CN1348408A - Method and material for producing model bodies - Google Patents
Method and material for producing model bodies Download PDFInfo
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- CN1348408A CN1348408A CN00806679A CN00806679A CN1348408A CN 1348408 A CN1348408 A CN 1348408A CN 00806679 A CN00806679 A CN 00806679A CN 00806679 A CN00806679 A CN 00806679A CN 1348408 A CN1348408 A CN 1348408A
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- Prior art keywords
- plastic powders
- laser
- dyestuff
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- bead polymer
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- 238000000034 method Methods 0.000 title claims description 45
- 239000000463 material Substances 0.000 title claims description 15
- 239000004033 plastic Substances 0.000 claims abstract description 53
- 229920003023 plastic Polymers 0.000 claims abstract description 53
- 239000000843 powder Substances 0.000 claims abstract description 38
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims description 47
- 239000011324 bead Substances 0.000 claims description 41
- 239000000975 dye Substances 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 16
- 230000002745 absorbent Effects 0.000 claims description 15
- 239000002250 absorbent Substances 0.000 claims description 15
- 239000006229 carbon black Substances 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000049 pigment Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 3
- 239000001000 anthraquinone dye Substances 0.000 claims description 2
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical class N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- 125000005504 styryl group Chemical group 0.000 claims description 2
- 231100000987 absorbed dose Toxicity 0.000 claims 1
- 230000005855 radiation Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000006096 absorbing agent Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- GHUXAYLZEGLXDA-UHFFFAOYSA-N 8-azido-5-ethyl-6-phenylphenanthridin-5-ium-3-amine;bromide Chemical compound [Br-].C12=CC(N=[N+]=[N-])=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 GHUXAYLZEGLXDA-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004380 ashing Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000596422 Pithecellobium Species 0.000 description 2
- 235000002194 Pithecellobium dulce Nutrition 0.000 description 2
- 235000007891 Pithecellobium lobatum Nutrition 0.000 description 2
- 102400000830 Saposin-B Human genes 0.000 description 2
- 101800001697 Saposin-B Proteins 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 125000005395 methacrylic acid group Chemical class 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- ZYVYEJXMYBUCMN-UHFFFAOYSA-N 1-methoxy-2-methylpropane Chemical compound COCC(C)C ZYVYEJXMYBUCMN-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- XYWDPYKBIRQXQS-UHFFFAOYSA-N Diisopropyl sulfide Chemical compound CC(C)SC(C)C XYWDPYKBIRQXQS-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 206010065042 Immune reconstitution inflammatory syndrome Diseases 0.000 description 1
- 208000008498 Infantile Refsum disease Diseases 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- GSYWJWFOKRBGQB-UHFFFAOYSA-N N(=O)OC(C)CCCCCC.C(C(=C)C)(=O)O Chemical compound N(=O)OC(C)CCCCCC.C(C(=C)C)(=O)O GSYWJWFOKRBGQB-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical class CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002084 enol ethers Chemical class 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- PVBRSNZAOAJRKO-UHFFFAOYSA-N ethyl 2-sulfanylacetate Chemical compound CCOC(=O)CS PVBRSNZAOAJRKO-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- LYJZNXAVZMEXDH-UHFFFAOYSA-N octadecan-8-yl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCC(OC(=O)C(C)=C)CCCCCCC LYJZNXAVZMEXDH-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 239000011145 styrene acrylonitrile resin Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 238000004018 waxing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/02—Moulding by agglomerating
- B29C67/04—Sintering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/141—Processes of additive manufacturing using only solid materials
- B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0822—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using IR radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0032—Pigments, colouring agents or opacifiyng agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0047—Agents changing thermal characteristics
- B29K2105/005—Heat sensitisers or absorbers
Abstract
Model bodies of any form or shape can be produced from special plastic powders with the aid of selective sintering using infrared lasers. Also described are plastic powders containing an infrared absorber and suitable for laser-assisted model production.
Description
The present invention relates to a kind of method of modeling body, wherein use the plastics of selected plastic powders form, adopt the laser selective ground sintering of IR scope, can constitute the structure of any three-dimensional.The invention still further relates to and comprise the IR absorbent, be particularly suitable for the tailormadepiston powder that adopts IR laser sintered.
The invention particularly relates to a kind of method,, adopt computer-aided equipment, directly make prototype and model (equipment of fast shaping) by the IR laser beam operation wherein according to the geometric data that stores by plastics manufacturing threedimensional model.
