature of the composition is reduced by at least 2 C. compared with the thermoplastic polymer without additive and/or wherein the difference TK/TM between the crystallization temperature (TK) and the melting temperature (TM) is higher by at least 1 C.

5. The composition as claimed in claim 1, wherein the thermoplastic polymer is selected from at least one polyetherimide, polycarbonate, polysulphone, polyphenylene sulphone, polyphenylene oxide, polyethersulphone, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene-acrylate copolymer, polyvinyl chloride, polyacrylate, polyester, polyamide, polypropylene, polyethylene, polyaryl ether ketone, polyether, polyurethane, polyimide, polyamide imide, polyolefin, polyarylene sulphide, as well as their copolymers and/or at least one polymer blend based on said polymers and/or copolymers.

6. The composition as claimed in claim 5, wherein the at least one of the polyamides is selected from polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 1010, polyamide 1012, polyamide 1112, polyamide 1212, polyamide PA6T/6I, poly-m-xylylene adipamide (PA MXD6), polyamide 6/6T, polyamide PA6T/66, PA4T/46 and Platamid M1757, copolymers thereof and/or wherein the at least one polypropylene is selected from isotactic polypropylene and/or copolymers thereof with polyethylene or with maleic acid anhydride.

7. The composition as claimed in claim 1, wherein the polymer comprises at least one semicrystalline copolymer and/or a semicrystalline polymer blend.

8. The composition as claimed in claim 7, wherein the polymer and/or the copolymer and/or the polymer blend has a melting temperature of at least approximately 50 C., and/or wherein the polymer and/or the copolymer and/or the polymer blend has a melting temperature of at most approximately 400 C.

9. The composition as claimed in claim 5, wherein the polyaryl ether ketone is selected from the group formed by polyether ketone ketone (PEKK) and/or from the group formed by polyether ether ketone-polyether diphenyl ether ketone (PEEK-PEDEK).

10. The composition as claimed in claim 5, wherein the polyether ketone ketone has the following repeat units repeat unit A: repeat unit B: wherein the ratio of repeat unit A to repeat unit B is approximately 60 to approximately 40.

11. The composition as claimed in claim 5, wherein the polyaryl ether ketone has a melting temperature of up to 330 C., and/or wherein the polyaryl ether ketone has a glass transition temperature of at least 120 C.

12. The composition as claimed in claim 7, wherein the polymer blend comprises a polyaryl ether ketone-polyetherimide, a polyaryl ether ketone-polyetherimide-polycarbonate, a polyphenylene sulphide-polyetherimide and/or a polyetherimide-polycarbonate.

13. The composition as claimed in claim 1, wherein the composition furthermore comprises an auxiliary material.

14. The composition as claimed in claim 1, wherein the composition has at least one anti-agglomeration agent, wherein the proportion of the at least one anti-agglomeration agent in the composition is at least 0.01% by weight, and/or wherein the proportion of the at least one anti-agglomeration agent in the composition is at most 1% by weight.

15. The composition as claimed in claim 1, wherein the composition has a bulk density of at least approximately 350 kg/m3 and/or at most approximately 650 kg/m3.

16. A method for the production of a composition, wherein the method comprises the following steps: (i) providing at least one polymer, wherein the polymer is selected from at least one thermoplastic polymer, (ii) mixing the polymer with an additive, (iii) removing the additive in order to obtain a composition, wherein the composition has a content of the at least one additive of at least 0.005% by weight of the composition, and/or wherein the additive content is at most 2% by weight.

17. A method for the production of an article comprising the steps of: (i) applying a layer of a composition as claimed in claim 1 on a build chamber, (ii) selective consolidation of the applied layer of the composition at locations which correspond to a cross section of the object to be produced, and (iii) dropping the support and repeating the steps of application and consolidation until the component has been completed.

18. A composition obtained by the method as claimed in claim 17.

19. An article obtained in accordance with a method as claimed in claim 17.

20. Use of a composition as claimed in claim 1, by a member from the group consisting of laser sintering, high speed sintering, binder jetting, selective mask sintering, selective laser melting.

Description

[0175] FIG. 1 shows a DSC thermogram of compositions in accordance with the invention (PP 001, PP002) compared with a composition which does not contain any additive (PP without additive).

EXAMPLES

Example 1

[0176] Polypropylene (PP) (polypropylene-polyethylene copolymer, Borealis, Austria) with a MVR of 30 cm.sup.3/10 min was mixed together with polyethylene glycol (PEG; molecular weight (MW) 20000 D and 35000 D; Clariant, Switzerland) in a ratio of 30% by weight of PP copolymer to 70% by weight of polyethylene glycol in an extruder (ZSE 27 MAXX, Leistritz Extrusionstechnik GmbH, Nuremburg, Germany) in the molten state (zone temperature: from 220 to 360 C.). For the PP 01 sample, the ratio of polyethylene glycol 20000 to 35000 was 50% by weight to 50% by weight. For the sample PP 02, the ratio of polyethylene glycol 20000 to 35000 was 80% by weight to 20% by weight. After extrusion, the mixture was cooled on a conveyor belt to room temperature, in ambient air, and packaged. In order to dissolve the polyethylene glycol, the mixture was then dissolved in water, with stirring (1 kg of the mixture in 9 kg of water) and centrifuged (TZ3 centrifuge, Carl Padberg Zentrifugenbau GmbH, Lahr, Germany). The powder cake formed by the PP copolymer was washed twice with 10 litres of water in the centrifuge in order to remove the surplus polyethylene glycol. The powder cake was then dried at 60 C. under 300 mbar for 10 hours in a vacuum dryer (Heraeus, VT6130 P, Thermo Fisher Scientific, Germany). Next, the powder was screened with the aid of a tumbler screening machine (screen mesh size: 245 m, Siebtechnik GmbH, Mhlheim, Germany). In a container mixer (Mixaco Labor Container Mixer, 12 litres, Mixaco Maschinenbau Dr. Herfeld GmbH & Co KG, Neuenrade, Germany) the powder was supplemented with 0.1% by weight of an anti-agglomeration agent (Aerosil R974, Evonik Resource Efficiency, Hanau, Germany), stirring for 1 minute. Powders with the following grain size were obtained:

