Improved Powders for Additive Manufacturing

Abstract

The present invention relates to a composition comprising at least one polymer, the polymer being in the form of a powder, the polymer comprising at least one thermoplastic polymer, the thermoplastic polymer being selected from at least one polyaryletherketone and / or their copolymers and / or block copolymers and / or polymer blends, the composition being at least 5 cm 3 The present invention also relates to a process for the manufacture and use of the composition. The present invention also deals with a fabricated element and a process for the manufacture of the fabricated element.

Description

[Technical Field]

[0001] The present invention relates to a composition comprising at least one thermoplastic polymer, wherein the composition exhibits a specific melt volume rate to enable an optimized additive manufacturing process. Furthermore, the present invention relates to a process for producing the composition of the present invention, as well as an apparatus comprising the composition of the present invention and the use of the composition of the present invention. [Background technology]

[0002] Additive manufacturing processes for the industrial production of prototypes and equipment based on powdered fabrication materials are enabling the manufacture of plastic products and are continuously increasing in importance. By using these manufacturing processes, layers are selectively melted and solidified, and the desired structure is produced by applying binders and / or adhesives, respectively. These processes are also called "additive manufacturing," "digital fabrication," or "three-dimensional (3D) printing."

[0003] The industrial development process for manufacturing prototypes (rapid prototyping) has been used for decades. However, technological advancements in systems have led to the production of components that meet the qualitative requirements of the final product, either in place of or in addition to prototypes (rapid manufacturing). In other words, today's technological advancements in systems make it possible to manufacture components that meet the qualitative requirements of the final product.

[0004] In practice, the term "additive manufacturing" is often replaced by the terms "progressive manufacturing" or "rapid technology." Processes involved in additive manufacturing using powdered materials include, for example, sintering, melting, or bonding with binders.

[0005] In many cases, polymer systems are used as powdered materials for the manufacture of articles. Industrial users of such polymer systems require good processability, molding accuracy, and good mechanical properties of articles manufactured by such systems.

[0006] For the purpose of manufacturing such articles, since interdiffusion can only occur within the melt mass, it is advantageous to obtain a bond between the melt mass and the underlying 3D structure. However, if the bonding of the (one or more) layers is insufficient due to insufficient melting properties of the polymer, the 3D article tends to delaminate and lose stability. Therefore, the build temperature during manufacturing must be induced to optimize the melting properties of the polymer during manufacturing.

[0007] Therefore, during the manufacture of a 3D article, a build temperature higher than the crystallization temperature of the polymer is required. On the other hand, in order to prevent the powder cake from melting in the build area, the build temperature must essentially be below the melting temperature. Generally, the temperature ranges applicable for building objects by additive manufacturing are each referred to as the process window or sintering window of the polymer. SUMMARY OF THE INVENTION

[0008] Thus, an object of the present invention is to anticipate a composition suitable for use as a material in an additive manufacturing process for the manufacture of articles in order to exhibit process safety, mechanical stability, and high shape accuracy. In particular, an object of the present invention is to provide a composition exhibiting an optimal process window and melting properties.

[0009] According to the present invention, such an object is solved by the composition according to claim 1 comprising at least one polymer having a defined melt volume rate. Furthermore, the object is solved by the process for the manufacture of the composition according to claim 19, the process for the manufacture of an object according to claim, and the use of the composition of the present invention according to claim That.

[0010] Therefore, the present invention relates to a composition, particularly a construction material for the above-described additive manufacturing process, the composition comprising comprising at least one polymer, the polymer is in the form of a powder, and The polymer contains at least one thermoplastic polymer, the thermoplastic polymer is selected from at least one polyaryl ether ketone, and their copolymers and / or block copolymers and / or polymer blends, and the composition has a melt volume rate (MVR) of at least 5 cm 3 / 10 min, more preferably at least 10 cm 3 / 10 min, and / or 55 cm 3 / 10 min or less, preferably 40 cm 3 / 10 min or less, more preferably 30 cm 3 / 10 min or less, particularly preferably 26 cm 3 / 10 min or less, most preferably 24 cm 3 / 10 min or less.

[0011] In its simplest embodiment, the composition of the present invention comprises a polymer or polymer system each selected from thermoplastic polymers.

Brief Description of Drawings

[0012] [Figure 1] It is a diagram showing the position of the cross test component on the EOS P800 with reduced mounting space (left) and the high temperature measurement spot (「P」, upper right). [Figure 2] It is a diagram showing the matrix (5×2 in xy) of the smaller construction platform of P800 at the center of each sector. [Figure 3] It is a diagram showing the X direction, z direction, the position of the tensile sample in the powder box, and the density cube of the EOS P800. [Figure 4] It is a diagram showing the X direction, z direction, the position of the tensile sample in the powder box, and the density cube of the EOS P800. [Figure 5] Printout of the original configuration of the software. [Figure 6] Printout of the original configuration of the software. [Figure 7] Printout of the original configuration of the software.

Mode for Carrying Out the Invention

[0013] According to the present invention, the "composition" used herein may contain one or more additives. The term "additive" as used herein particularly refers to substances that can be amorphous and / or semi-crystalline and / or crystalline polymers, polyols, surfactants and / or protective colloids.

[0014] The term "powder" as used herein refers to a bulk solid composed of fine particles that can flow freely when shaken or tilted. According to the present invention, such fine particles have a particle size d50 of less than 500 μm.

[0015] According to the present invention, the composition is at least about 5 cm 3 [[ID=十七]] / 10 minutes, more preferably at least about 10 cm 3 / 10 minutes, particularly preferably at least about 15 cm 3 / 10 minutes, most preferably at least about 20 cm 3 / 10 minutes, and / or about 55 cm 3 / 10 minutes or less, more preferably about 40 cm 3 / 10 minutes or less, particularly preferably about 30 cm 3 / 10 minutes or less, particularly preferably about 26 cm 3 / 10 minutes or less, and most preferably about 24 cm 3 / 10 minutes or less of melt volume rate (MVR). The term "about" or "approximately" (approx.) as used herein means that the specified number or range can vary by up to 10 - 15%.

[0016] As used herein, the term “Melt Volume Rate (MVR)” (synonym: Melt Volume Index, MVI) is a measure of the ease with which a molten thermoplastic polymer flows. It is the volume (cm³) of polymer that flows through a capillary of a specific diameter and length in 10 minutes under pressure applied by a given weight of one given gravimetric unit at a given temperature. 3 ) is defined as. MVR is cm 3 Reports are submitted within 10 minutes. This method is described, for example, in ASTM D1238-10.

[0017] MVR measurements of polyaryletherketones (PAEKs), particularly polymers of the PEKK class, are performed on Ceast instruments using Ceast-View 6.3.1 software. Prior to measurement, the powder (4.8 g) is pre-dried at 120°C for 11 minutes using a Sartorius MA100 thermobalance. The powder is then loaded into the MVR unit within 30 seconds. A 5 kg weight is applied, and the measurement is performed at 380°C in accordance with ASTM D1238-10.

[0018] Surprisingly, according to the present invention, advantageous compositions exhibit excellent fluidity and melting properties, as well as a homogeneous structure, for example, in powdered bulk materials, resulting in improved rheological properties such as viscosity, and thus enabling improvements in material deposition and mechanical properties. Good fluidity of the bulk material is assumed when the bulk material flows freely and easily.

[0019] As used herein, the term “flowability” is used synonymously with the term “injectability.” The injectability of a powder is measured (as described in the Methods section) by a mm funnel in accordance with DIN EN ISO 6186 and / or by a shear cell in accordance with ASTM D 7891-15 and / or by the Hausner factor. According to this application, the term “Hausner factor” is used synonymously with the term “Hausner ratio.”

[0020] As used herein, the terms “polymer” or “polymer system” refer to at least one homopolymer and / or heteropolymer constructed from a number of monomers. Homopolymers contain covalent bonds of the same monomer, while heteropolymers (also called copolymers) contain different monomers that have covalent bonds. According to the present invention, a polymer or polymer system may include a mixture of the homopolymers and / or heteropolymers described above, or each may include one or more polymer systems. In this application, such a mixture is referred to as a polymer blend.

[0021] In connection with the present invention, heteropolymers may be selected from statistical copolymers containing randomly assigned monomers, gradient copolymers which are mainly similar to statistical copolymers but in which the monomer content in the chain increases or decreases, alternating copolymers containing alternating monomers, block copolymers or segment copolymers which contain longer sequences or blocks of each monomer, and graft copolymers in which blocks of each monomer are grafted onto a frame of different monomers.

[0022] As an advantage, the compositions of the present invention can be used in additive manufacturing processes. In relation to this application, additive manufacturing processes include processes suitable for rapid prototyping and rapid manufacturing from a group of powder bed processes, particularly preferably including laser sintering, fast sintering, multi-jet fusion, binder jetting, selective mask sintering, or selective laser melting. In particular, the compositions of the present invention can be used in laser sintering. As used herein, the term “laser sintering” is used interchangeably with the term “selective laser sintering,” the latter being an older designation.