Present known area of computer aided automodel manufacture method summarized in term " fast shaping ".Term " laser sintered " means a kind of fast shaping method, wherein can with the charging of given dusty material under the effect of laser beam, at given heating of planar point place and sintering, laser beam preferably adopts programme-control from level to level.
Adopt CO
2The application of the plastic powders that laser instrument is laser sintered is known (A.Gebhardt, fast shaping (Rapid Prototyping), Carl Hanser publishing house, Munich, Vienna 1996,115-116 page or leaf).This book has been narrated a kind of method of modeling body, wherein by means of CO
2The laser of laser instrument, optionally the employed plastics of sintering can constitute three-dimensional structure arbitrarily.
So far, a shortcoming of some known methods is that the degree of accuracy of the moulded parts that is obtained is restricted.Owing to lack the degree of accuracy, the present moulded parts of in this way producing in many cases, must be reprocessed through manual, and this is very expensive.The low a part of reason of the degree of accuracy is owing to adopt CO
2Laser instrument, the wavelength of this laser instrument are 10.6 μ m, so focus on relatively poor.The laser instrument that improve to focus on, for example the Nd-YAG laser instrument of wavelength 1064nm be not used for as yet so far laser sintered because common plastics do not absorb under this wavelength.
The purpose of this invention is to provide a kind of according to the geometric data that stores, employing is 500-1500nm according to the wavelength of these Data Control, the laser beam of preferred 800-1200nm, by the method for plastics manufacturing threedimensional model,, aim at the volume area of given fine grained plastic powders charging wherein corresponding to the laser beam of geometric data, make material fusion or sintering, it is characterized in that the particle mean size of plastic powders is 2-200 μ m, comprises the IR absorbent in plastic powders.
In specific embodiment of the present invention, plastic powders is spherical basically.
Another purpose of the present invention provides the plastic powders that is used as raw material with the laser modeling time, and wherein the particle mean size of powder particle (being the weighed average of particle diameter) is 2-200 μ m, comprises the IR absorbent in powder particle.
Dissimilar laser instruments all is fit to the method according to this invention.Solid state laser or semiconductor diode laser are suitable especially.The example of solid state laser comprises that wavelength is the Nd-YAG laser instrument of 1064nm and the Nd-YLF laser instrument that wavelength is 1053nm.Suitable diode laser is the laser instrument of emission wavelength 823nm or 985nm.
In irradiation process, be radiated at the preferred 0.01-100mJ/mm of energy on the powder dress table charge level
2, 1-50mJ/mm most preferably
2
According to application, the preferred 0.001-0.05mm of the effective diameter of laser beam, most preferably 0.01-0.05mm.
The preferred pulse laser that adopts, verified, high impulse frequency particularly 1-100kHz is suitable especially.
Preferable methods can be described as follows:
Laser beam is radiated at the superiors of according to the present invention material therefor charging, in irradiation process, makes the material fusion or sinters to the layer thickness of defined.The thickness of this layer can be 0.005mm-1mm, preferred 0.01mm-0.5mm.
Adopt this method, produce the ground floor of required parts.Processing space gos deep into an amount subsequently, and this is measured less than total burning layer.Adopt the additional polymeric material processing space of packing into, until reaching original height.Adopt laser to shine again, sintering goes out the second layer of these parts, and the second layer is combined with preceding one deck.Repeat this process then and go out other layer up to making this parts with sintering.
The speed of used laser beam is 1-1000mm/s, preferred 10-100mm/s.
Be fit to plastic powders of the present invention and can be different types of polymer, the example comprises polyolefin such as polyethylene and polypropylene, polyurethane, polystyrene, SAN and the polyacrylate of polyamide such as polyamide-6 and polyamide-6,6 polyester such as PET and Merlon, meltability.Plastic powders based on part crystalline form polymer is particularly suitable for making imporous model body.
The method according to this invention, the granularity of powder particle is a particular importance.Average particulate diameter is generally 2-200 μ m, preferred 5-100 μ m, most preferably 5-50 μ m.Here the average particulate diameter of enumerating (granularity) means weight mean diameter.
