Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y70/00—Materials specially adapted for additive manufacturing
  • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/28—Nitrogen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y80/00—Products made by additive manufacturing
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
  • C08K2003/321—Phosphates
  • C08K2003/322—Ammonium phosphate
  • C08K2003/323—Ammonium polyphosphate

Definitions

• the invention relates to a polymer powder which comprises at least one polymer and at least one flame retardant comprising ammonium polyphosphate, to a process for preparing this powder, and also to moldings produced by layer-by-layer application and fusion of this powder.
• Selective laser sintering is a process particularly well suited to rapid prototyping.
• polymer powders in a chamber are selectively irradiated briefly with a laser beam, resulting in melting of the particles of powder on which the laser beam falls.
• the molten particles coalesce and rapidly solidify again to give a solid mass.
• Three-dimensional bodies, including those of complex shape, can be produced simply and rapidly by this process, by repeatedly applying fresh layers and irradiating these.
• Nylon-12 powder (PA 12) has proven particularly successful in industry for laser sintering to produce moldings, in particular to produce engineering components.
• the parts manufactured from PA 12 powder meet the high requirements demanded with regard to mechanical loading, and therefore have properties particularly close to those of the mass-production parts subsequently produced by extrusion or injection molding.
• a PA 12 powder with good suitability here has a median particle size (d 50 ) of from 50 to 150 ⁇ m, and is obtained as in DE 197 08 946 or else DE 44 21 454, for example. It is preferable here to use a nylon-12 powder whose melting point is from 185 to 189° C., whose enthalpy of fusion is 112 ⁇ 17 J/g, and whose solidification point is from 138 to 143° C., as described in EP 0 911 142.
• SIB process As described in WO 01/38061 or EP 1 015 214.
• the two processes operate using infrared heating over an area to melt the powder, and selectivity of the melting is achieved in the first process by applying an inhibitor, and in the second process by way of a mask.
• Another process which has found wide acceptance in the market is 3D printing, as in EP 0 431 924; where the moldings are produced by curing of a binder applied selectively to the powder layer.
• Another process is described in DE 103 11 438. In this, the energy required for the fusion process is introduced by way of a microwave generator, and selectivity is achieved by applying a susceptor.
• pulverulent substrates in particular polymers or copolymers, preferably selected from polyester, polyvinyl chloride, polyacetal, polypropylene, polyethylene, polystyrene, polycarbonate, poly(N-methylmethacrylimides) (PMMI), polymethyl methacrylate (PMMA), ionomer, polyamide, copolyester, copolyamides, terpolymers, acrylonitrile-butadiene-styrene copolymers (ABS), or a mixture of these.
• polymers or copolymers preferably selected from polyester, polyvinyl chloride, polyacetal, polypropylene, polyethylene, polystyrene, polycarbonate, poly(N-methylmethacrylimides) (PMMI), polymethyl methacrylate (PMMA), ionomer, polyamide, copolyester, copolyamides, terpolymers, acrylonitrile-butadiene-styrene copolymers (AB
• the present invention therefore provides a pulverulent composition, in particular a construction powder or rapid-prototyping and rapid-manufacturing powder (RP/RM powder) for rapid-prototyping or rapid-manufacturing applications, for processing in a process for the layer-by-layer build-up of three-dimensional objects, by selectively bonding portions of the powder to one another, wherein the powder comprises at least one polymer and at least one flame retardant comprising ammonium polyphosphate, the maximum particle size of the powder being ⁇ 150 ⁇ m.
• RP/RM powder rapid-prototyping and rapid-manufacturing powder
• the present invention also provides a process for preparing inventive powder (pulverulent composition) which comprises preparing a pulverulent mixture in which a polymer and a flame retardant comprising ammonium polyphosphate are present.