[0023] Furthermore, the present invention relates to a process for producing the composition of the present invention, the process is as follows: (i) A step of providing at least one polymer, wherein the thermoplastic polymer is selected from at least one polyaryl ether ketone and / or copolymers thereof and / or block copolymers and / or polymer blends, (ii) A step of crushing the polymer as desired, (iii) optionally, a step of rolling polymer particles in a mixer, preferably by thermal-mechanical treatment, at a temperature of at least 30°C and below the melting point Tm of the polymer.

[0024] As used herein, the term “provide” refers to the manufacture of polymers or polymer systems carried out on-site, and / or, alternatively or additionally, the manufacture of polymers or polymer systems supplied from external sites.

[0025] Preferably, in order to obtain polymer particles, the polymer pellets or polymer flakes from the polymerization process are pulverized. Such polymer flakes are coarse, porous shavings obtained from the polymerization process. Preferably, such powder is 1 m 2 It has a BET surface area exceeding / g. When polymer pellets are used, such a grinding process is preferably carried out at below room temperature, and more preferably by adding liquid nitrogen. An advantage is that the use of liquid nitrogen results in a higher yield of powder (of a particular particle size).

[0026] To obtain round-shaped particles, the polymer particles are preferably subjected to thermal-mechanical treatment. Such treatment is carried out in a mixer, preferably a high-speed mixer, at a preferred temperature of at least 30°C and below the melting point Tm of the polymer.

[0027] The terms mixing, blending, and compounding are used as synonyms below. The process of mixing, blending, compounding can be carried out by extrusion in an extruder, in a kneader, disperser and / or agitator, and, where appropriate, includes one or more operations such as melting and dispersion.

[0028] When packaging the compositions of the present invention, such packaging processes are preferably carried out either in an environment free from humidity or under defined humidity conditions.

[0029] The composition produced by the process of the present invention is advantageously used as a powdery substance to be solidified in a process for the layered manufacturing of three-dimensional objects, thereby continuously generating continuous layers of an object from powder that is selectively solidified at predetermined locations by energy, preferably by electromagnetic radiation, and particularly preferably by laser light.

[0030] Furthermore, the present invention relates to compositions obtained or that can be obtained by the aforementioned processes, particularly for laser sintering.

[0031] Finally, the compositions of the present invention are used in the manufacture of objects, particularly three-dimensional objects, by layered application and by selectively solidifying a fabrication material, preferably a powder. As used herein, the term “solidify” refers to at least partial melting and subsequent solidification or re-solidification of the fabrication material, respectively, and may also be called sintering.

[0032] A favorable process for manufacturing a production element, preferably a 3D object, is at least: (i) A step of applying a layer of the composition according to the present invention, preferably in powder form, and / or a composition produced by the manufacturing process of the present invention, to a manufacturing panel, (ii) Preferably by using an irradiation unit to selectively solidify the layer to which the composition is applied in a portion representing the cross-section of the object to be manufactured, (iii) The process includes lowering the carrier and repeating the applying and solidifying steps until the fabricated element, preferably a 3D object, is completed.

[0033] As used herein, the term “fabrication material” refers to a powder or powdery substance that is appropriately solidified by an additive manufacturing process, preferably by applying a powder bed process, and particularly by laser sintering or laser melting, to form a fabrication element or a 3D object, respectively. The compositions of the present invention described above are particularly suitable as fabrication materials.

[0034] Preferably, the process or part of the process for manufacturing the fabricated element is carried out under a nitrogen atmosphere.

[0035] The manufacturing panel according to the present invention refers to a plate placed on a carrier in a machine for additive manufacturing and positioned at a predetermined distance from a radiation unit suitable for solidifying the carrier material. The manufacturing material is applied to the panel so that its upper layer corresponds to the level at which it solidifies. During manufacturing, particularly during laser sintering, the carrier may be adjusted so that the last applied layer of the manufacturing material is at the same distance from the radiation unit, preferably a laser, thereby solidifying upon exposure to the irradiation unit.

[0036] Articles produced from the compositions of the present invention, particularly 3D objects, exhibit favorable tensile strength and elongation at fracture. As used herein, the term “tensile strength” refers to the measured maximum force required to pull a material to its fracture point. Determining tensile strength is known to those skilled in the art and can be measured in accordance with DIN EN ISO 527. As used herein, the term “elongation at fracture” refers to the ratio between the changed length of a test specimen after fracture and its initial length. This represents the material’s ability to withstand a change in shape without crack formation. Determining elongation at fracture can be performed, for example, in accordance with DIN EN ISO 527-2.

[0037] Furthermore, fabricated elements manufactured from the compositions of the present invention exhibit improved dimensional stability and / or reduced shape distortion. As used herein, the term “dimensional stability” refers to the degree to which a material maintains its original dimensions when exposed to changes in temperature, pressure, force, modification, or humidity. In the laser sintering process, dimensional stability can be determined by the shape distortion of the fabricated element.

[0038] Furthermore, the present invention relates to a fabricated element that can be obtained or obtained by the above-described manufacturing process.

[0039] The use of the compositions of the present invention can be realized by rapid prototyping and rapid manufacturing. This involves carrying out additive manufacturing processes from a group of powder bed processes, preferably including laser sintering, fast sintering, binder jetting, selective mask sintering, selective laser melting, and especially laser sintering, to preferably generate three-dimensional objects by selectively projecting a laser beam having a predetermined energy onto a layer of powdered material. By applying this process, prototypes and fabricated elements can be produced in a time- and cost-effective manner.

[0040] As used herein, the term “rapid manufacturing” refers, in particular, to the production of one or more equivalent articles where the production of fabricated elements, i.e., production by mold assembly, for example, is uneconomical, more complex, or impossible due to the geometric characteristics of the fabricated elements. This applies when the articles as a whole exhibit complex shapes. Examples include elements of spare parts for motorsports, such as luxury cars, racing cars, rally cars, or motorsports, where, in addition to being produced in small numbers, timing of availability is critical. Industries in which the articles of the present invention can be implemented include, for example, the aerospace industry, medical engineering, mechanical engineering, automotive industry, sports industry, household goods industry, electrical industry, or lifestyle industry, respectively. More importantly, the production of numerous similar fabricated elements of personalized elements, such as prostheses or (inner ear) hearing aids, where the geometric shape can be individually tailored to the user.

[0041] Finally, the present invention includes a composition in the form of a powder, which is suitable for solidifying in a process of layering a three-dimensional object from such a powder, and then for constructing a continuous layer of the object in a specific location by applying energy, preferably by applying electromagnetic radiation, and especially by applying laser light.

[0042] Further preferred embodiments of the present invention are derived from the dependent claims together with the following description, so that certain categories of patent claims may be formed by different categories of dependent claims, and features of different examples may be combined into new examples. It should be understood that the definitions and explanations of the terms above and below apply as appropriate to all embodiments described herein and in the accompanying claims. Specific embodiments of the methods of the present invention are further specified below.

[0043] Preferably, at least one polyaryl ether ketone is selected from the group polyether ketone ketone (PEKK), polyether ether ketone (PEEK), and / or from the group of copolymers of PEKK or PEEK, such as polyether ether ketone-polyether diphenyl ether ketone (PEEK-PEDEK), and / or from the group polyether ether ketone-polyether meta ether ketone (PEEK-PEmEK).

[0044] More preferably, at least one polyaryl ether ketone is selected from the group consisting of polyether ketone ketone (PEKK) and / or polyether ether ketone-polyether diphenyl ether ketone (PEEK-PEDEK) and / or polyether ether ketone-polyether meta ether ketone (PEEK-PEmEK), as follows:

[0045] [ka]

[0046] More preferably, at least one polymer is selected from at least one homopolymer and / or heteropolymer and / or polymer blend, where the at least one homopolymer and / or heteropolymer and / or polymer blend preferably comprises a semicrystalline homopolymer and / or heteropolymer and / or amorphous homopolymer and / or heteropolymer. Particularly preferably, the at least one homopolymer and / or heteropolymer and / or polymer blend is selected from at least one semicrystalline polymer or a semicrystalline polymer blend of at least one semicrystalline polymer and at least one further semicrystalline polymer or a semicrystalline polymer blend of at least one semicrystalline polymer and an amorphous polymer.

[0047] As used herein, the term “semi-crystalline” is understood to refer to a material containing both crystalline and amorphous regions. A polymer is considered essentially amorphous if the degree of crystallinity in the solid phase of the polymer is about 5% by weight or less, particularly about 2% by weight or less. In particular, a polymer is considered essentially amorphous if its melting point cannot be determined by dynamic differential calorimetry (DSC) and / or its enthalpy of melt is less than 1 J / g in the first heating. A semi-crystalline material may contain a crystalline region of up to 70% by weight, preferably up to 90% by weight, and particularly up to 95% by weight.

[0048] Preferably, the heteropolymer or copolymer comprises at least two different repeating units and / or at least a polymer blend, each based on the aforementioned polymer and copolymer. An advantage is that such heteropolymers or copolymers and / or polymer blends are semi-crystalline.

[0049] By using one or more of the above-mentioned polymers (homopolymers, copolymers, or polymer blends), a material that is at least partially semi-crystalline, preferably in powder form, can be produced.

[0050] Favorable compositions preferably include polymers and / or copolymers and / or polymer blends having a melting temperature of at least about 120°C, preferably at least about 150°C, and particularly preferably at least about 180°C. However, preferred polymers and / or copolymers and / or polymer blends have a melting temperature of about 320°C or less, preferably about 300°C or less, and particularly preferably about 280°C or less.