[0177] Sample PP 01: d50=45 m

[0178] Sample PP 02: d50=40 m

[0179] The polyethylene glycol content in the dry compositions (PP 01, PP 02) was determined by means of DSC (DIN EN ISO 11357) on a DSC measuring instrument (Mettler Toledo DSC823). The evaluation was carried out with the aid of STARe 15.0 software. The method and/or data for the evaluation are shown in Table 1. The polyethylene glycol content in the dry compositions is recorded in Table 2 (below). The polyethylene oxide (PEO) content can also be determined in the same manner when this is used as the additive during production.

TABLE-US-00001 TABLE 1 Detailed description of the DSC method for the compositions in accordance with the invention as well as the integration limit and H.sub.m PEG of PEG/PEO for the determination of the PEG/PEO content in the sample. Start End Heating/cooling PEG/PEO Method Operation temperature temperature rate [K/min] or integration limit H.sub.m PEG segment type [ C.] [ C.] hold time [min] [ C.] [J/g] 1 isothermal 0 0 3 min n.d. n.d. 2 dynamic 0 220 10K/min n.d. n.d. 3 isothermal 220 220 3 min n.d. n.d. 4 dynamic 220 0 10K/min n.d. n.d. 5 isothermal 0 0 3 min n.d. n.d. 6 dynamic 0 220 10K/min from 55 to 70 171 n.d. = not determined

[0180] Methods for calculating the content of additive in the composition in accordance with the invention:

[0181] 1) Method 1: For PEG/PEO in polypropylene:

[0182] Table 1 records the DSC method as well as the integration limits and melting enthalpy of a PEG sample (H.sub.m PEG). In addition, the content of polyethylene oxide (PEO), when this is used as the additive during production, can be determined in the same manner.

[0183] The PEG/PEO melting enthalpy is determined in the 2nd heating cycle (segment 6 of the DSC method). Based on these values and with the aid of formula 1, the PEG/PEO content in the sample is determined as follows:

[00001]$\begin{array}{cc}\mathrm{PEG}.Math..Math.\mathrm{content}.Math.\left[\%\right]=\frac{.Math..Math.H_{\mathrm{PEG}}}{.Math..Math.H_{m.Math..Math.\mathrm{PEG}}}*100& \mathrm{formula}.Math..Math.1\end{array}$

[0184] H.sub.PEG is the PEG melting enthalpy in the sample, determined using the method shown in Table 1.

[0185] H.sub.m PEG is the PEG melting enthalpy of a pure PEG sample (171 J/g), determined using polyglycol 20000 S (technical quality, Clariant, Switzerland).

[0186] 2) Method 2: For PEG/PEO in semicrystalline and amorphous polymers and polymer blends:

[0187] Analogous to the determination of the content of PEG/PEO in polypropylene (see method 1). In contrast to method 1, though, 220 C. was used for the start temperature (segments 3+4) and the end temperature (segments 2+3+6) in the DSC; the temperature employed was that used for the semicrystalline polymer, in accordance with DIN EN ISO 11357. However, the maximum end temperature was limited to 360 C. in order to avoid thermal degradation of the PEG/PEO.

[0188] 3) Method 3: For semicrystalline additives by means of DSC:

[0189] Analogous to the determination of the PEG/PEO content in semicrystalline polymers (see method 2). The difference was for the start temperature (segments 3+4) and end temperature (segments 2+3+6) in the DSC; the temperature employed was that used for the semicrystalline polymer or the additive, in accordance with DIN EN ISO 11357. Whichever was the higher temperature, this was the one employed.

[0190] The determination of the additive content was made analogously to the determination of the PEG/PEO content. However, in contrast, DSC method 3 was employed.

[00002]$\begin{array}{cc}\mathrm{Additive}.Math..Math.\mathrm{content}.Math.\left[\%\right]=\frac{.Math..Math.H_{\mathrm{additive}}}{.Math..Math.H_{m.Math..Math.\mathrm{additive}}}*100& \mathrm{formula}.Math..Math.2\end{array}$

[0191] H.sub.Additive is the melting enthalpy of the additive in the sample, determined using the DSC method 3.

[0192] H.sub.m Additive is the melting enthalpy of the pure additive, determined using the DSC method 3.

[0193] The crystallization and melting temperatures of the compositions were determined by means of DSC (DIN EN ISO 11357) on a DSC measuring instrument (Mettler Toledo DSC823). The evaluation was carried out with the aid of STARe 15.0 software. The changes to the crystallization and melting temperatures of the composition in accordance with the invention with additive (PP 01, PP 02) compared to a composition without the addition of an additive (PP without additive) are shown in Table 2 and FIG. 1.