In order to make the necessary granularity of this method, can grind the plastics that exist with coarse granule usually.Yet in some cases, this can produce some plastic grains that the edge arranged or the corner angle shape is arranged.These particles with irregular or broken surface are mobile sometimes very poor, and this processes these particles to adopting laser sintered equipment, has adverse influence.Therefore must in plastics, add flow enhancing agent usually,, guarantee that automatic equipment can adopt these plastic grains to operate to improve the flowability of being pulverized plastics.
Shape is that spherical polymer (bead polymer) is particularly suitable for the method according to this invention basically.
Verified, bead polymer also is fit to according to laser sintering processes of the present invention.In addition, the flowability of itself is more favourable than the plastics that other grinds, and therefore, even need not add flow enhancing agent and improve their flowability.
Another important advantage of bead polymer is, when ashing, for example as the core ashing of hollow ceramic moulded parts the time, they can not stay to the residue that makes troubles later on.Under the plastic grain situation that grinds that adds flow enhancing agent, the ashing that has observed them can stay residue.
If mainly adopt the model that constitutes by plastics of laser sintered production, handle when making meticulous in processing subsequently, not staying residue is particular importance.For this purpose, for example,, after the model waxing that the method according to this invention is made, it is immersed in the ceramic material of suspension, again the model of coating ceramic material is calcined in stove in order further to improve mold surface.In roasting process, model will be burnt fully, stays the hollow molded by pottery system.Because the plastics that routine grinds can not completing combustion owing to be added with flow enhancing agent, so the metal pattern of pouring into a mould in ceramic die subsequently, its surface is inaccurate often.
Adopt another advantage of bead polymer to relate to the mold surface degree of accuracy and the surface roughness that the present invention prepares.Because they are circular, and having good flowability, is smoother so adopt the model of preferred bead polymer manufacturing, thereby also more accurate.
Bead polymer preferably is made up of homopolymers or copolymer with monoene ethylenically unsaturated compounds (monomer).On meaning of the present invention, copolymer is interpreted as by two kinds or the multiple different synthetic polymer of monomer.The example of suitable monomer comprises styrene, AMS, chlorostyrene, acrylate such as ethyl acrylate, butyl acrylate, acrylic acid-2-ethyl caproite, decyl acrylate, acrylic acid dodecane ester, methacrylate such as methyl methacrylate, EMA, isopropyl methacrylate, n-BMA, isobutyl methacrylate, hexyl methacrylate, methacrylic acid-2-Octyl Nitrite, decyl-octyl methacrylate, methacrylic acid dodecane ester, with the methacrylic acid stearyl, and acrylonitrile, methacrylonitrile, Methacrylamide and vinyl acetate.
Verified, the molecular weight of bead polymer is important to the applicability of method of the present invention.Particularly, molecular weight (weight average molecular weight, Mw) preferred 1O, 000-500,000, most preferably 20,000-250,000 dalton.In the process of producing bead polymer,, can adopt molecular weight regulator in order to regulate needed molecular weight.Shi Yi molecular weight regulator comprises sulfide especially, for example n-butyl mercaptan, dodecyl mercaptans, ethyl thioglycolate, diisopropyl sulphur ortho acid based bisulfide.Cited conditioning agent in Deutsche Bundespatent 3 010 373 also is fit to regulate molecular weight very much, for example corresponding to the enol ether of general formula I.
Can adopt known method to produce suitable especially bead polymer.Therefore can obtain the bead polymer of the about 10-200 μ of granularity m by suspension polymerisation or pearl polymerization.Term " suspension polymerisation " is interpreted as a kind of method, wherein will comprise monomer that can be dissolved in the initator in the monomer or the mixture that comprises monomer, basically with monomer immiscible contain dispersant mutually in, also can in the mixture that contains little solid particle, be ground into droplet shape, and by improving temperature and stirring so that its curing.For example, in Liv Ullmann industrial chemistry complete works, the A21 volume, the 5th edition, VCH, Wei, Yin Haimu 1992, in the 363-373 page or leaf, narrated suspension polymerisation in more detail.
Employing is called diffuse-aggregate method, can the production granularity be the bead polymer of 2-10 μ m.Adopt a kind of solvent in dispersin polymerization, the monomer that is adopted can be dissolved in this solvent, and the polymer that is generated can not be dissolved in wherein.The narrow particle size distribution of the bead polymer that common dispersin polymerization is produced.
Energy absorbing wavelength 500-1500nm, all compounds of preferred 800-1200nm light all are suitable as the IR absorbent in principle, and the two can use independent of one another IR pigment and IR dyestuff.