[0051] As used herein, the term “melting temperature” refers to the temperature or temperature range at which a substance, preferably a polymer, copolymer, or polymer blend, transitions from a solid state to a liquid state.

[0052] Alternatively or additionally, advantageous compositions include polymers and / or copolymers and / or polymer blends having a glass transition temperature Tg of at least about -10°C, preferably at least about 50°C, more preferably at least about 90°C, particularly preferably at least about 120°C, and / or about 250°C or less, preferably about 225°C or less, more preferably about 200°C or less, particularly preferably about 175°C or less.

[0053] As used herein, the term “glass transition temperature” refers to the temperature at which a polymer changes to a gum-like viscous state. Determining the glass transition temperature is known to those skilled in the art and can be performed, for example, by DSC (according to DIN EN ISO 11357).

[0054] According to a preferred embodiment, the advantageous composition has a melting point peak extrapolation start temperature T that is at least 1°C, preferably at least 5°C higher, compared to thermoplastic polymers that have not been treated by annealing. eim , and / or at least 1°C, preferably at least 5°C higher, the difference ΔT between the crystallization temperature (Tc) and the melting temperature (Tm) eim It has / Tc.

[0055] Surprisingly, the inventors have found that the annealing of the composition results in T eim Increase and / or difference ΔT eim We found that this results in an increase in / Tc, i.e., an expansion of the process window. As used in this invention, the term “process window” refers to the difference between the lowest possible construction temperature (non-curl temperature: NCT) and the highest possible construction temperature (higher construction temperature: UBT). As used herein, the terms “crystallization temperature” and “extrapolation start temperature of the melt peak” refer to peak temperatures as defined in DIN EN ISO 11357.

[0056] Methods for determining the crystallization temperature, melting temperature, and extrapolation start temperature of the melting peak are known to those skilled in the art and can be carried out by dynamic differential calorimetry (DSC) in accordance with DIN EN ISO 11357. To enable comparison of polymer measurements with and without annealing treatment, the methods used take into account the application of the same holding time, thermal rate, start temperature, and end temperature.

[0057] The degree of crystallization can be measured by various analytical methods such as DSC or X-ray diffraction. The degree of crystallization is then calculated by the melt enthalpy [J / g] (compared to a polymer with 100% theoretical crystallinity).

[0058] As used herein, the term "enthalpy of fusion" refers to the energy required to melt a substance from its solid state to its liquid state at its melting temperature and a constant pressure (isobar).

[0059] Furthermore, the inventors have surprisingly discovered that the process window can be increased not only by annealing within a specific temperature range below the melting point Tm, but also, alternatively or additionally, by varying the melt volume rate (MVR) of the polymer. As an advantage, within the MVR range specified above, the process window is at least about 1°C, preferably at least about 3°C, more preferably at least about 5°C, and most preferably at least about 9°C, and / or about 200°C or less, preferably about 100°C or less, and more preferably about 50°C or less, relative to the primary powder, i.e., unused powder.

[0060] According to a preferred embodiment, the above-mentioned polyetherketone ketone has the following repeating units: [ka] (In the formula, the ratio of repeating unit A to repeating unit B is preferably between approximately 80:20 and 10:90, preferably between 70:30 and 40:60, and particularly preferably between 60:40.) Includes.

[0061] In a particularly preferred embodiment, the polyaryletherketone has a melting temperature Tm of at least 250°C, preferably at least 260°C, particularly preferably at least 270°C, and / or up to 320°C, preferably up to 310°C, particularly up to 300°C, and / or the polyaryletherketone has a glass transition temperature Tg of at least 120°C, preferably at least 140°C, particularly preferably at least 150°C.

[0062] According to the following preferred embodiment, the polyetherimide is preferably, [ka] The repeating unit of, and / or [ka] The repeating unit of, and / or [ka] Includes repeating units.

[0063] According to the following preferred embodiment, the polymer blend comprises a polyaryletherketone-polyetherimide.

[0064] More preferably, the polyaryl ether ketone comprises repeating unit A and repeating unit B in a 60:40 ratio. [ka] The polyetherketone ketone has a ratio of and / or the polyetherimide, [ka] Includes repeating units.

[0065] A more preferred composition is the following repeating unit: [ka] It contains polyether ketones having the properties of polyether ketones.

[0066] Preferably, the ratio of 1,4-phenylene units in repeating unit A to 1,3-phenylene units in repeating unit B is 90:10 to 10:90, more preferably 70:30 to 10:90, particularly 60:40 to 10:90, and most preferably about 60:40. The number n1 or n2 of repeating units A or B may be at least 10 and / or 2000, respectively.

[0067] More preferably, the viscosity number of the polymer is between 0.7 dl / g and 1.2 dl / g, preferably between 0.78 dl / g and 1.1 dl / g, as measured in a 96 wt% sulfuric acid solution at 25°C in accordance with ISO 307, as applied to PAEK.

[0068] For example, a preferred polyether ketone polymer can be obtained under the trade name Kepstan 6000 series (Arkema, France).

[0069] In a more preferred embodiment, the polyaryletherketone has a melting temperature Tm of at least 250°C, preferably at least 260°C, particularly preferably at least 270°C, and / or up to 320°C, preferably up to 310°C, particularly up to 300°C.

[0070] Furthermore, preferred polyaryletherketones have a glass transition temperature Tg of at least about 120°C, preferably at least about 140°C, particularly preferably at least about 150°C, and / or about 200°C or less, preferably about 180°C or less, particularly preferably about 170°C or less.

[0071] According to the following preferred embodiment, the polyetherketone ketone is melted at an extrapolated onset temperature (T) of at least 250°C, preferably at least 260°C, particularly preferably at least 265°C, and / or up to 285°C, preferably up to 280°C, particularly up to 275°C. eim ) has.

[0072] Melting temperature Tm and extrapolation start temperature of melting peak (T eim The determination of ) can be performed, for example, by the DSC (Differential Scanning Calorimetry) method. Tm and T eim The corresponding DSC method for measurement is preferably performed in accordance with DIN EN ISO 11357 on an instrument such as the Mettler Toledo DSC 823 (determined by the first heating curve of the DSC) (for PAEK, especially PEKK, the initial temperature is 0°C, the maximum temperature is 360°C, and the minimum temperature is 0°C; heating or cooling rate: 20K / min, weight: 4.5mg~5.5mg).

[0073] The high melting temperature and / or glass transition temperature of at least one polyaryletherketone offer advantages, such as enabling improved melting and bonding properties, particularly laser sintering, and thus resulting in improved mechanical properties of fabricated elements made from such polymers.

[0074] In the next preferred composition, the thermoplastic polymer is selected from at least one polyetherimide. Particularly preferred, such polyetherimide is [ka] The repeating unit of, and / or [ka] The repeating unit of, and / or [ka] Includes repeating units.

[0075] The number n of repeating units in formulas I, II, and III is preferably at least 10 and / or 1000 or less.

[0076] Preferably, the number-average molecular weight (Mn) of such polyetherimide is at least 10,000 D, preferably at least 15,000 D and / or 200,000 D or less, and particularly preferably at least 15,000 D and / or 100,000 D or less. The weight-average molecular weight (Mw) of such preferred polymer is preferably at least 20,000 D, more preferably at least 30,000 D and / or 500,000 D or less, and particularly preferably at least 30,000 D and / or 200,000 D or less.

[0077] Preferred polyetherimides relating to Formula I are available under the trade names Ultem® 1000, Ultem® 1010, and Ultem® 1040 (Sabic, Germany), and preferred polyetherimides relating to Formula II are available under the trade names Ultem® 5001 and Ultem® 5011 (Sabic, Germany).

[0078] A more preferred composition comprises a polymer blend containing a polyaryletherketone-polyetherimide, preferably a polyetherketone ketone having a ratio of repeating unit A to repeating unit B of 60:40. The preferred composition may further comprise a polyetherimide, preferably containing repeating units of formula I.

[0079] As described above, a favorable composition may contain one or more additives. According to a preferred embodiment, the additive may be a semicrystalline polymer and / or a semicrystalline polyol and / or a semicrystalline surfactant and / or a semicrystalline protective colloid. Preferably, the additive is water-soluble and / or miscible with at least one thermoplastic polymer at room temperature.

[0080] As an advantage, the additive effectively prevents the solidification of polymer particles and the formation of cavities during the injection of the composition in the additive manufacturing process, thereby positively increasing the bulk density of the composition.

[0081] As used herein, the term “bulk density” refers to the mass of a large number of particles in a material divided by the total volume they occupy. This total volume includes particle volume, interparticle void volume, and internal pore volume. Determining bulk density is known to those skilled in the art and can be carried out in accordance with DIN EN ISO 60:2000-01.

[0082] According to a preferred embodiment, the composition is at least about 30 kg / m³ 3 and / or approximately 65 kg / m 3 Preferably, at least 35 kg / m 3 and / or 55 kg / m 3 The following, in particular, is at least 40 kg / m 3 and / or 50 kg / m 3 It has the following bulk density.