• the present invention also provides the use of inventive powder for producing moldings by layer-by-layer processes which selectively bond the powder, and provides moldings produced by a process for the layer-by-layer build-up of three-dimensional objects, by selectively bonding portions of a powder to one another, where these comprise at least one flame retardant comprising ammonium polyphosphate and comprise at least one polymer.
• An advantage of the inventive powder is that moldings which have lower combustibility and flammability can be produced therefrom by an RP or RM process as described above for the layer-by-layer build-up of three-dimensional objects, portions of the powder used being selectively bonded to one another. At the same time, the mechanical properties of the moldings are substantially retained. This opens up applications sectors which were inaccessible hitherto because of poor combustibility grading. Particularly surprisingly, it is possible to achieve the UL 94 (Underwriters Laboratories Inc., test method 94V) classification V-0 for the finished molding if minimum contents of flame retardant comprising ammonium polyphosphate are maintained within the powders.
• UL 94 Underwriters Laboratories Inc., test method 94V
• moldings produced from the inventive powder have equally good, or even better, mechanical properties, in particular increased modulus of elasticity, tensile strength, and density.
• the moldings also have good appearance, for example good dimensional stability and surface quality.
• a feature of the inventive construction powder, or of the inventive pulverulent composition for processing in a process for the layer-by-layer build-up of three-dimensional objects in which portions of the powder are selectively bonded to one another is that the powder comprises at least one polymer and at least one flame retardant comprising ammonium polyphosphate, and has maximum particle size of ⁇ 150 ⁇ m, preferably from 20 to 100 ⁇ m.
• the powder is preferably bonded by introducing energy, particularly preferably by exposure to heat, whereupon the particles are bonded to one another by fusion or sintering.
• the powder may also be used in processes in which the particles are bonded to one another by chemical reaction or by a binder or by physical measures, preferably drying or adhesion. Details concerning the individual processes may be found in the abovementioned publications.
• the polymer, and also the flame retardant may be present in the inventive powder in the form of a mixture of the respective powders, or in the form of a powder in which most of the grains, or every grain, comprises not only polymer but also flame retardant.
• the distribution of the flame retardant may be homogeneous within the particles, or the concentration of the flame retardant may be greater in the center of the particle or at the surface of the particle.
• the polymer present in the powder is preferably a homo- or copolymer selected from polyester, polyvinyl chloride, polyacetal, polypropylene, polyethylene, polystyrene, polycarbonate, poly(N-methylmethacrylimides) (PMMI), polymethyl methacrylate (PMMA), ionomer, polyamide, copolyester, copolyamides, terpolymers, acrylonitrile-butadiene-styrene copolymers (ABS), or is a mixture of these.
• the inventive powder particularly preferably comprises a polymer which has a melting point of from 50 to 350° C., preferably from 70 to 200° C.
• the polymers present in the inventive powder may in particular be prepared by milling, precipitation and/or anionic polymerization, or by a combination of these, or by subsequent fractionation.
• the inventive powder preferably comprises at least one polyamide.
• the polyamide present in the inventive powder is preferably a polyamide which has at least 8 carbon atoms per carboxamide group.
• the inventive powder preferably comprises at least one polyamide which contains 9 or more carbon atoms per carboxamide group.
• the powder very particularly preferably comprises at least one polyamide selected from nylon 6,12 (PA 612), nylon-11 (PA 11) and nylon-12 (PA 12), or copolyamides based on the abovementioned polyamides.
• the inventive powder preferably comprises an unregulated polyamide.
• a nylon-12 sinter powder particularly suitable for the laser sintering process is one whose melting point is from 185 to 189° C., preferably from 186 to 188° C., whose enthalpy of fusion is 112 ⁇ 17 J/g, preferably from 100 to 125 J/g, and whose solidification point is from 133 to 148° C., preferably from 139 to 143° C.
• the preparation process for the polyamide powders underlying the inventive sinter powders is well known and, in the case of PA 12, can be found, for example, in the specifications DE 29 06 647, DE 35 10 687, DE 35 10 691, and DE 44 21 454, the content of which is incorporated by way of reference into the disclosure of the present invention.