The preferred carbon black that adopts, the particularly synthetic carbon black of producing is as IR pigment.Adopt the BET method to measure, the specific area of used carbon black is preferably 500m
2/ g.What the carbon black of suitable type comprised that flue is black, furnace black and flame produce is dim.
In addition, the mixed-metal oxides pigment of rutile or spinel-type also suits.The example of suitable metal oxide pigment is included in the product HEUCODUR that can buy on the market
-palm fibre 859 and HEUCODUR
-Hei 953.
(absorb ultrared dyestuff, IRDs) be that this area is familiar with to the IR dyestuff.The IR dyestuff of being produced by various types of materials all suits, for example, and indoaniline dyes, oxonol dye, porphine derivative, anthraquinone dye, a styryl dye, pyrilium compound and squarylium derivative.
According to the IR dyestuff of Deutsche Bundespatent-OS 4 331 62, also be suitable especially, because they have absorption seldom in the visible region, therefore can 3 not painted or just slight painted dimension models made according to the method for the present invention.
Can enumerate as an example corresponding to the IR dyestuff of general formula I I:
According to the present invention, with respect to plastic powders, the amount of IR absorbent is 0.01-10 weight %, preferred 0.05-5 weight %.
The plastic powders that can comprise the IR absorbent with various approach productions.Therefore, can adopt extruder, plastic material be mixed with the IR absorbent, and in grater, the extrudate that obtains is crushed to required granularity in molten condition.Also can in the process of producing plastic material, add the IR absorbent, so that the IR absorbent is included in the plastic material of making.Adopting suspension polymerization to produce in the process of bead polymer, the IR absorbent can be added in the monomer.
Having been found that can be with a kind of very simple method, goes in the plastic grain the IR of solubility is dye adulterated.In this method, plastic grain is dispersed in the liquid phase of not dissolving plastics, preferably be dispersed in the water, also can adopt wetting agent or surfactant.The example that is fit to the surfactant of this purposes comprises the nonyl phenol of sodium alkyl sulfonate, the different monooctyl ester sodium of sulfosuccinic acid and ethoxylation.The IR dye solution is joined in the dispersion of acquisition, preferably add not and water-soluble mixed solvent, for example available ethyl acetate, toluene, butanone, chloroform, dichloroethanes or methyl isobutyl ether.In this processing procedure, the solvent swelling that comprises the IR dyestuff is in plastic grain.Can adopt filtration or decant to remove subsequently and anhydrate, by evaporation, for example vapourisation under reduced pressure desolvates to remove, thereby the IR dyestuff still is retained in the plastic grain.
Plastic powders according to the IR of comprising absorbent of the present invention is particularly suitable for adopting the IR laser instrument, the laser sintering processes of Nd-YAG laser instrument particularly, and make thin portion accuracy good especially model or parts.
Fig. 1 is a kind of schematic diagram of fast shaping equipment.
Adopt the production of the detailed broken plastic material of the following example and illustrate that these materials adopt the sintering experiment of IR laser instrument.
Embodiment 1
The bead polymer that comprises carbon black produced according to the invention
A) carbon black dispersion
(Printex G is provided by Degussa, and the BET specific area is 30m with the 6g carbon black
2/ g), 24g polymethyl methacrylate and 216g methyl methacrylate handled in ball mill 2 hours, thereby obtain can not sedimentation uniform dispersion.
B) bead polymer
200g is mixed from 2,2 of a) dispersion and 2.0g '-azo two (isobutyronitrile) is violent.Mixture is transferred in the stirred reactor, the alkaline aqueous solution of being made up of 50 weight % methacrylic acids and 50 weight % methylmethacrylate copolymers of 1.0 liter of 1 weight % is housed in the reactor in advance, adopts sodium hydroxide solution that the pH of this solution is adjusted to pH8.Agitator speed is adjusted to 700rpm, and insulation is 3 hours under 60 ℃, is incubated 10 hours down at 78 ℃ then, is incubated 2 hours down at 85 ℃ again, then is cooled to room temperature in 2 hours.Adopt the decant method to separate the bead polymer that generates, the water cyclic washing, dry in a vacuum under 50 ℃.Make the black bead polymer of 168g, its particle mean size is 18 μ m, and molecular weight Mw is 230,000.