[0083] If the composition contains polyaryl ether ketones produced by grinding polymerized flakes, such a composition preferably contains at least about 30 kg / m³ 3 and / or approximately 50 kg / m 3 Preferably, at least 32 kg / m³ 3 and / or 45 kg / m 3 The following, in particular, is at least 34 kg / m³ 3 and / or 40 kg / m 3 The following bulk densities are observed. This is particularly preferable when the composition is manufactured from polymerized flakes.

[0084] In general, for compositions used in laser sintering, appropriate bulk density and sufficient implantability are important, respectively, with respect to specific particle sizes or particle size distributions.

[0085] As used herein, the term "particle size" refers to the size of a single particle in a composition. Thus, the particle size distribution affects the properties of bulk materials that exist in an injectable form, such as compositions that exist in powder form.

[0086] According to a more preferred embodiment, the polymer particles of the composition have the following particle size distribution. - d10 = at least 10 μm, preferably at least 20 μm and / or 50 μm or less, preferably 40 μm or less - d50 = at least 25 μm and / or 100 μm or less, preferably at least 30 μm and / or 80 μm or less, particularly at least 40 μm and / or 60 μm or less - d90 = at least 50 μm and / or 150 μm or less, preferably 120 μm or less

[0087] Methods for determining particle size or particle size distribution are known to those skilled in the art and can be determined in accordance with DIN ISO 13322-2.

[0088] A particularly preferred composition comprises polymer particles selected from polyarylether ketones, the polymer particles of the composition having the following particle size distribution. - d10 = at least 15 μm, preferably at least 20 μm, particularly at least 25 μm and / or 50 μm or less, preferably 40 μm or less, particularly 30 μm or less - d50 = at least 40 μm and / or 100 μm or less, preferably at least 45 μm and / or 80 μm or less, particularly at least 50 μm and / or 65 μm or less - d90 = at least 70 μm and / or 150 μm or less, preferably at least 80 μm and / or 130 μm or less, more preferably 120 μm or less, particularly preferably 110 μm or less

[0089] More preferably, such preferred polyaryletherketone powder is obtained by grinding polymerization flakes.

[0090] According to a more preferred embodiment, advantageous compositions exhibit a distribution width (d90-d10) / d50 of 3 or less, preferably 2 or less, particularly 1.5 or less, and especially preferably 1 or less.

[0091] A more preferred composition contains about 5% by weight or less, preferably about 3% by weight or less, particularly preferably about 2% by weight or less, and most preferably 1% by weight or less of fine particles. As used herein, the term "fine particles" refers to particles having a particle diameter of less than 10 μm.

[0092] The polymer particles of the composition of the present invention preferably exhibit an essentially spherical to lenticular shape. Particularly preferably, the polymer particles exhibit a sphericity of at least about 0.8, preferably at least about 0.85, particularly preferably at least about 0.90, and most preferably at least about 0.95. Determination of sphericity can be carried out, for example, by microscopic examination in accordance with DIN ISO 13322-1 and / or DIN ISO 13322-2 (on a Camsizer XT instrument (Retsch Technology, Germany)).

[0093] According to a particularly preferred embodiment, the advantageous composition has an injectability of at least 1 second, preferably at least 2 seconds, most preferably at least 3 seconds and / or 12 seconds or less, preferably 9 seconds or less, and most preferably 8 seconds or less (measured using a 25 mm funnel in accordance with DIN EN ISO 6186).

[0094] More preferably, the compositions exhibit a Hausner factor of at least 1.01 and / or 1.7 or less, preferably about 1.5 or less, more preferably about 1.4 or less, particularly preferably about 1.3 or less, even more preferably about 1.2 or less, and most preferably about 1.18 or less.

[0095] It has been further discovered that the polymer particles of the composition of the present invention have the advantage of exhibiting a small surface area. The surface of such polymer particles can be determined, for example, by gas adsorption in accordance with Brunauer, Emmett and Teller (BET) (referencing DIN EN ISO 9277). The particle surface measured according to this method is also called the BET surface.

[0096] According to a preferred embodiment, the BET surface of the advantageous composition is at least about 0.1 m 2 / g and / or about 10m 2 / g or less, preferably 5m 2 / g or less, more preferably 2m 2 / g or less, particularly preferably 1.5m 2 / g or less, most preferably 1m 2 The amount is less than or equal to / g. In particular, such compositions include polymer particles selected from polyarylether ketones.

[0097] This is particularly preferable when the polyaryl ether ketone particles are produced from polymerization flakes, but such polyaryl ether ketone particles are preferably at least 0.5 m 2 They have a BET surface area of ​​ / g. Particularly preferably, such polyaryletherketone particles are obtained by grinding.

[0098] The process of the present invention for producing the composition was first illustrated. According to a more preferred embodiment for producing the composition, the polymer is preferably selected from polyaryl ether ketones or blends thereof with copolymers or other polymers, more preferably in powder form. Particularly preferably, the polymer is provided in the form of polymerization flakes from a polymerization process.

[0099] The production of an advantageous composition may include a step of melt dispersion of the polymer, such as that provided in step i) above, in an additive, such as a dispersant. Preferably, such a dispersant is selected from polyols, more preferably from semicrystalline polyols. In particular, such a polyol is selected from at least one semicrystalline polyethylene glycol and / or at least one semicrystalline polyethylene oxide and / or at least one polyvinyl alcohol, and especially preferably from at least one semicrystalline polyethylene glycol. Preferably, such additives or dispersants are removed by centrifugation and / or filtration, respectively.

[0100] The dispersion process, preferably by melt dispersion, is carried out in a dispersion apparatus, more preferably in an extruder. Alternatively, the dispersion process may be carried out in a kneader. Preferably, the dispersion apparatus includes several consecutive zones, particularly in the forward direction.

[0101] Further processes may involve separating the polymer or polymer particles from the mixture or dispersion, respectively, followed by washing and / or drying the separated polymer or polymer particles.

[0102] The separation of each component of the mixture or dispersion is preferably carried out by centrifugation and / or filtration. Drying of the solid composition to obtain a dried composition can be achieved, for example, in an oven such as a vacuum dryer.

[0103] Alternatively or additionally, advantageous compositions can be obtained by melt-compounding a polymer such as that provided in step i), further processing the polymer to fiberize it, and shredding the fibers into micropellets.

[0104] Alternatively or additionally, advantageous compositions can be obtained by melt-forming a polymer such as that provided in step i) and spraying the molten material in a melt-spray process, preferably by applying high pressure through a nozzle.

[0105] Alternatively or additionally, advantageous compositions can be obtained by dissolving the polymer in a solvent, preferably at a high temperature, and precipitating the polymer from the solvent to form a powder, preferably by cooling and stirring.

[0106] In a particularly preferred embodiment, an advantageous process for producing the composition further includes the step of annealing polymer particles at a temperature higher than Tg and lower than Tm. Preferably, the annealing of polymer particles is carried out in a furnace.

[0107] The annealing process can be carried out in the same manner as the rolling process described above. Alternatively, annealing can be carried out before or even after rolling the polymer particles.

[0108] According to a particularly preferred embodiment, the annealing of the polymer, in particular PAEK, is carried out in the same process as the polymer rolling process. Such a particularly preferred process is preferably carried out at an annealing temperature of at least about 30°C, more preferably at at least the approximate glass transition temperature of the polymer and / or below the approximate melting temperature of the polymer.

[0109] Furthermore, the present invention relates to compositions, particularly compositions comprising a PAEK polymer, that are obtained or can be obtained by the above process, which includes such an annealing step.

[0110] According to the most preferred embodiment, the process for producing a favorable composition includes the step of annealing polymer particles, preferably PEKK particles, at a preferred temperature of at least about 250°C, more preferably at least about 260°C, particularly preferably at least about 265°C, and / or preferably 285°C or lower, more preferably 280°C or lower, particularly preferably 275°C or lower.

[0111] In the next step, the advantageous process involves the addition of an additive. In particular, such an additive is selected from fluidizers. Preferably, the addition of the additive, especially the fluidizer, is carried out in a mixer.

[0112] The manufacturing of the fabricated element of the present invention was first described. Surprisingly, the inventors found that a more more, and more favorable, process for manufacturing the fabricated element was to use a refreshed composition. Beneficially, the use of a refreshed composition enhances the mechanical stability of the fabricated element. Furthermore, the use of a refreshed composition preferably results in a cost-effective manufacturing process.

[0113] As used herein, the term “refreshing the composition” refers to a portion of the overall composition, i.e., a portion of the composition that has not been previously used in a laser sintering process, compared to a portion of the composition that has been used in a laser sintering process at least once. In relation to the present invention, the portion of the composition that has not been previously used in a laser sintering process is referred to as “primary powder” or “primary composition.” The content of such primary composition is preferably more than 10% by weight and less than 60% by weight, more preferably less than 50% by weight, even more preferably less than 40% by weight, and particularly preferably less than 30% by weight of the overall composition.

[0114] Depending on the job-volume size, sintering strain, particularly in the x and y directions, can be observed at high refresh rates exceeding 60% by weight. Therefore, according to a particularly preferred embodiment, it is preferable that the refresh rate is within the above numerical range. This is particularly advantageous for PEKK, and most preferably for the PEKK 60:40 (repeating unit A:repeating unit B) copolymer.