• the polyamide pellets needed can be purchased from various producers, and by way of example nylon-12 pellets are supplied by Degussa AG under the trade name VESTAMID.
• a material which likewise has particularly good suitability is nylon-12 whose melting point is from 185 to 189° C., preferably from 186 to 188° C., whose enthalpy of fusion is 120 ⁇ 17 J/g, preferably from 110 to 130 J/g, and whose solidification point is from 130 to 140° C., preferably from 135 to 138° C., and whose crystallization point after aging is also preferably from 135 to 140° C.
• a powder which comprises a copolymer, in particular one which is a copolyamide, has particularly good suitability for the processes for producing three-dimensional objects without use of a laser.
• the inventive powder preferably comprises from 5 to 50% by weight of a flame retardant comprising ammonium polyphosphate, with preference comprises from 10 to 40% by weight of a flame retardant comprising ammonium polyphosphate, and particularly preferably comprises from 20 to 35% by weight of a flame retardant comprising ammonium polyphosphate, and very particularly preferably comprises from 23 to 34% by weight of a flame retardant comprising ammonium polyphosphate.
• the ranges given here refer to the entire content of a flame retardant comprising ammonium polyphosphate present in the powder, where powder means the entire amount of components.
• the inventive powder may comprise polymer particles mixed with a flame retardant comprising ammonium polyphosphate, or else may comprise polymer particles or polymer powder which comprise incorporated flame retardant comprising ammonium polyphosphate. If the proportion of a flame retardant comprising ammonium polyphosphate is below 5% by weight, based on the entire amount of components, the desired effect of low flammability and incombustibility is markedly reduced. If the proportion of a flame retardant comprising ammonium polyphosphate is above 50% by weight, based on the entire amount of components, mechanical properties, such as strain at break, of the moldings produced from these powders are markedly impaired.
• the maximum size of the polymer particles is 150 ⁇ m, and their median particle size is preferably from 20 to 100 ⁇ m, particularly preferably from 45 to 80 ⁇ m.
• the particle size of the flame retardant comprising ammonium polyphosphate is preferably below the median grain size d 50 of the polymer particles or polymer powder by at least 20%, preferably by more than 50% and very particularly preferably by more than 70%.
• the median particle size of the flame retardant component is from 1 to 50 ⁇ m, preferably from 5 to 15 ⁇ m. The small particle size gives good dispersion of the pulverulent flame retardant within the polymer powder.
• the flame retardants present in the inventive powder comprises ammonium polyphosphate as principal component.
• the phosphorus content in the ammonium polyphosphate here is preferably from 10 to 35% by weight, preferably from 15 to 32% by weight, and very particularly preferably from 20 to 32% by weight.
• the flame retardant is preferably halogen-free. However, it may comprise synergists, such as carbon-forming materials, e.g. polyalcohols or pentaerythritol, and/or, by way of example, an intumescent (foaming) component, for example melamine. Sulfur may also be present in the composition.
• the flame retardant is a powder, it may also comprise a coating, in order to provide compatibility, or in order to increase the moisture-resistance of the ammonium polyphosphate.
• These coated flame retardants are obtainable from Budenheim Iberica under the name Budit, for example.
• flame retardants comprising ammonium polyphosphate are Budit 3076 DCD or Budit 3076 DCD-2000 from the Company Budenheim Iberica, or products from the Exolit AP line, such as Exolit AP 750 or Exolit AP 422 from the Company Clariant.
• inventive powder may comprise at least one auxiliary, at least one filler, and/or at least one pigment.
• these auxiliaries may be flow aids, e.g. fumed silicon dioxide, or else precipitated silicic acid. Fumed silicon dioxide (fumed silicic acid) is supplied by Degussa AG under the product name Aerosil® with various specifications, for example.
• the flow aids may be hydrophobic flow aids.