Embodiment 2
The bead polymer that comprises carbon black produced according to the invention
A) carbon black dispersion
12g carbon black (Printex G is provided by Degussa), 28.8g polymethyl methacrylate, 216g methyl methacrylate and 43.2g n-BMA were handled in ball mill 2 hours, thus obtain can not sedimentation uniform dispersion.
B) bead polymer
250g is mixed from a) carbon black dispersion and 2.5g 2,2 '-azo two (isobutyronitrile) is violent.Mixture is transferred in the stirred reactor, the alkaline aqueous solution of being made up of 50 weight % methacrylic acids and 50 weight % methylmethacrylate copolymers of 1.25 liter of 1 weight % is housed in the reactor in advance, adopt sodium hydroxide solution, the pH of this solution is adjusted to pH8.Agitator speed is adjusted to 600rpm, is incubated 10 hours down, be incubated 2 hours down at 85 ℃ then, then in 2 hours, be cooled to room temperature at 78 ℃.Adopt the decant method to separate the bead polymer that generates, the water cyclic washing, dry in a vacuum under 50 ℃.Make the black bead polymer of 205g, its particle mean size is 25 μ m, and molecular weight Mw is 220,000.
Embodiment 3
The bead polymer that comprises the IR dyestuff produced according to the invention
A) production of bead polymer
2340g methyl alcohol, 180g polyvinylpyrrolidone, 210g methyl methacrylate and 90g EMA are mixed, in 4 liters of reactors of grid type agitator are housed, blend together uniform solution.In nitrogen, under agitator speed 100rpm, in 1 hour, this solution is heated to 55 ℃.The 165g methanol solution that will contain 2,2 of 6g '-azo two (isobutyronitrile) then joins in the reactor.Under 55 ℃ and 100rpm, polyblend was stirred 20 hours again.With the polymeric dispersions cool to room temperature of making, adopt intermediate processing to separate bead polymer then.Obtain the 193g bead polymer, its molecular weight Mw is 75,000, and particle mean size is 12 μ m, and (90)/ (10) value is 1.18.90% value ( (90)) of volume distributed median is to the ratio of 10% value ( (10)), and promptly (90)/ (10) is that the good of the dispersion of distribution measured. (90)/ (10) distributes less than 2.0, means narrow size distribution.
B) in bead polymer, be doped into the IR dyestuff
100g from a) bead polymer, is dispersed in the aqueous solution of 900g water and the different monooctyl ester sodium of 200mg sulfosuccinic acid.Under agitation, dyestuff and the 100g ethyl acetate with 284mg general formula I I is added drop-wise in this solution.At room temperature mixture was stirred 4 hours, adopt ultrasonic wave to handle then 10 minutes.Filter out bead polymer, the water cyclic washing in order to remove ethyl acetate fully, is dried to constant weight in a vacuum under 50 ℃.
Embodiment 4
The bead polymer that comprises the IR dyestuff produced according to the invention
A) production of bead polymer
2500g methyl alcohol, 64g polyvinylpyrrolidone, 240g styrene and 60g EMA in being housed, 4 liters of reactors of grid type agitator are blended together uniform solution.In nitrogen, under agitator speed 100rpm, in 1 hour, this solution is heated to 70 ℃.The 75g styrene solution that will contain 2,2 of 3.75g '-azo two (isobutyronitrile) then joins in the reactor.Under 70 ℃ and 100rpm, polyblend was stirred 15 hours again.Then formed polymeric dispersions is cooled to room temperature, adopts intermediate processing to separate bead polymer.Obtain the 247g bead polymer, its particle mean size is 14 μ m, and (90)/ (10) value is 1.6, and molecular weight Mw is 60,000.
B) in bead polymer, be doped into the IR dyestuff
10g is dispersed in the aqueous solution of 90g water and the different monooctyl ester sodium of 20mg sulfosuccinic acid from a) bead polymer.Under agitation, dyestuff and the 10g ethyl acetate with 28.4mg general formula I I is added drop-wise in this solution.At room temperature mixture was stirred 4 hours.Filter out bead polymer, the water cyclic washing in order to remove ethyl acetate fully, is dried to constant weight in a vacuum under 50 ℃.
The sintering experiment of the bead polymer of embodiment 5 embodiment 1-4
With the bead polymer of 20g embodiment 1-4, add the adding in the material container of experimental facilities shown in Figure 1.