[0115] Therefore, according to an advantageous embodiment, a preferred refresh is less than 50% by weight, preferably less than 40% by weight, and particularly preferably less than 30% by weight. However, the refresh needs to be greater than 10% by weight because the surface of the article may be reduced ("orange skin" effect). This is particularly relevant when using machines with large construction volumes, such as EOS P800 or P810 machines, and is even more relevant when performing constructions with a z height exceeding about 100 mm, or most relevant when performing constructions with a z height exceeding about 200 mm. As an advantage, such a refresh is used in PEKK, most preferably PEKK 60:40 (repeating unit A:repeating unit B) copolymer.

[0116] Furthermore, and surprisingly, it has been found that the above-mentioned step i) of applying layers is applied by at least a double coating, which is a favorable process for manufacturing the fabricated element, preferably a 3D object. Here, the application of the layers is subdivided into the step of applying a first layer having a first height H1 and the step of applying a second layer having a second height H2. A second layer with height H2 is applied on top of a first layer with height H1, preferably the height H1 of the first layer is equal to the height H2 of the second layer.

[0117] According to the following preferred embodiment, such a layer preferably has a thickness of at least about 60 μm and / or 120 μm or less, more preferably about 100 μm. Surprisingly, applying a layer of such thickness improves the bonding of the layers.

[0118] Particularly preferred is a layer of advantageous processes for manufacturing the fabricated element, using a roof blade having a preferred angle of 1.9°.

[0119] Furthermore, the present invention includes fabricated elements, preferably 3D objects, which are obtained or can be obtained by the above-described manufacturing process.

[0120] Finally, an advantageous process may include packaging of the composition. Packaging of compositions, particularly powders, produced according to the method of the present invention is preferably carried out in an area protected from air humidity. Such packaged materials may be stored under reduced humidity to prevent solidification effects, thereby improving the storage stability of the compositions of the present invention. In addition, advantageous packaging materials may prevent moisture, particularly air humidity, from accessing the compositions of the present invention.

[0121] As described above, the compositions of the present invention are suitable for additive manufacturing processes, particularly laser sintering processes. Typically, the irradiation device, especially the target area of ​​the laser beam, for example, the powder bed of an additive manufacturing device, is heated before use, so that the temperature of the primary powder material approaches its melting temperature, and only a small energy input is needed to increase the total energy input for the particles to coalesce and solidify. Thus, energy-absorbing and / or energy-reflecting materials can be applied to the target area of ​​the irradiation unit, as is known from the processes of fast sintering or multi-jet fusion, respectively.

[0122] As used herein, the term “melting” refers to a process in which, during an additive manufacturing process, powder in a powder bed is at least partially melted by an energy input, preferably by electromagnetic radiation, and particularly by laser radiation. This enables the compositions of the present invention to at least partially melt and manufacture process-safe fabricated elements with high mechanical stability and molding accuracy.

[0123] Furthermore, it has been found that the determination of tensile strength and elongation at break is useful as a measure of the processability of the compositions or fabricated elements of the present invention, respectively, manufactured according to this specification.

[0124] Therefore, a more preferred embodiment includes fabricated elements produced by using the composition of the present invention. As an advantage, such fabricated elements preferably exhibit a tensile strength in the x and y directions of at least about 50 MPa, more preferably at least about 70 MPa, particularly at least about 80 MPa, and most preferably at least about 90 MPa. Advantageous fabricated elements preferably have a tensile strength of about 150 MPa or less, more preferably about 120 MPa or less, and particularly about 110 MPa or less.

[0125] Alternatively or additionally, such fabricated elements preferably exhibit elongation at break of at least about 1%, more preferably at least about 2%, particularly at least about 2.5%, most preferably at least about 3%, and / or about 50% or less, more preferably about 20% or less, particularly preferably about 15% or less.

[0126] The determination of tensile strength and elongation at break is known to those skilled in the art and can be carried out in accordance with DIN EN ISO 527.

[0127] In a more preferred embodiment, a favorable composition comprises at least, preferably one or more additives selected from fluidizers, heat stabilizers, oxidation stabilizers, UV stabilizers, colorants, and infrared absorbers. The preferred content of such additives in the composition may be at least about 0.005% by weight, preferably at least about 0.01% by weight, more preferably at least about 0.05% by weight, particularly preferably at least about 0.1% by weight, and most preferably at least about 0.2% by weight, and / or a preferred composition may contain a content of one or more additives preferably about 3% by weight or less, more preferably about 2% by weight or less, particularly preferably about 1% by weight or less, and most preferably about 0.5% by weight or less. The content of such additives refers to the content of each single additive in the composition.

[0128] Preferably, other functional additives that can be used in amounts greater than 3% by weight are selected from the group of softeners, fillers, and reinforcing materials, as well as flame retardants, reinforcing fibers, SiO2 particles, carbon particles, carbon fibers, glass fibers, carbon nanotubes, mineral fibers (e.g., wollastonite), aramid fibers (especially Kevlar fibers), glass spheres, mineral fibers, inorganic pigments and / or organic pigments and / or flame retardants (especially ammonium polyphosphate and / or phosphates such as brom and / or other halogens and / or organic substances such as magnesium hydroxide or aluminum hydroxide). Particularly preferred are additives that include reinforcing fibers, especially carbon fibers.

[0129] Furthermore, particularly preferred additives include polysiloxanes. Polysiloxanes can be used, for example, as a fluidizing agent to reduce the viscosity of polymer melts, and / or especially as a softening agent for polymer blends.

[0130] According to a more preferred embodiment, the advantageous composition comprises at least one fluidizing agent. Such a fluidizing agent, which usually exists in the form of particles, adheres to the polymer particles, thereby preventing aggregation of the composition.

[0131] Such fluids are preferably selected from the group of metallic soaps, preferably silicon dioxide, stearate, tricalcium phosphate, calcium silicate, aluminum oxide, magnesium oxide, magnesium carbonate, zinc oxide, or mixtures thereof. More preferably, at least one fluid is selected from silicon dioxide (synonym: silica). Favorable compositions contain at least about 0.01% and / or about 1% by weight or less (one or more) of the fluid.

[0132] Further preferred embodiments of the present invention are derived from the dependent claims together with the description, so that certain categories of patent claims may be formed by different categories of dependent claims, and features of different examples may be combined into new examples. It should be understood that the definitions and explanations of the terms above and below apply as appropriate to all embodiments described herein and in the accompanying claims. Specific embodiments of the present invention are further specified below. [Examples]

[0133] Example 1: PEKK having a ratio of terephthalic acid units to isophthalic acid units of 60:40 was prepared as follows: Orthodichlorobenzene (1600 g) and 1,4-(phenoxybenzoyl)benzene (EKKE) (65 g) were added to a 2 L reactor while stirring under a stream of dry nitrogen. The following acid chlorides were added: terephthaloyl chloride (5.4 g), isophthaloyl chloride (22.2 g), and benzoyl chloride (0.38 g). The reactor was cooled to -5°C, and AlCl3 (115 g) was added while maintaining the reactor temperature below 5°C. After a homogenization period (approximately 10 minutes), the reactor temperature was increased by 5°C per minute to 90°C (polymerization began during this temperature increase). The reactor was maintained at 90°C for 30 minutes, and then cooled to 30°C. 400 g of acidic water (3% HCl) was slowly added to prevent the reactor temperature from exceeding 90°C. The reactor was stirred for 2 hours, and then cooled to 30°C.

[0134] The reaction medium was removed from the reactor, and the filtration / purification process was carried out according to the art. The purified moist PEKK was then dried overnight under vacuum (30 mbar) at 190°C to obtain flakes.

[0135] Example 2: The PEKK polymerization flakes from Example 1 were appropriately pulverized and subjected to air classification to obtain a fine powder. The powder data is shown in Table A.

[0136] [Table 1]

[0137] Example 3 Polyether ketone (PEKK) was prepared according to Examples 1 and 2.

[0138] Subsequently, the powder was mixed in a Henschel-type FML mixer according to Table 1. The mass of the powder is hereafter referred to as m. Phase 1 refers to the heating phase, i.e., the phase until the mixture (powder) in the mixer reaches its maximum temperature Tmax. Tmax is the processing temperature T B It corresponds to the following. The mixer speed in Phase 1 is called D1. The duration of Phase 1 is called t1. Phase 2 is the holding phase, i.e., the phase in which the achieved temperature is maintained. The mixer speed in Phase 2 is called D2. The duration of Phase 2 is called t2.

[0139] The names m, Tmax, D1, D2, t1, and t2 are also used in the following examples.

[0140] The obtained bulk density S, BET surface, volume percentage of powder particles with a particle size of 10 μm ("%<10 μm"), and values ​​for quantiles d10, d50, and d90 of the particle size distribution are shown in Table 2.

[0141] [Table 2]

[0142] [Table 3]

[0143] Example 4 The powder from Example 3 was annealed for 3 hours in a ventilated furnace (Nabertherm type N250 / A) under a nitrogen atmosphere at different temperatures (as shown in Table 3a). After annealing, the powder was sieved through a Perflux 501 type vibrating sieve (Siebtechnik GmbH, Mülheim, Germany) to a 160 μm sieve. The obtained powder values ​​are shown in Table 3a.

[0144] Test specimens were produced from three resulting powders (primary powders) using a P800 type laser sintering system (EOS P800 with startup kit PAEK 3302 CF) with the processing parameters shown in Table 3b. The layer thickness was 120 μm, applied using a double coating process (layer thickness 60 μm). The powders were analyzed for processability (process window) and mechanical properties of the laser-sintered parts. The obtained values ​​are shown in Tables 3b and 3c.