[0194] FIG. 1 is a DSC thermogram of the PP without additive, PP 01 and PP 02 samples which are conventionally plotted as a function of temperature ( C.). Instead of the ordinate, a reference bar of 20 mW is provided. In the upper three curves are the respective melting peaks, i.e. the temperature TM at which the composition melts for the samples PP without additive, PP 01 and PP 02. The lower curves show the crystallization temperatures TK of the samples PP without additive, PP 01 and PP 02.

[0195] Upon the addition of additive, a variation in both the crystallization temperature, TK, and also in the melting temperature, TM, was observed. The comparative sample PP without additive had a crystallization temperature of approximately 115 C. (see Table 2: PP without additive sample, column TK 1st heating rate (HR); FIG. 1: solid line, uppermost DSC thermogram). With a content of additive of 0.64% by weight in the dry composition in accordance with the invention (PP 01) in the present case of PEG with a molecular weight (MW) of 35000 D and 20000 D in a ratio of 50:50, there was a reduction in the crystallization temperature of approximately 8 C., namely from approximately 115 C. to approximately 107 C. (see Table 2: sample (PP 01), column TK 1st HR; FIG. 1: dotted line, second to top DSC thermogram). At a PEG content of 1.09% by weight in the dry composition in accordance with the invention (PP 02) (PEG MW 35000 D to MW 20000 D: ratio: 20:80), a reduction in the crystallization temperature of approximately 15 C., from approximately 115 C. to approximately 100 C., was produced (see Table 2: sample PP 02, column TK 1st HR; FIG. 1: dashed line, third DSC thermogram from top).

[0196] In respect of a variation in the melting temperature TM of the composition in accordance with the invention in comparison with a sample without additive, it should be noted that for the sample without additive, a double peak at approximately 132 C. and 141 C. was observed (see Table 2: sample without additive, column TM 2nd HR; FIG. 1: lowest solid line). With an additive content of 0.64% by weight, however, one melting peak could be observed which had a peak at approximately 137.5 C. (see Table 2: sample PP 01, column TM 2nd HR; FIG. 1: lowest dotted line); finally, for the sample PP 02 which had an additive content of 1.09% by weight, there was a peak at approximately 135 C. (see Table 2: sample PP 02, column TM 2nd HR; FIG. 1: lowest dashed line).

TABLE-US-00002 TABLE 2 Crystallization and melting temperatures of polypropylene copolymer samples (PP) without the addition of additive (PP without additive) and with the addition of additive (PP 01, PP 02). The additive consisted of a mixture of PEG with a molecular weight (MW) of 35000 D and 20000 D in the ratios shown. Additive/ TM s onset/ TK PEG Additive(s) TM onset/TK 35000 content in dry TM endset XC dH TK endset XC D/PEG composition 2nd HR 2nd HR 2nd HR 2nd HR 1st HR 1st HR 1st HR Polymer 20000 D [% by wt] [ C.] [ C.] [%] [J/g] [ C.] [ C.] [%] PP n.a. n.d. 131.75/ 74.94/ 39.33 82.20 115.36 118.76/ 39.45 without 140.8 144.52 109.77 additive PP 01 50/50 0.64 Shoulder/ 131.73/ 37.96 79.34 107.51 112.62/ 39.48 137.47 139.97 102.32 PP 02 20/80 1.09 135.04 130.67/ 36.55 76.39 100.00 103.66/ 37.93 139.46 96.41 n.a. = not applicable TM = melting temperature TK = crystallization temperature HR = heating rate XC = crystallinity dH = melting enthalpy

Example 2

[0197] The production of the composition in accordance with the invention of Example 2 was carried out in the same manner as for Example 1. The polypropylene-polyethylene copolymer used (type QR674K) in Example 2 was obtained from Sabic Innovative Plastics (Bergen op Zoom, Netherlands); the additive used was polyethylene glycol (Clariant, Switzerland) with a molar mass of 35000 D. A powder with the following grain size was obtained:

PP 03: d50=29 m

[0198] The determination of the content of PEG was carried out in analogous manner to Example 1.

[0199] The melting temperature TM and crystallization temperature TK of the composition in accordance with the invention PP 03 compared with a PP without additive sample is shown in Table 3. Again, with the addition of additive, a variation in the crystallization temperature TK and also in the melting temperature TM compared with a sample without additive was observed. The PP without additive comparative sample had a crystallization temperature of approximately 120 C. (see Table 3: sample PP without additive, column TK 1st heating rate (HR)). With an additive content of 0.08% by weight in the dry composition in accordance with the invention (PP 03), in the present case of PEG with a molecular weight (MW) of 35000 D, there was a reduction in the crystallization temperature of approximately 12 C., namely from approximately 120 C. to approximately 108 C. (see Table 3: sample PP 03, column TK 1st HR).

TABLE-US-00003 TABLE 3 Crystallization and melting temperature of polypropylene copolymer samples (PP) without the addition of additive (PP without additive) and with the addition of additive (PP 03). The additive consisted of PEG with a molecular weight (MW) of 35000 D. TK PEG content TM onset/ onset/TK in dry TM TM endset XC dH TK endset XC composition 2nd HR 2nd HR 2nd HR 2nd HR 1st HR 1st HR 1st HR Polymer [% by wt] [ C.] [ C.] [%] [J/g] [ C.] [ C.] [%] PP without n.d. 135.5/148.9 139.3/ 38.8 81.1 119.8 123.3/ 39.1 additive 153.1 113.8 PP 03 0.08% 144.2 137.0/ 37.0 77.4 108.1 110.1/ 38.3 150.6 104.9