By speculum 2, (effective cross section is 5mm to make the light beam of Nd-YAG laser instrument 1
2, frequency is 10Hz) and with the surface of the speed of 10mm/s aiming bead polymer charging 3, the area of laser beam flying is 20 * 20mm.The energy of irradiation is corresponding to 40mJ/mm
2Adopt this method, by embodiment 1b), 2b), 3b) and bead polymer 4b) make hard moulded parts.Adopt mechanical means that sample is broken in liquid nitrogen, adopt the scanning electron microscopy study plane of disruption.At embodiment 3a) the situation of bead polymer under (contrast experiment who does not add the IR absorbent), product still remains unchanged as powder.
| The bead polymer of the following example | The formation of moulded parts | The surface | Section is estimated | |
| 1b) | The present invention | + | Smooth | Smooth, porose |
| 2b) | The present invention | + | Smooth | Smooth, porose |
| 3b) | The present invention | + | Smooth, glossy | Smooth |
| 4b) | The present invention | + | Smooth, glossy | Smooth |
| 3a) | Contrast | - | ?- | ?- |
Claims (12)
1. one kind is used for according to the geometric data that stores, employing is according to described Data Control, wavelength is 500-1500nm, the laser beam of preferred 800-1200nm is made the method for threedimensional model by plastics, wherein corresponding to the volume area of the laser-beam acquiring particulate plastic powders charging of geometric data, make material fusion or sintering, it is characterized in that the average particulate diameter of plastic powders is 2-200 μ m, comprises the IR absorbent in plastic powders.
2. according to the method for claim 1, it is characterized in that plastic powders is a bead polymer.
3. according to the method for claim 1 or 2, it is characterized in that, adopt solid state laser, particularly wavelength is the Nd-YAG laser instrument of 1064nm, or wavelength is that the Nd-YLF laser instrument of 1053nm is as laser instrument, or it is characterized in that adopt semiconductor diode laser, particularly the laser instrument of emission wavelength 823nm or 985nm is as laser instrument.
4. according to each method of claim 1-3, it is characterized in that in irradiation process, the energy density on powder charging surface is 0.01-100mJ/mm
2, preferred 1-50mJ/mm
2
5. according to each method of claim 1-4, it is characterized in that the effective diameter of laser beam is 0.001-0.05mm, preferred 0.01-0.05mm.
6. according to each method of claim 1-4, it is characterized in that adopt pulse laser, wherein the pulse frequency of laser instrument is 1-100kHz.
7. one kind as the plastic powders with the raw material of laser modeling, and wherein the average particulate diameter of powder particle is 2-200 μ m, comprises the IR absorbent in powder particle.
8. according to the plastic powders of claim 7, it is characterized in that plastic powders is made up of bead polymer.
9. according to the plastic powders of claim 7 or 8, it is characterized in that, plastic powders comprise as the IR absorbent, can absorbing wavelength be 500-1500nm, compound, particularly IR pigment and/or the IR dyestuff of the light of preferred 800-1200nm.
10. according to the plastic powders of claim 9, it is characterized in that, plastic powders comprises the carbon black as IR pigment, or comprise be selected from indoaniline dyes, oxonol dye, porphine derivative, anthraquinone dye, a styryl dye, pyrilium compound and squarylium derivative dyestuff as the IR dyestuff.
11. according to each plastic powders of claim 7-10, it is characterized in that by plastic powders, its contained IR absorbed dose of radiation is 0.01-10 weight %, preferred 0.05-5 weight %.