[0145] [Table 4]

[0146] [Table 5]

[0147] As can be seen, the non-curl temperature (NCT) is increased at higher annealing temperatures. Therefore, the powder needs to be built up at higher process chamber temperatures (PK), which leads to faster degradation of the used powder over time (a greater decrease in MVR value (see Table 3a)), and consequently, a decrease in refresh rate with increasing heat treatment temperature.

[0148] [Table 6]

[0149] The effect of heat treatment on mechanical properties is shown. The tensile strength at z increases at an annealing temperature of 275°C.

[0150] Example 5 In Example 5, three PEKK types with different melt viscosities were produced, similar to Example 4. The only exception was the adjustment of the polymerization time (compared to Example 1) to obtain powders with different melt viscosities (MVR). Furthermore, the mixer processing temperature Tmax in Example 5 was between 110 and 120°C. t2 was adjusted for each powder so that t1+t2 was always maintained for 25 minutes. The annealing temperature in Example 5 for all three powders was 265°C. The powder analysis data is shown in Table 4a.

[0151] Test specimens were produced on a P800-type laser sintering system (EOS P800 with startup kit PAEK 3302 CF) from three resulting powders (primary powders) using the processing parameters shown in Table 4b. The layer thickness was 120 μm, applied using a double coating process (layer thickness 60 μm). The powders were analyzed for their processability (process window) and the mechanical properties of the laser-sintered parts. The obtained values ​​can be seen in Tables 4b and 4c.

[0152] [Table 7]

[0153] [Table 8]

[0154] As seen in Tables 4a and 4b, NCT increases with increasing MVR value of the powder. This means that the construction temperature (Tpk) is higher, which negatively impacts powder aging and refresh. Also, the process window (difference between UBT and NCT) decreases from 13°C to just 5°C as the MVR of the powder increases.

[0155] [Table 9]

[0156] The effect of melt viscosity on mechanical properties is clearly visible in Table 4c. Tensile strength and elongation at break in the x and y directions increase significantly from 73 MPa to 96 MPa, and from 2.1% to 3.8% when MVR is low, while in the z direction, elongation at break decreases only slightly from 1.3% to 1.2%.

[0157] Example 6 In Example 6, similar to Example 4, two PEKK types with different particle size distributions were produced. The exception was that the polymerization time was adjusted (compared to Example 1), and the mixture was heated for 24 cm after the heat treatment. 3 Powders with an MVR of 10 minutes were obtained. Furthermore, the mixer processing temperature Tmax in Example 6 was between 110 and 120°C. t2 was adjusted for each powder so that t1+t2 was always maintained for 25 minutes. The annealing temperature in Example 6 was 265°C for both powders. The analytical data for the primary powders are shown in Table 5a.

[0158] [Table 10]

[0159] The effect of particle size distribution on powder fluidity can be clearly observed. Coarser powder exhibits better fluidity (injection time is reduced from 15 seconds to 8 seconds).

[0160] Using the processing parameters shown in Table 5b, test specimens were produced from the resulting powder (50% refreshed) on a P800-type laser sintering system (EOS P800 with startup kit PAEK 3302 CF). The layer thickness was 120 μm, applied using a double coating process (layer thickness 60 μm). The powder was analyzed for the mechanical properties of the laser-sintered parts. The obtained values ​​are shown in Table 6.

[0161] [Table 11]

[0162] [Table 12]

[0163] Table 6 shows that the powder with improved injection properties in 8 seconds exhibits improved tensile strength and elongation at break in the x and y directions.

[0164] Example 7 In Example 7, PEKK was produced as similarly described in Example 5. The exception was that the polymerization time was adjusted (compared to Example 1), and after heat treatment, it was incubated for 22 cm. 3 A powder with an MVR of 10 minutes was obtained. Furthermore, the mixer processing temperature Tmax from Example 7 was 116°C. t2 was adjusted to the powder so that t1+t2 was maintained for 25 minutes. The annealing temperature in Example 5 was 265°C.

[0165] [Table 13]

[0166] Test specimens were produced on a P800-type laser sintering system (EOS P800 with startup kit PAEK 3302 CF) with three different layer thicknesses of 120 μm, 100 μm, and 60 μm by applying a double-coating process (layer thicknesses of 60 μm, 50 μm, and 30 μm, respectively), using the processing parameters shown in Table 7b, from the resulting powder (primary powder). The mechanical properties of the laser-sintered parts were analyzed for each different layer thickness. The obtained values ​​are shown in Table 7c.

[0167] [Table 14]

[0168] [Table 15]

[0169] The effect on the mechanical properties and density of the component in the z-direction can be clearly observed. Applying reduced layer thicknesses of 100 μm and 60 μm increases the tensile strength and elongation at fracture in the zx direction.

[0170] Example 8 In Example 8, the polymerization time was adjusted (compared to Example 1), and 23 cm was added before heat treatment. 3 PEKK was produced as similarly described in Example 4, except that a powder with an MVR of 10 minutes was obtained. Furthermore, the processing temperature Tmax of the mixer in Example 8 was between 110 and 120°C. t2 was adjusted so that t1+t2 was always maintained at 25 minutes. The annealing temperature was also adjusted. The powder was annealed at different temperatures (according to Table 8a) in a ventilated furnace (Nabertherm type N250 / A) under a nitrogen atmosphere for 3 hours. After annealing, the powder was sieved through a Perflux 501 type vibrating sieve (Schiebtegnik GmbH, Mülheim, Germany) to a 160 μm sieve. The obtained powder values ​​are shown in Table 8a.

[0171] Test specimens were produced from three resulting powders (primary powders) using the processing parameters shown in Table 8b on a P810 type laser sintering system. The layer thickness was 120 μm, applied using a double coating process (layer thickness 60 μm). The powders were analyzed for processability (process window), powder bed hardness after construction, and mechanical properties of the laser-sintered parts. The obtained values ​​are shown in Tables 8b and 8c.

[0172] [Table 16]

[0173] [Table 17]

[0174] As can be seen, the non-curl temperature (NCT) can be increased at higher annealing temperatures. Therefore, the powder needs to be built up at higher process chamber temperatures (PK), which leads to faster degradation of the spent powder over time (greater decrease in MVR value (see Table 8a)), and consequently, a decrease in refresh rate with increasing heat treatment temperature. At the lowest annealing temperatures, the bulk density of the spent powder decreases most significantly, and the powder's fluidity is also the lowest.

[0175] [Table 18]

[0176] The effect of heat treatment on mechanical properties is shown. The highest values ​​are reached at an annealing temperature of 265°C.

[0177] Example 9 In Example 9, PEKK (Sample No. 1) was produced in the same manner as in Example 2, but the polymerization time was adjusted to obtain a viscosity similar to that of Example 6. Then, PEKK was mixed as described in Example 3, except that the mixer processing temperature Tmax was between 110 and 120°C. t2 was adjusted to maintain t1+t2 for 25 minutes (Sample No. 2). Annealing was then performed in the same manner as in Example 4 (Sample No. 3). The annealing temperature for Sample 3 was 265°C. A different PEKK was also produced according to Example 9, Sample No. 3 (Sample No. 4). The annealing temperature for Sample 4 was also 265°C. The powder data are shown in Table 9 below. The Hausner ratios were analyzed for these powders.

[0178] [Table 19]

[0179] The obtained values ​​are shown in Table 9. The effect of heat treatment on the Hausner ratio can be observed. Heat treatment has a particularly beneficial effect on fluidity measured by the Hausner ratio. As can be seen, sphericity is affected by both mixing and heat treatment.

[0180] Example 10 In Example 10, PEKK was produced in the same manner as in Example 2, but the polymerization time was adjusted to 29 cm before heat treatment. 3 A powder with an MVR of 10 minutes was obtained (Sample No. 1). PEKK was then mixed as described in Example 3, except that the mixer processing temperature Tmax was between 110 and 120°C. T2 was adjusted to maintain t1+t2 for 25 minutes (Sample No. 2). Sample No. 2 was then annealed in the same manner as in Example 4, except that the annealing time was adjusted (Sample No. 3). The annealing temperature for Sample No. 3 was 265°C. BET analysis was performed using these samples. The obtained data are shown in Table 10.

[0181] [Table 20]

[0182] The obtained values ​​are shown in Table 10. The effects of mixing and heat treatment on the BET surface of the particles can be observed.

[0183] Methods section: Rounding by thermal-mechanical treatment The thermal-mechanical treatment of polymer particles can preferably be carried out in a mixer at a temperature of at least 30°C and below the melting point Tm of the polymer. A suitable mixer is, for example, an FML type, machine size 40 Henschel mixer (Zeppelin Systems GmbH, Germany).

[0184] Hausner ratio The Hausner ratio H provides information about the compressibility of bulk materials. It represents the bulk density pb0 (according to EN ISO-60) and tap density p of uncompressed bulk materials. t The determination is made using (compliant with DIN EN ISO 787-11).

[0185]

number

[0186] Tap density Tap density is determined in accordance with DIN EN ISO 787-11.