Example 3

[0200] Polyether ketone ketone (PEKK) (Kepstan 6004, Arkema, France) was mixed together with polyethylene glycol (PEG; molecular weight (MW) 20000 D and 35000 D; Clariant, Switzerland) or polyethylene oxide (PEO: molecular weight (MW) 100000 D; The Dow Chemical Company, Polyox WSR N10) in a ratio of 30-40% by weight of PEKK to 60-70% by weight of PEG and/or PEO, in an extruder (ZSE 27 MAXX, Leistritz Extrusionstechnik GmbH, Nuremburg, Germany) in the molten state (zone temperature: 340 C.). The exact ratios are shown in Table 4. After extrusion, the mixture was cooled on a conveyor belt at a cooling rate of 5 C./second (s) to room temperature and packaged. In order to dissolve the PEG or PEO, a portion of the mixture was then dissolved at 70 C. in water, with stirring (30 g in 150 mL of water), screened in a vibration screening machine (AS200, mesh size 300 m, Retsch, Haan, Germany) and the <300 m filtrate was filtered off using a Bchner funnel. The powder cake was washed twice more with 150 mL of water in an Erlenmeyer flask and filtered each time in a Bchner funnel in order to remove the surplus PEG or PEO. The powder cake was then dried at 60 C. under 300 mbar for 10 hours in a vacuum dryer (Heraeus, VT6130 P, Thermo Fisher Scientific, Germany). Powder samples were obtained with the properties shown in Table 5. The determination of the grain size distribution and sphericity (SPHT3) was carried out using a Camsizer XT (Retsch Technology, Software Version 6.0.3.1008, Germany) in accordance with DIN ISO 13322-2, with the X-Flow module in a solution of Triton X in distilled water (3 percent by weight). Evaluation on the basis of Xarea.

TABLE-US-00004 TABLE 4 Proportions of PEKK and PEG 20000 or PEG 35000 and PEO in the test compositions. PEG PEG PEKK 20000 D 35000 D PEO [% by wt] [% by wt] [% by wt] [% by wt] PEKK 100 n.a. n.a. n.a. without additive PEKK-01 30 0 0 70 PEKK-02 30 0 17.5 52.5 PEKK-03 30 0 35 35 PEKK-04 30 0 70 0 PEKK-05 30 17.5 52.5 0 PEKK-06 40 0 60 0 PEKK-07 30 35 35 0 PEKK-08 30 70 0 0 n.a. = not applicable

TABLE-US-00005 TABLE 5 Grain size distribution and DSC measurements of the tested (dry) compositions. DSC PEG/PEO TM XM TM XM TM XM content in Grain size distribution 1st 1st 2nd 2nd 1st 1st dry d10 d50 d90 HR HR HR HR HR HR composition [m] [m] [m] [ C.] [%] [ C.] [%] [ C.] [%] [% by wt] PEKK n.d. n.d. n.d. 291.1 0.0 301.3 23.6 241.3 22.0 n.d. without additive PEKK-01 4.9 9.5 27.7 284.6 14.4 300.0 24.1 236.6 23.6 0.019 PEKK-02 9.8 11.7 28.8 284.9 14.6 297.9 24.6 237.0 22.9 0.035 PEKK-03 14.6 24.2 80.3 283.7 16.0 297.1 26.0 238.7 25.7 0.022 PEKK-05 12.1 31.6 79.2 284.0 18.6 298.4 28.3 242.1 26.6 0.141 PEKK-06 14.9 40.8 95.9 284.1 19.2 299.1 28.8 242.7 29.9 0.153 PEKK-07 18.5 41.3 82.8 284.3 17.8 298.8 22.8 244.2 31.7 0.106 PEKK-08 22.5 62.7 135.7 284.7 16.6 297.9 27.2 242.3 26.4 0.141 PEKK-09 24.0 76.7 181.6 284.2 14.9 297.6 28.5 242.7 28.4 0.110

[0201] The PEG or PEO content of the dry compositions was determined by means of DSC (DIN EN ISO 11357) on a DSC measuring instrument (Mettler Toledo DSC823). The evaluation was carried out with the aid of STARe 15.0 software. The method and/or data for the evaluation are shown in Table 6. Because PEKK, as a quasi-amorphous polymer, does not crystallize at 10 C./min or 20 C./min, in order to initiate crystallization, the measurement was carried out in segment 5 at a cooling rate of 2 C./minthis was not in accordance with the standard.

TABLE-US-00006 TABLE 6 Detailed description of the DSC method for the compositions in accordance with the invention as well as the integration limit and H.sub.m PEG of PEG/PEO for the determination of the PEG/PEO content in the PEKK samples. PEG/PEO Start End Heating/cooling integration Method Operation temperature temperature rate [K/min] or limit H.sub.m PEG segment type [ C.] [ C.] hold time [min] [ C.] [J/g] 1 isothermal 0 0 3 min n.d. n.d. 2 dynamic 0 360 20K/min n.d. n.d. 3 isothermal 360 360 3 min n.d. n.d. 4 dynamic 360 280 20K/min n.d. n.d. 5 dynamic 280 180 2K/min n.d. n.d. 6 dynamic 180 0 20K/min n.d. n.d. 7 isothermal 0 0 3 min n.d. n.d. 8 dynamic 0 360 20K/min from 55 to 70 171

[0202] The method for calculating the additive content of the composition in accordance with the invention was carried out in accordance with the description of Example 1. In contrast to this, the PEG/PEO melting enthalpy was determined in segment 8 instead of segment 6 of the DSC method.