• Inventive powder preferably comprises less than 3% by weight, with preference from 0.001 to 2% by weight, and very particularly preferably from 0.05 to 1% by weight, of these auxiliaries, based on the entirety of components, i.e. on the entirety of polymers and flame retardant.
• the fillers may be glass particles, metal particles, in particular aluminum particles, or ceramic particles, e.g. solid or hollow glass beads, steel shot, aluminum spheres, or granulated metal, or else color pigments, e.g. transition metal oxides.
• the median grain size of the filler particles here is preferably smaller than, or approximately equal to, that of the particles of the polymers.
• the extent to which the median grain size d 50 of the fillers exceeds the median grain size d 50 of the polymers should preferably be not more than 20%, with preference not more than 15%, and very particularly preferably not more than 5%.
• a particular limit on the particle size arises via the permissible overall height or layer thickness in the particular apparatus used for the layer-by-layer process.
• Inventive powder preferably comprises less than 70% by weight, with preference from 0.001 to 60% by weight, particularly preferably from 0.05 to 50% by weight, and very particularly preferably from 0.5 to 25% by weight, of these fillers, based on the entirety of components, such that the proportion by volume of the polymers is always greater than 50%.
• inventive powders may be prepared in a simple manner, preferably by the inventive process for preparing inventive powder, by mixing at least one polymer with at least one flame retardant comprising ammonium polyphosphate.
• the dry blend mixing process may be used for dry mixing.
• a polymer powder obtained, by way of example, by reprecipitation and/or milling, which may also subsequently be fractionated is mixed with the flame retardant comprising ammonium polyphosphate. It can be advantageous here to provide a flow aid initially to the pulverulent flame retardant alone, or else to the finished mixture, for example one from the Aerosil R line from Degussa, e.g. Aerosil R972 or R812.
• the flame retardant comprising ammonium polyphosphate may be compounded into a melt of at least one polymer, and the resultant mixture may be processed by milling to give powder.
• the processing of ammonium polyphosphate-based flame retardants in the compounding is described by way of example in Plastics Additives & Compounding, April 2002, Elsevier Advanced Technology, pp. 28 to 33.
• fine-particle mixing may take place by a mixing process which applies finely pulverized flame retardant to the dry powder in high-speed mechanical mixers.
• the powder may be a polymer powder which is itself suitable for the layer-by-layer rapid prototyping process, fine particles of the flame retardant simply being admixed with this powder.
• the median grain size of the particles here is preferably smaller than, or at most approximately equal to, that of the particles of the polymers.
• the extent to which the median grain size d 50 of the flame retardant particles is less than the median grain size d 50 of the polymer powders should preferably be more than 20%, with preference more than 50%, and very particularly preferably more than 70%. A particular upward limit on the grain size arises via the permissible overall height or layer thickness in the rapid prototyping system.
• the flame retardant is mixed with a, preferably molten, polymer via incorporation by compounding, and the resultant polymer comprising flame retardant is processed by (low temperature) milling and, where appropriate, fractionation to give inventive powder.
• the compounding generally gives pellets which are then processed to give powder.
• An example of a method for this conversion process is milling.
• the process variant in which the flame retardant is incorporated by compounding has the advantage over the pure mixing process of giving more homogeneous distribution of the flame retardant within the powder.
• a suitable flow aid such as fumed aluminum oxide, fumed silicon dioxide, or fumed titanium dioxide, may be added externally to the precipitated or low-temperature-milled powder, in order to improve flow performance.
• a flow-control agent such as a metal soaps, preferably the alkali metal or alkaline earth metal salts of the underlying alkanemonocarboxylic acids or dimer acids, may be added to the precipitated or low-temperature-milled powder in order to improve melt flow during the production of the moldings.
• Flame retardants that may be used are commercially available products, for example those which may be purchased from Budenheim Iberica or Clariant under the trade name Exolit AP® or Budit®, or those described above.