[0187] [Table 21]

[0188] The mechanical properties of the three-dimensional object according to the present invention can be determined based on a test sample, as described below.

[0189] The test method and the dimensions of the test specimen parts conform to the standard DIN EN ISO 527-1:2012-06 for tensile testing. For this purpose, a Zwick TC-FR005TN.A50 material testing machine, document number: 605922, equipped with TestExpert II V3.6 software, was used.

[0190] In standardized tensile tests, the modulus of elasticity [GPa], tensile strength [MPa], and elongation at break were determined using tensile specimens with the dimensions shown in Table 11. The test speed was 5 mm / min for the PEKK component. The modulus of elasticity (E-modulus) was determined at a test speed of 1 mm / min.

[0191] Determination of the extrapolation start temperature of the melting peak The material requires specific properties, which are typically determined by dynamic differential calorimetry, usually called DSC (Differential Scanning Calorimetry), with an extrapolation start temperature T. eim It can be determined based on T.ei、m The corresponding DSC measurement for determining the temperature is preferably performed in accordance with standard ISO 11357. The apparatus is, for example, a Mettler Toledo DSC 823. The melting temperature Tm and crystallization temperature Tc are also determined by this method. eim And Tm are determined from the first heating curve.

[0192] If the thermoplastic material contains or is a polymer of the PEKK class, the 0°C-360°C-0°C-360°C temperature gradient deviates from the standard. The initial temperature (0°C), maximum temperature (360°C), and minimum temperature (0°C) are maintained for 3 minutes, but the final temperature (360°C) is not maintained. Furthermore, the heating or cooling rate is 20K / min, and the measured weight is 4.5mg-5.5mg.

[0193] Optical method for determining particle size and particle shape Measurements are performed on a Camsizer XT instrument and X-Jet module (Letch Technology) using the associated software CamsizerXT64 (version 6.6.11.1069). The optical method for determining particle size and shape conforms to the standard ISO 13322-2. After determining the velocity, approximately 2 g of sample is dispersed in compressed air at 80 kPa and passed through a 4 mm wide passage on a calibrated optical unit equipped with two different magnification cameras ("basic" and "zoom"). At least 10,000 individual images are recorded for evaluation. To ensure good optical separation of the particles under consideration, images are used only when the surface density of the imaged particles is less than 3% ("basic" camera) or less than 5% ("zoom" camera). Particle size and shape are determined by defined measurement parameters. The determined size is the equivalent diameter of a circle with the same extent of particle projection x_area = √(4A / Π). The meridian or mean of this evaluation method is comparable to that of laser diffraction (reported as d10, d50, and d90, i.e., the 10th, 50th, and 90th percentiles of the volume particle size distribution). The measurements are repeated several times to form statistical measurements.

[0194] >2g / cm 3 For powders with a high specific gravity or powders that are difficult to disperse, the method may need to be adjusted in terms of sample volume, dispersion pressure, or the addition of 1% of the flow aid Alu C. The method is adapted so that the sample volume (maximum 8 g) and dispersion pressure (maximum 150 kPa) vary to achieve the smallest possible d90.

[0195] Camera parameter calibration and setting should be performed specifically for the device, and adjustments and maintenance should be carried out according to the manufacturer's specifications. (This can also be seen in printouts of the original software configuration in Figures 5, 6, and 7.) The following configuration of Camsizer XT software was used:

[0196] CAMSIZER XT Software Configuration CAMSIZER XT:0301 Overlapping area: x area: 0.080mm~0.160mm xc min: 0.080mm~0.160mm xFe min: 0.080mm~0.160mm xFe max: 0.080mm~0.160mm x area: 0.100mm~0.160mm xc min: 0.100mm~0.160mm xFE min: 0.100mm~0.160mm xFE max: 0.100mm~0.160mm x area: 0.100mm~0.160mm xc min: 0.100mm~0.160mm xFe min: 0.100mm~0.160mm xFe max: 0.100mm~0.160mm Fixed ratio between cameras for calculations: None Switching the light source off: Yes TIFF2023501423000035.tif29147 TIFF2023501423000036.tif219164 TIFF2023501423000037.tif246164 Camera (Measurement Parameters) CCD Basic: Yes threshold Regarding particle size Smaller than [mm]: 0.0023 [mm] greater than: 20 Regarding mold parameters Smaller than [mm]: 0.0023 [mm] greater than: 20 CCD zoom: Yes threshold Regarding particle size Smaller than [mm]: 0.0023 [mm] greater than: 2 Regarding mold parameters Smaller than [mm]: 0.0023 [mm] greater than: 2 Image ratio: 100% (1:1) Warning for image rate <0.95: Yes Display interval: 80 Filling with transparent particles: Yes

[0197] Determination of lower building temperature (NCT) Lower build temperatures (also non-curl temperatures = NCT) are determined by cross-tests, for example, the matrix of the cross test components (4×2 on a smaller build platform of P800, Figure 1) is determined. For this purpose, the laser sintering machine is heated to a temperature approximately 10°C (estimated) lower than the normal build temperature or alternatively approximately 5°C lower than the expected non-curl temperature. After automatic powder application, the cross layers are exposed from a height of z = 3 mm. These show strong process-critical curl, for example, the edges of the exposed test cross are significantly upward, the cross is detached from the installation space, and the temperature is increased by 2°C. After applying a 1.2 mm powder layer (P800, 10 layers with a layer thickness of 0.12 mm, or 12 layers with a layer thickness of 0.10 mm or 20 layers with a layer thickness of 0.06 mm), the test is repeated. If only slight curl can be observed, the temperature is further increased by 1°C until no process-critical curl is observed in the cross-test. That is, the cross can be built at its full height (1.2 mm height) without being detached from the powder bed by the coater during the coating process. The temperature at which no process-critical curl is observed is called the non-curl temperature and defines the lowest possible build temperature. Figure 1 shows the position of the cross test components on the EOS P800 with reduced mounting space (left) and the high-temperature measurement spot ("P", upper right).

[0198] The term "no process-critical curl" means that no curl can be observed or that minimal curl occurs but only to such a low degree that the coater cannot detach the exposed cross from the powder bed during powder application.

[0199] Determination of the higher build temperature (upper building temperature) (UBT) The maximum build temperature is the build temperature of the powder material at which the powder material does not just adhere, thereby not forming aggregates of powder particles, and the powder material for the coating process is still sufficiently fluid and without coating defects (such as binding by aggregates). The maximum processing temperature depends particularly on the type of powder material used.

[0200] However, the maximum build temperature can be reached even when the (local) formation of a molten film of the powder is not achieved, which can be seen in a shiny film (such as polyamide 12, PA2200) or a local darkening of the powder (such as EOS PEEK-HP3 described in the application manual).

[0201] For determination, the process chamber temperature is gradually increased (1-2°C) after determining a lower construction temperature, and the powder bed is accurately observed when one of the above effects occurs. Additionally or alternatively, a higher construction temperature can be determined by determining the hardness of the powder bed by Shore hardness measurement. This is useful when one of the above effects has not yet occurred. If the unsintered powder bed is too hard after the completion of the construction process, it is no longer possible to separate the exposed components from the unsintered powder. This limits the accuracy of the components. For this purpose, when a higher construction temperature than observed or assumed is reached, the process chamber temperature is reduced by 1°C, and another 3 mm layer of powder is applied as the top layer in the automated construction operation. After the construction process, the powder cake is cooled to room temperature. The surface of the top-cooled powder cake is determined on a replaceable frame in the machine by a suitable Shore hardness meter (here, Bareis HPII) located on a matrix (5 × 2 in x and y, Figure 2) of the P800's smaller construction platform in the center of each sector. The Shore hardness value is obtained as the average of the highest measurements from 50% of the matrix. If there are cracks in the powder bed in the area of ​​the measurement point (resulting in loss of powder cake due to the cooling process relative to room temperature), the measurement in each sector must be detected at a sufficient distance of approximately 15 mm from the crack. The Shore hardness at higher construction temperatures depends particularly on the type of powdery material used. How high this can be depends on the respective material, the quality of the components, and the requirements for waste powder recycling. Ideally, the same Shore hardness for higher construction temperatures should be used as a comparison. For all equally proportional refreshments, this is always essentially the same. Furthermore, since this can have an effect on the determined Shore hardness value, it should be preferred that there is no change in the heating distribution of the laser sintering machine between the powders being compared.

[0202] It is possible to determine which Shore hardness measurement is suitable for which powder. Shore hardness values ​​of Shore 00, Shore 000, and Shore 000 S, as defined in ASTM D 2240, have been proven to be preferable.

[0203] These and other Shore hardness tests are described in the Bareiss HPII Operating Instructions (HPE II Shore [D], Version 26.05.2017), which list the corresponding standards. For example, for some polymer powders, the Shore hardness at higher construction temperatures is determined using a Bareiss HPII Shore hardness tester: 1) Polyaryl ether ketones Shore -00 = 85

[0204] Operating temperature (T PK ) Process chamber temperature T PK The processing temperature represented by is preferably selected to be at least 1°C, more preferably at least 2°C, and even more preferably at least 4°C higher than the lower construction temperature of the powder, and / or at most 1°C, more preferably at most 2°C, and even more preferably at most 4°C lower than the higher construction temperature. Preferably, the processing temperature is higher than the lower construction temperature of the powder and lower than the higher construction temperature. Sufficient process security (no curling, maximum possible distance from NCT) must be ensured. Furthermore, the temperature should be as high as possible without causing adhesion of the powdery material.