[0203] It can be seen from Table 5 that the grain size can be adjusted as a function of the molar mass of PEG and PEO. With increasing molar mass (PEO fraction), the crystallization point of the material can also be reduced. This method also shows a further major advantage of PEKK. Unfilled PEKK (60:40 T/L of copolymer) (PEKK without additive), which was extruded without PEG/PEO, is present as a quasi-amorphous granulate, because cooling after extrusion occurs very rapidly (typically >100 C./s). The DSC revealed cold post-crystallization with an exothermic peak at approximately 256 C. with a subsequent endothermic peak at 306 C., TM 1st HR. A common integration of the post-crystallization peak and subsequent melting peak produced a melting enthalpy of 0 J/g and thus a crystallinity of 0%, XC 1st HR, in the granulate. However, amorphous materials are rather difficult to process with laser sintering. By means of melt emulsification, a semicrystalline PEKK powder was obtained with a melting point TM (1st HR) of approximately 284 C. and a crystallinity XM (1st HR) of 14.4-19.2%. The calculation of the value for the crystallinity by means of DSC in this regard produced 130 J/g for theoretically 100% crystalline PEKK (source: Cytec, Technical Data Sheet, PEKK Thermoplastic Polymer, Table 3). For all of the powders, with the exception of PEKK-03, sphericities of >0.9 (Camsizer XT, SPHT3) were obtained.

Example 4

[0204] A carbon fibre-filled PEKK (PEKK-CF, HT23, Advanced Laser Materials, Temple TX, USA) was mixed together with polyethylene glycol (PEG; molecular weight (MW) 20000 D and 35000 D; Clariant, Switzerland) or polyethylene oxide (PEO: molecular weight (MW) 100000 D; The Dow Chemical Company, Polyox WSR N10) at a ratio of 30% by weight of PEKK to 70% by weight of PEG and/or PEO, in an extruder (ZSE 27 MAXX, Leistritz Extrusionstechnik GmbH, Nuremburg, Germany) in the molten state (zone temperature: 340 C.). The exact ratios are provided in Table 7. After extrusion, the mixture was cooled on a conveyor belt at a cooling rate of 5 C./second (s) to room temperature and packaged. In order to dissolve the PEG or PEO, a portion of the mixture was then dissolved at 70 C. in water, with stirring (30 g in 150 mL of water), screened in a vibration screening machine (AS200, mesh size 300 m, Retsch, Haan, Germany) and the <300 m filtrate was filtered off using a Bchner funnel. Subsequently, the powder cake was washed twice with 150 mL of water in an Erlenmeyer flask and filtered each time in a Bchner funnel in order to remove the surplus PEG or PEO. The powder cake was then dried at 60 C. under 300 mbar for 10 hours in a vacuum dryer (Heraeus, VT6130 P, Thermo Fisher Scientific, Germany). Powder was obtained with the properties shown in Table 8. The determination of the grain size distribution and sphericity (SPHT3) was carried out using a Camsizer XT (Retsch Technology, Software Version 6.0.3.1008, Germany) in accordance with DIN ISO 13322-2, with the X-Flow module in a solution of Triton X in distilled water (3 percent by weight). Evaluation on the basis of Xarea.

TABLE-US-00007 TABLE 7 PEKK-CF and PEG 20000 or PEG 35000 and PEO proportions of the tested compositions. PEG PEG PEKK 20000 D 35000 D PEO [% by wt] [% by wt] [% by wt] [% by wt] PEKK-CF 100 n.a. n.a. n.a. without additive PEKK-CF-01 30 0 0 70 PEKK-CF-02 30 0 17.5 52.5 PEKK-CF-04 30 0 52.5 17.5 PEKK-CF-05 30 0 70 0 PEKK-CF-06 30 35 35 0

TABLE-US-00008 TABLE 8 Grain size distribution and DSC measurements of the tested (dry) compositions. DSC Grain size TM XM TM XM TK XC PEG/PEO distribution 1st 1st 2nd 2nd 1st 1st content in dry d10 d50 d90 HR HR HR HR HR HR composition [m] [m] [m] [ C.] PA [ C.] PA [ C.] PA [% by wt] PEKK-CF n.d. n.d. n.d. n.d.- n.d.- 298.9 20.6 262.0 26.1 n.d. without additive PEKK-CF-01 4.8 16.0 99.6 283.9 16.5 296.5 19.6 246.8 24.8 0.043 PEKK-CF-02 5.8 15.7 104.1 284.6 16.5 297.2 20.5 244.4 25.3 0.031 PEKK-CF-04 18.5 47.2 141.8 283.8 12.5 296.9 21.5 247.8 29.8 0.057 PEKK-CF-05 8.5 45.2 155.2 283.7 15.7 297.3 21.8 247.9 27.1 0.011 PEKK-CF-06 26.0 122.5 261.8 284.4 16.7 297.2 20.9 252.5 27.0 0.068

[0205] The PEG or PEO content in the dry compositions was determined by means of DSC (DIN EN ISO 11357) on a DSC measuring instrument (Mettler Toledo DSC823). The evaluation was carried out with the aid of STARe 15.0 software. The method and/or data for the evaluation are shown in Table 9. The PEG or PEO content in the dry compositions is recorded in Table 8.