• the amounts used of the metal soaps are from 0.01 to 30% by weight, preferably from 0.5 to 15% by weight, based on the entirety of polyamides present in the powder.
• Metal soaps preferably used are the sodium or calcium salts of the underlying alkanemonocarboxylic acids or dimer acids. Examples of commercially available products are Licomont NaV or Licomont CaV from Clariant.
• the metal soap particles may be incorporated into the polyamide particles, or else fine metal soap particles may have been mixed with polyamide particles.
• this may treated with inorganic pigments, in particular color pigments, e.g. transition metal oxides, stabilizers, e.g. phenols, in particular sterically hindered phenols, flow control agents and flow aids, e.g. fumed silicic acids, and also filler particles.
• inorganic pigments in particular color pigments, e.g. transition metal oxides, stabilizers, e.g. phenols, in particular sterically hindered phenols, flow control agents and flow aids, e.g. fumed silicic acids, and also filler particles.
• the present invention also provides the use of inventive powder for producing moldings in a layer-by-layer process which selectively bonds the powder (rapid prototyping or rapid manufacturing), these being processes which use inventive powders, the polymers, and a flame retardant comprising ammonium polyphosphate, preferably each in particulate form.
• the present invention in particular provides the use of the powder for producing moldings via selective laser sintering of a precipitation powder comprising flame retardant and based on a nylon-12 which has a melting point of from 185 to 189° C., and enthalpy of fusion of 112 ⁇ 17 J/g, and a solidification point of from 136 to 145° C., and the use of which is described in U.S. Pat. No. 6,245,281.
• Laser sintering processes are sufficiently well known, and are based on the selective sintering of polymer particles, where layers of polymer particles are briefly exposed to laser light and the polymer particles exposed to the laser light are thus bonded to one another. Successive sintering of layers of polymer particles produces three-dimensional objects. Details concerning the selective laser sintering process are found, by way of example, in the specifications U.S. Pat. No. 6,136,948 and WO 96/06881.
• the inventive powder may also be used in other rapid prototyping or rapid manufacturing processing of the prior art, in particular in those described above.
• the inventive powder may in particular be used for producing moldings from powders via the SLS (selective laser sintering) process, as described in U.S.
• inventive powders Careful handling of the inventive powders is advisable because the flame retardants are air-sensitive. In particular, prolonged contact of the inventive powder with air or with atmospheric moisture is to be avoided.
• the sensitivity of the inventive powder can be reduced by using hydrophobic flow aids, thus permitting avoidance of any reduction in modulus of elasticity which is sometimes caused by the decomposition products of ammonium polyphosphate.
• inventive moldings produced via a process for the layer-by-layer build-up of three-dimensional objects, in which portions of a powder, in particular of the inventive powder, are selectively bonded to one another, e.g. selective laser sintering, comprise at least one flame retardant comprising ammonium polyphosphate and comprise at least one polymer, or are composed of at least one flame retardant comprising ammonium polyphosphate and of at least one polymer.
• inventive moldings preferably comprise at least one polyamide which contains at least 8 carbon atoms per carboxamide group.
• Inventive moldings very particularly preferably comprise at least one nylon-6,12, nylon-11 and/or one nylon-12, or copolyamides based on these polyamides, and comprise at least one flame retardant comprising ammonium polyphosphate.
• the flame retardant present in the inventive molding is based on ammonium polyphosphate.
• the inventive molding preferably comprises, based on the entirety of components present in the molding, from 5 to 50% by weight of flame retardant comprising ammonium polyphosphate, preferably from 10 to 40% by weight, particularly preferably from 20 to 35% by weight, and very particularly preferably from 23 to 24% by weight.
• the proportion of flame retardant comprising ammonium polyphosphate is preferably at most 50% by weight, based on the entirety of components present in the molding.
• the molding comprises from 30 to 35% by weight of flame retardant comprising ammonium polyphosphate.