[0205] Alternatively or additionally, the processing temperature for each powder can be determined by determining the Shore hardness of the cooled powder cake according to the method described in the Upper Building Temperature Determination (UBT). The Shore hardness value is preferably 5% to a maximum of 50% lower than the Shore hardness value of the UBT, preferably up to 15% lower, and more preferably up to 10% lower.

[0206] Component generation on a laser sintering machine If the thermoplastic material contains or is a polyaryletherketone (PAEK) class polymer, particularly PEKK, the experiment was performed on an improved P800 with PSW 3.8 (EOSP800 with Startup Kit PAEK 3302 CF). After the warm-up phase, 50 layers (120 μm thickness), 60 layers (100 μm thickness), or 120 layers (60 μm thickness) were laid without exposure as a bottom layer (=6 mm), while the laser sintering machine's process chamber was heated from room temperature to the specified construction temperature or temperature search start temperature within 120 minutes. After laying the bottom layer, six tensile specimens (dimensions see Table 1) were positioned adjacent to each other in the center of the construction site with parallel lengths parallel to the x-direction, and four rectangular test components (dimensions: 20 mm × 4 mm × 13.56 mm) were positioned to the left and right of the tensile specimens. A layer is laid between components in the z direction without exposure. Twenty-five tensile samples (positioned adjacent to each other in the center of the construction site and aligned in a length parallel to the z direction) are constructed at z = 9,960 mm. Following the last exposed layer, another 3 mm of powder is automatically applied, and the machine is cooled to 180°C in approximately 8 hours by a controlled cooling phase defined in the default job before the heater is switched off completely. After reaching room temperature, the components were manually removed, blasted with glass beads, and measured / tested. Figures 3 and 4 show the positions of the tensile samples in the X and z directions, as well as the density cube of the EOS P800.

[0207] The size of the construction area is approximately 350mm x 120mm (approximately 1 / 8 of the overall platform size, according to the EOS PEEK-HP3 application manual, modified construction space reduction variation 1 for P800 in the x and y directions).

[0208] The job height is 72.96 mm.

[0209] I selected the following settings: The process chamber temperature during component construction is described in detail in the Examples section; Temperature of removable frame / building platform: 255°C (for PEKK); Default job settings: PAEK3302CF; Exposure parameter: Volume energy input as described in the Examples section.

[0210] When the experiment was performed on a P810 (equipped with PSW 3.8), the build was executed using the following parameters: After the warm-up phase, 50 layers (120 μm thickness), 60 layers (100 μm thickness), or 120 layers (60 μm thickness) were laid without exposure as a bottom layer (= 6 mm), while the laser sintering machine's process chamber was heated from room temperature to the specified build temperature or temperature search start temperature within 120 minutes. After laying the bottom layer, six tensile specimens (see Table 1 for dimensions) were positioned adjacent to each other in the center of the build site, with parallel lengths parallel to the x-direction. Another 3 mm powder was automatically applied following the last exposed layer, and the machine was cooled to 180°C within approximately 8 hours by a controlled cooling phase defined in the default job before the heater was completely switched off. After reaching room temperature, the components were manually removed, blasted with glass beads, and measured / tested. Figure 3 shows the position of the tensile sample in the x-direction on the EOS P810.

[0211] The size of the construction area is approximately 350mm x 120mm (approximately 1 / 8 of the overall platform size, according to the EOS PEEK-HP3 application manual, modified construction space reduction variation 1 for P800 in the x and y directions).

[0212] The job height is 35.16 mm.

[0213] I selected the following settings: The process chamber temperature during component construction is described in detail in the Examples section; The temperature of the removable frame is 265°C, and the temperature of the construction platform is 255°C; Default job settings: EOS_PAEK3304_120_000; Exposure parameter: Volume energy input as described in the Examples section.

Claims

1. A composition comprising: at least one polymer, wherein the polymer is in powder form, and wherein the polymer comprises at least one thermoplastic polymer, the thermoplastic polymer being selected from the group consisting of at least one polyaryl ether ketone, a copolymer comprising a polyaryl ether ketone, a block copolymer comprising a polyaryl ether ketone, a polymer blend comprising a polyaryl ether ketone, and combinations thereof, wherein the composition is in powder form, the composition has a melt volume rate (MVR) of at least 5 cm 3 / 10 min and 55 cm 3 / 10 min or less, The composition has a Hausner factor of at least 1.01 and at most 1.7, where the Hausner factor is the ratio of the tapped density ρ t (in accordance with DIN EN ISO 787-11) of the bulk material not compressed to the bulk density ρ b0 (in accordance with EN ISO-60).

2. The composition according to claim 1, wherein the polyaryl ether ketone is selected from the group consisting of polyether ketone ketone (PEKK), polyether ether ketone (PEEK), a copolymer comprising PEKK, and a copolymer comprising PEEK.

3. The composition according to claim 1 or 2, wherein the polymer comprises at least one semi-crystalline polymer, and / or at least one amorphous polymer.

4. The composition according to claim 2 or 3, wherein the polyether ketone ketone comprises the following repeating units: 【Chemical 1】 wherein the ratio of repeating unit A to repeating unit B is between 80:20 and 10:

90.

5. The composition according to any one of claims 1 to 4, wherein the polyaryl ether ketone has a melting temperature Tm of at least 250 °C and up to 320 °C, and / or wherein the polyaryl ether ketone has a glass transition temperature Tg of at least 120 °C and 200 °C or less.

6. The polyether ketone ketone (PEKK) has an extrapolated onset temperature T of melting of at least 250° C. and at most 285° C., in accordance with DIN EN ISO 11357, as determined by the first heating curve of dynamic differential scanning calorimetry eim The composition according to any one of claims 2 to 5, having the same

7. The composition according to any one of claims 2 to 6, having a process window that refers to the opening between the lowest possible build temperature and the highest possible build temperature of at least 1 °C and 200 °C or less.

8. The composition according to any one of claims 1 to 7, wherein the polymer blend comprises a polyaryl ether ketone and a polyether imide.

9. The polymer in powder form comprised in the composition has the following particle size distribution: - d10 = at least 10 μm - d50 = at least 25 μm and 100 μm or less - d90 = at least 50 μm and 150 μm or less, the composition according to any one of claims 1 to 8.

10. The polymer in powder form comprised in the composition has the following particle size distribution: - d10 = at least 15 μm - d50 = at least 40 μm and 100 μm or less - Polymer particles having d90 = at least 70 μm and 150 μm or less, The composition according to any one of claims 1 to 9, wherein the polymer particles are obtained by pulverizing polymerization flakes.

11. The composition according to any one of claims 1 to 10, wherein the composition has a distribution width (d90 - d10) / d50 of 3 or less.

12. The composition according to any one of claims 1 to 11, wherein the polymer in powder form contained in the composition is polymer particles having a sphericity of at least 0.

8.

13. The composition according to any one of claims 1 to 12, wherein the composition contains a primary composition, and the content of the primary composition is more than 10% by weight and less than 60% by weight of the whole composition.

14. The composition according to any one of claims 1 to 13, having an injectability measured using a 25 mm funnel conforming to DIN EN ISO 6186 for at least 1 second and 12 seconds or less.

15. The composition according to any one of claims 1 to 14, wherein the composition contains at least one fluidizing agent.

16. The composition according to claim 15, wherein the content of the at least one fluidizing agent in the composition is 1% by weight or less.

17. The composition has a BET surface area of at least 0.1 m 2 / g and 10 m 2 / g or less, and the composition according to any one of claims 1 to 16.

18. A process for producing the composition according to any one of claims 1 to 17, wherein the process comprises: (i) a step of providing at least one thermoplastic polymer, wherein the thermoplastic polymer is selected from the group consisting of at least one polyaryl ether ketone, a copolymer containing polyaryl ether ketone, a block copolymer containing polyaryl ether ketone, a polymer blend containing polyaryl ether ketone, and combinations thereof; (ii) optionally, a step of pulverizing the polymer; (iii) optionally, a step of rounding the pulverized polymer by thermo-mechanical treatment in a mixer at a temperature of at least 30 °C and below the melting point Tm of the polymer.

19. The process according to claim 18, further comprising a subsequent step of annealing the composition at a temperature higher than Tg and lower than Tm.

20. A process for manufacturing a production element, wherein the process comprises Step of applying a layer of the composition according to any one of claims 1 to 17 and / or a composition produced by the process according to claim 18 or 19 to a manufacturing panel; Step of selectively solidifying the applied layer of the composition at a site representing a cross-section of the object to be manufactured; Step of repeating the applying step and the solidifying step until the carrier is lowered and the manufacturing element is completed. A process comprising these steps. **Claim 21** The process according to claim 20, wherein step (i) of applying the layer is performed by at least a double coating, and the application of the layer is subdivided into a step of applying a first layer having a first height H1 and a step of applying a second layer having a second height H2, and the second layer of height H2 is applied on the first layer of height H1. **Claim 22** A manufacturing element comprising the composition according to any one of claims 1 to 17. **Claim 23** Use of the composition according to any one of claims 1 to 17 for additive manufacturing.

Images