TABLE-US-00009 TABLE 9 Detailed description of the DSC method for the compositions in accordance with the invention as well as the integration limit and H.sub.m PEG of PEG/PEO for the determination of the PEG/PEO content in the carbon fibre-filled PEKK samples (PEKK-CF). PEG/PEO Start End Heating/cooling integration Method Operation temperature temperature rate [K/min] or limit H.sub.m PEG segment type [ C.] [ C.] hold time [min] [ C.] [J/g] 1 isothermal 0 0 3 min n.d. n.d. 2 dynamic 0 360 20K/min n.d. n.d. 3 isothermal 360 360 3 min n.d. n.d. 4 dynamic 360 280 20K/min n.d. n.d. 5 dynamic 280 180 2K/min n.d. n.d. 6 dynamic 180 0 20K/min n.d. n.d. 7 isothermal 0 0 3 min n.d. n.d. 8 dynamic 0 360 20K/min from 55 to 70 171

[0206] The method for calculating the additive content in the composition in accordance with the invention was carried out in accordance with the description of Example 1. However, the PEG/PEO melting enthalpy was determined in segment 8 instead of in segment 6 of the DSC method.

[0207] Table 8 clearly shows that the grain size can be adjusted as a function of the molar mass of PEG and PEO. With increasing molar mass (PEO fraction), the crystallization point of the material can also be reduced. The method also shows a further major advantage for filled PEKK-CF, analogously to unfilled PEKK. Even PEKK-CF without additive, which is extruded without PEG/PEO, is present as a quasi-amorphous granulate, because cooling after extrusion was carried out very rapidly (DSC revealed a cold post-crystallization with an exothermic peak at approximately 255 C. with a subsequent endothermic peak at 306 C., TM 1.sup.st HR. A common integration of post-crystallization peak and subsequent melting peak produced a melting enthalpy of 0 J/g and thus a crystallinity of 0%, XC 1st HR, in the granulate). However, amorphous materials are rather difficult to process by laser sintering. By means of melt emulsification, semicrystalline PEKK-CF powder was obtained with a melting point TM (1st HR) of approximately 284 C. and a crystallinity XM (1st HR) of 14.4-19.2%. The calculation of the value for the crystallinity by means of DSC was carried out in this regard with 130 J/g for theoretically 100% crystalline PEKK (source: Cytec, Technical Data Sheet, PEKK Thermoplastic Polymer, Table 3), not including the carbon fibre fraction of 23%.

Example 5

[0208] Polyetherimide (PEI) (Ultem 1010, Sabic Innovative Plastics, Bergen op Zoom, Netherlands) was mixed together with polyethylene glycol (PEG; molecular weight (MW) 35000 D; Clariant, Switzerland) or polyethylene oxide (PEO: molecular weight (MW) 100000 D; The Dow Chemical Company, Polyox WSR N10) in a ratio of 30% by weight of PEI to 70% by weight of PEG and/or PEO, in an extruder (ZSE 27 MAXX, Leistritz Extrusionstechnik GmbH, Nuremburg, Germany) in the molten state (zone temperature: 340 C.). The exact ratios are provided in Table 9. After extrusion, the mixture was cooled on a conveyor belt at a cooling rate of 5 C./second (s) to room temperature and packaged. In order to dissolve the PEG or PEO, a portion of the mixture was then dissolved at 70 C. in water, with stirring (10 g in 1500 mL of water), screened in a vibration screening machine (AS200, mesh size 300 m, Retsch, Haan, Germany) and the <300 m filtrate was filtered off using a Bchner funnel. The powder cake was washed twice more with 1500 mL of water in an Erlenmeyer flask and filtered each time in a Bchner funnel in order to remove the surplus PEG or PEO. The powder cake was then dried at 60 C. under 300 mbar for 10 hours in a vacuum dryer (Heraeus, VT6130 P, Thermo Fisher Scientific, Germany). Powder was obtained with the properties shown in Table 10. The determination of the grain size distribution and sphericity (SPHT3) was carried out using a Camsizer XT (Retsch Technology, Software Version 6.0.3.1008, Germany) in accordance with DIN ISO 13322-2, with the X-Flow module in a solution of Triton X in distilled water (3 percent by weight). Evaluation on the basis of Xarea.

TABLE-US-00010 TABLE 10 PEI and PEG 20000 or PEG 35000 and PEO fractions of the tested compositions as well as data regarding the grain size distribution and DSC of the dry compositions. DSC PEG/PEO PEG PEG Grain size distribution content in dry PEI 20000 D 35000 D PEO d10 d50 d90 composition [% by wt] [% by wt] [% by wt] [% by wt] [m] [m] [m] [% by wt] PEI 100 n.a. n.a. n.a. n.d. n.d. n.d. n.d. without additive PEI-01 30 0 0 70 6.8 14.9 88.5 0.082 PEI-02 30 0 17.5 52.5 10.4 20.3 71.0 0.030 PEI-03 30 0 25.9 44.1 24.5 56.9 89.3 0.061 PEI-04 30 0 35 35 42.1 97.0 168.0 0.009 PEI-05 30 0 70 0 31.1 128.4 230.1 0.044

[0209] The PEG or PEO content in the dry compositions was determined by means of DSC (DIN EN ISO 11357) on a DSC measuring instrument (Mettler Toledo DSC823). The evaluation was carried out with the aid of STARe 15.0 software. The method and/or data for the evaluation are shown in Table 11. The PEG or PEO content in the dry compositions is recorded in Table 10.