• the moldings may also comprise fillers and/or auxiliaries, and/or pigments, e.g. heat stabilizers and/or antioxidants, e.g. sterically hindered phenol derivatives.
• fillers may be glass particles, ceramic particles, or else metal particles, e.g. iron shot, or corresponding hollow spheres.
• the inventive moldings preferably comprise glass particles, very particularly preferably glass beads.
• Inventive moldings preferably comprise less than 3% by weight, with preference from 0.001 to 2% by weight, and very particularly preferably from 0.05 to 1% by weight, of these auxiliaries, based on the entirety of components present.
• Inventive moldings likewise preferably comprise less than 75% by weight, with preference from 0.001 to 70% by weight, particularly preferably from 0.05 to 50% by weight, and very particularly preferably from 0.5 to 25% by weight, of theses fillers, based on the entirety of components present.
• the internal temperature is brought to 117° C., using the same cooling rate, and then held constant for 60 minutes.
• the internal temperature is then brought to 111° C., using a cooling rate of 40 K/h. At this temperature the precipitation begins and is detectable via evolution of heat. After 25 minutes the internal temperature falls, indicating the end of the precipitation.
• the suspension is transferred to a paddle dryer.
• the ethanol is distilled off from the material at 70° C. and 400 mbar, with stirring, and the residue is then further dried at 20 mbar and 85° C. for 3 hours.
• BET 6.9 m 2 /g
• Bulk density 429 g/l
• 1023 g (35 parts) of Budit 3076 DCD-2000 are mixed within a period of 3 minutes with 1900 g (65 parts) of nylon-12 powder, prepared as in DE 29 06 647, example 1, and having a median grain diameter d 50 of 56 ⁇ m (laser scattering) and a bulk density of 459 g/l to DIN 53 466, in a dry blend process utilizing a FML10/KM23 Henschel mixer at 700 rpm and at 50° C. 1.5 g of Aerosil R 812 (0.05 part) were then mixed into the material within a period of 3 minutes at room temperature and 500 rpm.
• Budit 3076 DCD are mixed within a period of 3 minutes with 1900 g (70 parts) of nylon-12 powder, prepared as in DE 29 06 647, example 1, and having a median grain diameter d 50 of 56 ⁇ m (laser scattering) and a bulk density of 459 g/l to DIN 53 466, in a dry blend process utilizing a FML10/KM23 Henschel mixer at 700 rpm and at 50° C. 54 g (2 parts) of Licomont NaV and 2 g of Aerosil 200 (0.1 part) were then mixed into the material within a period of 3 minutes at room temperature and 500 rpm.
• Exolit AP 422 475 g (20 parts) of Exolit AP 422 are mixed within a period of 3 minutes with 1900 g (80 parts) of nylon-12 powder, prepared as in DE 29 06 647, example 1, and having a median grain diameter d 50 of 56 ⁇ m (laser scattering) and a bulk density of 459 g/l to DIN 53 466, in a dry blend process utilizing a FML10/KM23 Henschel mixer at 700 rpm and at 50° C. 2.4 g of Aerosil R 200 (0.1 part) were then mixed into the material within a period of 3 minutes at room temperature and 500 rpm.
• the powders from examples 1 to 4 were used in a laser sintering machine to build up bars for the UL 94V fire-protection test, and also to build up multipurpose bars to ISO 3167.
• the latter components were used to determine mechanical properties by means of a tensile test to EN ISO 527 (table 1).
• the UL bars were used for the vertical UL 94V (Underwriters Laboratories Inc.) combustion test. The bars have specified dimensions of 3.2*10*80 mm. Each was produced on an EOSINT P360 laser sintering machine from EOS GmbH.

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• 2004
  • 2004-01-08 DE DE102004001324A patent/DE102004001324A1/de not_active Withdrawn
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  • 2004-07-19 TW TW093121515A patent/TW200505978A/zh unknown
• 2006
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