12. a method that is used to produce the plastic powders that comprises the IR dyestuff is characterized in that, the aqueous dispersion that makes plastic powders with contacting with the solution of IR dyestuff in the mutual immiscible solvent of water, remove then and anhydrate and solvent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19918981A DE19918981A1 (en) | 1999-04-27 | 1999-04-27 | Process and material for the production of model bodies |
| DE19918981.1 | 1999-04-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1348408A true CN1348408A (en) | 2002-05-08 |
Family
ID=7905937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00806679A Pending CN1348408A (en) | 1999-04-27 | 2000-04-13 | Method and material for producing model bodies |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP1173314A2 (en) |
| JP (1) | JP2002542080A (en) |
| KR (1) | KR20010114248A (en) |
| CN (1) | CN1348408A (en) |
| AU (1) | AU4548200A (en) |
| BR (1) | BR0010074A (en) |
| CA (1) | CA2371181A1 (en) |
| CZ (1) | CZ20013851A3 (en) |
| DE (1) | DE19918981A1 (en) |
| HK (1) | HK1046116A1 (en) |
| IL (1) | IL145779A0 (en) |
| MX (1) | MXPA01010931A (en) |
| TR (1) | TR200102922T2 (en) |
| WO (1) | WO2000064653A2 (en) |
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| CN103772837A (en) * | 2014-01-08 | 2014-05-07 | 合肥杰事杰新材料股份有限公司 | Polystyrene microsphere material for 3D (three dimensional) printing and preparation method thereof |
| CN103772870A (en) * | 2014-01-07 | 2014-05-07 | 合肥杰事杰新材料股份有限公司 | Acrylic ester microsphere modified material, and preparation method and application thereof to 3D printing |
| CN103772877A (en) * | 2014-01-08 | 2014-05-07 | 合肥杰事杰新材料股份有限公司 | Polystyrene microsphere modified photosensitive resin for 3D printing and preparation method thereof |
| CN103772838A (en) * | 2014-01-08 | 2014-05-07 | 合肥杰事杰新材料股份有限公司 | Hydrotalcite modified polystyrene microsphere material as well as preparation method and application thereof in 3D (Three-dimensional) printing |
| CN108472871A (en) * | 2016-04-05 | 2018-08-31 | 惠普发展公司，有限责任合伙企业 | Light-sensitive material is set with |
| CN112351890A (en) * | 2018-07-10 | 2021-02-09 | 爱克发-格法特公司 | Near Infrared (NIR) laser processing of resin-based articles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004009234A1 (en) * | 2004-02-26 | 2005-09-15 | Degussa Ag | Carbon black-containing polymer powder, e.g. polyamide 12, for use in layer processes in which parts of each layer are selectively melted, e.g. for production of prototypes by laser sintering |
| DE102004012683A1 (en) * | 2004-03-16 | 2005-10-06 | Degussa Ag | Laser sintering with lasers with a wavelength of 100 to 3000 nm |
| DE102004012682A1 (en) * | 2004-03-16 | 2005-10-06 | Degussa Ag | Process for the production of three-dimensional objects by means of laser technology and application of an absorber by inkjet method |
| DE102004020452A1 (en) * | 2004-04-27 | 2005-12-01 | Degussa Ag | Method for producing three-dimensional objects by means of electromagnetic radiation and applying an absorber by inkjet method |
| DE102004062761A1 (en) * | 2004-12-21 | 2006-06-22 | Degussa Ag | Use of polyarylene ether ketone powder in a three-dimensional powder-based tool-less production process, and moldings produced therefrom |
| GB2422344B (en) * | 2005-01-24 | 2008-08-20 | Univ Montfort | Rapid prototyping method using infrared sintering |
| DE102006009095A1 (en) * | 2006-02-28 | 2007-08-30 | Bayerische Motoren Werke Ag | Process for producing a coated molding |
| JP2010184412A (en) * | 2009-02-12 | 2010-08-26 | Aspect Inc | Resin powder for laminate shaping |
| WO2014158106A1 (en) * | 2013-03-26 | 2014-10-02 | Nihat Aydin | The system of forming layer from direct molten metal |
| PL412719A1 (en) * | 2015-06-17 | 2016-12-19 | Sinterit Spółka Z Ograniczoną Odpowiedzialnością | Powder composition and method for producing three-dimensional objects by means of selective sintering or/and melting |
| EP3365156B1 (en) | 2015-10-22 | 2024-03-27 | Dow Global Technologies LLC | Selective sintering additive manufacturing method and powder used therein |
| CN108602262B (en) * | 2016-04-11 | 2021-07-30 | 惠普发展公司，有限责任合伙企业 | Granular building material |