TABLE-US-00011 TABLE 11 Detailed description of the DSC method for the compositions in accordance with the invention as well as the integration limit and H.sub.m PEG of PEG/PEO for the determination of the PEG/PEO content in the PEI samples. PEG/PEO Start End Heating/cooling integration Method Operation temperature temperature rate [K/min] or limit H.sub.m PEG segment type [ C.] [ C.] hold time [min] [ C.] [J/g] 1 isothermal 0 0 3 min n.d. n.d. 2 dynamic 0 360 20K/min n.d. n.d. 3 isothermal 360 360 3 min n.d. n.d. 4 dynamic 360 0 20K/min n.d. n.d. 5 isothermal 0 0 3 min n.d. n.d. 6 dynamic 0 360 20K/min from 55 to 70 171

[0210] The method for calculating the additive content in the composition in accordance with the invention was carried out in accordance with the description in Example 1, in segment 6 of the DSC method.

[0211] Table 10 clearly shows that the grain size can be adjusted as a function of the molar mass of PEG and PEO. Because PEI is melt amorphous, no melting point and no crystallization point could be determined.

Example 6

[0212] Linear polyphenylene sulphide (PPS) (MVR (315 C., 2.16 kg)=33 cm.sup.3/10 min) was mixed together with polyethylene glycol (PEG; molecular weight (MW) 20000 D and/or 35000 D; Clariant, Switzerland) or polyethylene oxide (PEO: molecular weight (MW) 100000 D; The Dow Chemical Company, Polyox WSR N10) in a ratio of 30-40% by weight of PPS to 60-70% by weight of PEG and/or PEO, in an extruder (ZSE 27 MAXX, Leistritz Extrusionstechnik GmbH, Nuremburg, Germany) in the molten state (zone temperature: 290 C.). The exact ratios are provided in Table 12. After extrusion, the mixture was cooled on a conveyor belt at a cooling rate of 4 C./second (s) to room temperature and packaged. In order to dissolve the PEG or PEO, a portion of the mixture was then dissolved at 70 C. in water, with stirring (30 g in 150 mL of water), screened in a vibration screening machine (AS200, mesh size 300 m, Retsch, Haan, Germany) and the <300 m filtrate was filtered off using a Bchner funnel. Subsequently, the powder cake was washed twice with 150 mL of water in an Erlenmeyer flask, filtered each time in the Bchner funnel, in order to remove the surplus PEG or PEO. The powder cake was then dried at 60 C. under 300 mbar for 10 hours in a vacuum dryer (Heraeus, VT6130 P, Thermo Fisher Scientific, Germany). Powder was obtained with the properties shown in Table 13. The determination of the grain size distribution and sphericity (SPHT3) was carried out using a Camsizer XT (Retsch Technology, Software Version 6.0.3.1008, Germany) in accordance with DIN ISO 13322-2, with the X-Flow module in a solution of Triton X in distilled water (3 percent by weight). Evaluation on the basis of Xarea.

TABLE-US-00012 TABLE 12 PPS and PEG 20000 or PEG 35000 and PEO proportions in the tested compositions. PEG PEG PPS 20000 D 35000 D PEO [% by wt] [% by wt] [% by wt] [% by wt] PPS 100 n.a. n.a. n.a. without additive PPS-01 30 0 0 70 PPS-02 30 0 35 35 PPS-03 30 0 70 0 PPS-04 30 35 35 0 PPS-05 40 30 30 0 PPS-06 30 70 0 0

TABLE-US-00013 TABLE 13 Grain size distribution and DSC measurements of the tested (dry) compositions. DSC Grain size TM XM TM XM TK XC PEG/PEO distribution 1st 1st 2nd 2nd 1st 1st content in d10 d50 d90 HR HR HR HR HR HR dry composition [m] [m] [m] [ C.] [%] [ C.] [%] [ C.] [%] [% by wt] PPS n.d. n.d. n.d. n.d. n.d. 275.6 38.5 221.8 40.6 n.d. without additive PPS-01 3.9 6.0 56.2 280.9 37.2 279.2 41.3 232.9 39.4 0.034 PPS-02 3.6 5.3 34.1 277.2 40.9 278.3 44.5 232.5 42.9 0.137 PPS-03 4.8 12.9 73.7 278.2 35.2 277.7 40.8 231.1 40.5 0.325 PPS-04 5.5 18.5 68.9 279.2 36.2 277.6 40.0 231.0 39.2 0.307 PPS-05 7.7 26.2 69.7 278.8 36.3 277.2 40.6 231.2 40.1 0.393 PPS-06 10.8 41.2 107.7 280.2 37.0 277.6 40.2 231.4 39.2 0.417

[0213] The PEG or PEO content in the dry compositions was determined by means of DSC (DIN EN ISO 11357) on a DSC measuring instrument (Mettler Toledo DSC823). The evaluation was carried out with the aid of STARe 15.0 software. The method and/or data for the evaluation are shown in Table 14. The PEG or PEO content in the dry compositions is recorded in Table 13.

TABLE-US-00014 TABLE 14 Detailed description of the DSC method for the compositions in accordance with the invention as well as the integration limit and H.sub.m PEG of PEG/PEO for the determination of the PEG/PEO content in the polyphenylene sulphide samples. PEG/PEO Start End Heating/cooling integration Method Operation temperature temperature rate [K/min] or limit H.sub.m PEG segment type [ C.] [ C.] hold time [min] [ C.] [J/g] 1 isothermal 0 0 3 min n.d. n.d. 2 dynamic 0 320 20K/min n.d. n.d. 3 isothermal 320 320 3 min n.d. n.d. 4 dynamic 320 0 20K/min n.d. n.d. 5 isothermal 0 0 3 min n.d. n.d. 6 dynamic 0 320 20K/min from 55 to 70 171

[0214] The method for calculating the additive content in the composition in accordance with the invention was carried out in accordance with the description of Example 1, in segment 6 of the DSC method. The calculation of the value for the crystallinity by means of DSC produced 112 J/g for theoretically 100% crystalline PPS.

[0215] Table 13 clearly shows that the grain size can be adjusted as a function of the molar mass of PEG and PEO. By raising the proportion of PPS from 30% to 40% by weight, the grain size can be increased (cf. PPS-04 and PPS-05) when the ratio of the proportions of PEG with a molecular weight of 20000 and 35000 of 1:1 is retained.

Example 7

[0216] A polyamide 12 (PA12-16) (Grilamide L16 LM, EMS-Chemie, Switzerland) or a polyamide 12 (PA12-20) (Grilamide L20 LM, EMS-Chemie, Switzerland) was mixed together with polyethylene glycol (PEG; molecular weight (MW) 20000 D Clariant, Switzerland) in a ratio of 45% by weight of PA12-16 to 55% by weight of PEG in an extruder (ZSE 27 MAXX, Leistritz Extrusionstechnik GmbH, Nuremburg, Germany) in the molten state (zone temperature: 260 C.). The exact ratios are provided in Table 15. After extrusion, the mixture was cooled on a conveyor belt at a cooling rate of 4 C./second (s) to room temperature and packaged. In order to dissolve the PEG or PEO, a portion of the mixture was then dissolved at 70 C. in water, with stirring (30 g in 150 mL of water), screened in a vibration screening machine (AS200, mesh size 300 m, Retsch, Haan, Germany) and the <300 m filtrate was filtered off using a Bchner funnel. The powder cake was washed twice more with 150 mL of water in an Erlenmeyer flask and filtered each time in a Bchner funnel in order to remove the surplus PEG. The powder cake was then dried at 60 C. under 300 mbar for 10 hours in a vacuum dryer (Heraeus, VT6130 P, Thermo Fisher Scientific, Germany). Powder was obtained with the properties shown in Table 16. The determination of the grain size distribution and sphericity (SPHT3) was carried out using a Camsizer XT (Retsch Technology, Software Version 6.0.3.1008, Germany) in accordance with DIN ISO 13322-2, with the X-Flow module in a solution of Triton X in distilled water (3 percent by weight). Evaluation on the basis of Xarea.

TABLE-US-00015 TABLE 15 PA12 and PEG 20000 or PEG 35000 and PEO proportions in the tested compositions, as well as MVR. MVR PEG PEG (235 C., 2.16 kg) PA12 20000 D 35000 D PEO [cm.sup.3/10 min] [% by wt] [% by wt] [% by wt] [% by wt] PA12-16 49.9 100 n.a. n.a. n.a. without additive PA12-20 20.3 100 n.a. n.a. n.a. without additive PA12-16-01 n.d. 45 55 0 0 PA12-20-01 n.d. 45 55 0 0

TABLE-US-00016 TABLE 16 Grain size distribution and DSC measurements of the tested (dry) compositions. DSC PEG/PEO Grain size TM XM TM XM TK XC content in distribution 1st 1st 2nd 2nd 1st 1st dry d10 d50 d90 HR HR HR HR HR HR composition [m] [m] [m] [ C.] [%] [ C.] [%] [ C.] [%] [% by wt] PA12-16 n.d. n.d. n.d. 179.0 25.7 176.5 34.8 155.5 36.6 n.d. without additive PA12-20 n.d. n.d. n.d. 182.0 24.6 176.7 28.1 147.4 33.4 n.d. without additive PA12-16-01 24.8 71.6 141.8 176.7 24.3 176.1 33.8 154.9 35.6 0.076 PA12-20-01 14.6 45.2 86.4 176.4 25.2 175.7 34.8 148.6 35.2 0.283

[0217] The PEG or PEO content in the dry compositions was determined by means of DSC (DIN EN ISO 11357) on a DSC measuring instrument (Mettler Toledo DSC823). The evaluation was carried out with the aid of STARe 15.0 software. The method and/or data for the evaluation are shown in Table 17. The PEG content of the dry compositions is recorded in Table 16.

[0218] The calculation of the value for the crystallinity of polyamide 12, carried out by means of DSC from the melting enthalpy or crystallization enthalpy, produced 209.5 J/g for theoretically 100% crystalline polyamide 12.

TABLE-US-00017 TABLE 17 Detailed description of the DSC method for the compositions in accordance with the invention as well as the integration limit and H.sub.m PEG of PEG/PEO for the determination of the PEG/PEO content in the PA-12 sample. PEG/PEO Start End Heating/cooling integration Method Operation temperature temperature rate [K/min] or limit H.sub.m PEG segment type [ C.] [ C.] hold time [min] [ C.] [J/g] 1 isothermal 0 0 3 min n.d. n.d. 2 dynamic 0 250 20K/min n.d. n.d. 3 isothermal 250 250 3 min n.d. n.d. 4 dynamic 250 0 20K/min n.d. n.d. 5 isothermal 0 0 3 min n.d. n.d. 6 dynamic 0 250 20K/min from 55 to 70 171

[0219] The method for calculating the additive content in the composition in accordance with the invention was carried out in accordance with the description of Example 1. The PEG/PEO melting enthalpy was determined in segment 6 of the DSC method.

[0220] Table 16 clearly shows that the grain size can be adjusted as a function of the melt viscosity of the polyamide 12 employed. With higher melt viscosity, and this also means with higher molar mass, a narrower grain size distribution was obtained when the same proportion of PEG was processed.