| WO2018080537A1 (en) | 2016-10-31 | 2018-05-03 | Hewlett-Packard Development Company, L.P. | 3d printer with a uv light absorbing agent |
| EP3562651B1 (en) * | 2016-12-28 | 2024-03-27 | Stratasys, Inc. | Additive production method, with a structural material containing an ir absorber |
| EP3495155A1 (en) * | 2017-12-08 | 2019-06-12 | Agfa Nv | Near infrared (nir) laser processing of resin based articles |
| DE102018213675A1 (en) | 2018-08-14 | 2020-02-20 | Eos Gmbh Electro Optical Systems | Additive manufacturing device and associated additive manufacturing process |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3750931T3 (en) * | 1986-10-17 | 1999-12-02 | Univ Texas | METHOD AND DEVICE FOR PRODUCING MOLDED BODIES BY PARTIAL INTERSTERING. |
| US5648450A (en) * | 1992-11-23 | 1997-07-15 | Dtm Corporation | Sinterable semi-crystalline powder and near-fully dense article formed therein |
| US5817206A (en) * | 1996-02-07 | 1998-10-06 | Dtm Corporation | Selective laser sintering of polymer powder of controlled particle size distribution |
-
1999
- 1999-04-27 DE DE19918981A patent/DE19918981A1/en not_active Withdrawn
-
2000
- 2000-04-13 KR KR1020017013719A patent/KR20010114248A/en not_active Application Discontinuation
- 2000-04-13 EP EP00926905A patent/EP1173314A2/en not_active Withdrawn
- 2000-04-13 JP JP2000613629A patent/JP2002542080A/en active Pending
- 2000-04-13 MX MXPA01010931A patent/MXPA01010931A/en unknown
- 2000-04-13 CA CA002371181A patent/CA2371181A1/en not_active Abandoned
- 2000-04-13 WO PCT/EP2000/003316 patent/WO2000064653A2/en not_active Application Discontinuation
- 2000-04-13 AU AU45482/00A patent/AU4548200A/en not_active Abandoned
- 2000-04-13 BR BR0010074-9A patent/BR0010074A/en not_active Application Discontinuation
- 2000-04-13 CZ CZ20013851A patent/CZ20013851A3/en unknown
- 2000-04-13 IL IL14577900A patent/IL145779A0/en unknown
- 2000-04-13 CN CN00806679A patent/CN1348408A/en active Pending
- 2000-04-13 TR TR2001/02922T patent/TR200102922T2/en unknown
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- 2002-10-29 HK HK02107806.7A patent/HK1046116A1/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103772870A (en) * | 2014-01-07 | 2014-05-07 | 合肥杰事杰新材料股份有限公司 | Acrylic ester microsphere modified material, and preparation method and application thereof to 3D printing |
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| CN103772837A (en) * | 2014-01-08 | 2014-05-07 | 合肥杰事杰新材料股份有限公司 | Polystyrene microsphere material for 3D (three dimensional) printing and preparation method thereof |
| CN103772877A (en) * | 2014-01-08 | 2014-05-07 | 合肥杰事杰新材料股份有限公司 | Polystyrene microsphere modified photosensitive resin for 3D printing and preparation method thereof |
| CN103772838A (en) * | 2014-01-08 | 2014-05-07 | 合肥杰事杰新材料股份有限公司 | Hydrotalcite modified polystyrene microsphere material as well as preparation method and application thereof in 3D (Three-dimensional) printing |
| CN103772877B (en) * | 2014-01-08 | 2018-09-28 | 合肥杰事杰新材料股份有限公司 | A kind of polystyrene microsphere modified light-sensitive resin and preparation method thereof for 3D printing |
| CN103772838B (en) * | 2014-01-08 | 2018-09-28 | 合肥杰事杰新材料股份有限公司 | A kind of hydrotalcite-modified polystyrene microsphere material and preparation method and its application in 3D printing |
| CN108472871A (en) * | 2016-04-05 | 2018-08-31 | 惠普发展公司，有限责任合伙企业 | Light-sensitive material is set with |
| CN112351890A (en) * | 2018-07-10 | 2021-02-09 | 爱克发-格法特公司 | Near Infrared (NIR) laser processing of resin-based articles |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1173314A2 (en) | 2002-01-23 |
| JP2002542080A (en) | 2002-12-10 |
| DE19918981A1 (en) | 2000-11-02 |
| TR200102922T2 (en) | 2002-02-21 |
| CZ20013851A3 (en) | 2002-03-13 |
| AU4548200A (en) | 2000-11-10 |
| CA2371181A1 (en) | 2000-11-02 |
| WO2000064653A3 (en) | 2001-03-29 |
| BR0010074A (en) | 2002-01-15 |
| WO2000064653A2 (en) | 2000-11-02 |
| MXPA01010931A (en) | 2002-06-21 |
| IL145779A0 (en) | 2002-07-25 |
| HK1046116A1 (en) | 2002-12-27 |
| KR20010114248A (en) | 2001-12-31 |
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