CA2537749C - Laser sintering processes using thermoplastic compositions - Google Patents
Laser sintering processes using thermoplastic compositions Download PDFInfo
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- CA2537749C CA2537749C CA002537749A CA2537749A CA2537749C CA 2537749 C CA2537749 C CA 2537749C CA 002537749 A CA002537749 A CA 002537749A CA 2537749 A CA2537749 A CA 2537749A CA 2537749 C CA2537749 C CA 2537749C
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- thermoplastic
- block copolymer
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- nylon
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- 239000000203 mixture Substances 0.000 title claims abstract description 116
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 81
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000000149 argon plasma sintering Methods 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 29
- 238000002844 melting Methods 0.000 claims abstract description 28
- 230000008018 melting Effects 0.000 claims abstract description 28
- 229920001400 block copolymer Polymers 0.000 claims description 59
- 239000004615 ingredient Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 230000008595 infiltration Effects 0.000 claims description 9
- 238000001764 infiltration Methods 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000806 elastomer Substances 0.000 claims description 8
- 229910021485 fumed silica Inorganic materials 0.000 claims description 8
- 229920001778 nylon Polymers 0.000 claims description 8
- 239000003086 colorant Substances 0.000 claims description 7
- 229920001971 elastomer Polymers 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000004677 Nylon Substances 0.000 claims description 6
- 230000004927 fusion Effects 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- -1 polybutylene phthalate Polymers 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- 229920002292 Nylon 6 Polymers 0.000 claims description 3
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 3
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000571 Nylon 11 Polymers 0.000 claims description 2
- 229920000299 Nylon 12 Polymers 0.000 claims description 2
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000391 magnesium silicate Substances 0.000 claims description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 2
- 235000019792 magnesium silicate Nutrition 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229960004029 silicic acid Drugs 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000008199 coating composition Substances 0.000 claims 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- 239000011236 particulate material Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 6
- 229920012824 Hytrel® 4068FG Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000011800 void material Substances 0.000 description 4
- 229920002614 Polyether block amide Polymers 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000110 selective laser sintering Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 241000239290 Araneae Species 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- 241000905957 Channa melasoma Species 0.000 description 1
- 229920012375 Elvamide® 8061 Polymers 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- 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
-
- 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
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C09D167/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- Organic Chemistry (AREA)
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- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mechanical Engineering (AREA)
- Ceramic Engineering (AREA)
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- Laminated Bodies (AREA)
Abstract
A method of laser sintering a thermoplastic composition to provide an article of manufacture having a plurality of sintered layers is disclosed. The thermoplastic composition has a relatively high melting point and a small particle size. The articles of manufacture have a high resolution and excellent durability and strength.
Description
LASER SINTERING PROCESSES USING THERMOPLASTIC COMPOSITIONS
FIELD OF THE INVENTION
The present invention relates to thermo-plastic compositions useful in laser sintering processes to form flexible articles of manufacture.
The articles of manufacture are prepared at rela-tively high temperatures, and have excellent reso-lution, strength, and durability.
BACKGROUND OF THE INVENTION
Laser sintering is a process wherein an article of manufacture is built layer by layer. The laser-sintering technique is based on using a laser beam to selectively fuse a predetermined portion of a layer of particulate material. The particulate mate'rial contacted by the laser is heated to a tem-perature above its melting point, after which adja-cent particles are fused together, as are adjacent layers of fused material.
Laser sintering generally is performed according to the following steps:
1. A piston of the process chamber is lowered by one layer thickness, and simultaneously, a piston of a cartridge containing the particulate material is raised;
FIELD OF THE INVENTION
The present invention relates to thermo-plastic compositions useful in laser sintering processes to form flexible articles of manufacture.
The articles of manufacture are prepared at rela-tively high temperatures, and have excellent reso-lution, strength, and durability.
BACKGROUND OF THE INVENTION
Laser sintering is a process wherein an article of manufacture is built layer by layer. The laser-sintering technique is based on using a laser beam to selectively fuse a predetermined portion of a layer of particulate material. The particulate mate'rial contacted by the laser is heated to a tem-perature above its melting point, after which adja-cent particles are fused together, as are adjacent layers of fused material.
Laser sintering generally is performed according to the following steps:
1. A piston of the process chamber is lowered by one layer thickness, and simultaneously, a piston of a cartridge containing the particulate material is raised;
2. A particulate material is introduced into the process chamber, and a leveling roller spreads the particulate material evenly over a build surface of the process chamber;
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-
3. The'particulate material is heated to a temperature near, but below, its softening point;
4. A laser beam then=traces a predeter-mined cross section of the article on the layer of heated particulate material in the build surface, thus forming a solid layer; and
5. Steps 2 through 4 are repeated until the article is completed.
The particulate material in areas that have not been sintered b,y the laser remains unfused and in place, and acts as a natural support for the article being manufactured. Accordingly, no need exists for support structures during manufacture of the article. Figures 1 and 2 are schematics illus-trating the laStr-sintering process for the manufac-ture of an article having a complex shape. Clausen et al. U.S. Patent No. 6,110,411 provides a detailed description of the selective layer sintering process, and also discloses laser-sinterable thermoplastic compositions for use in the process.
In particular, U.S. Patent No. 6,110,411 is directed to thermoplastic compositions having a glass transition temperature (Tg) of not more than 50 C that are useful in a selective laser sintering process. U.S.. Patent No. 6,110, 411 particularly teaches a laser-sinterable composition containing a flow agent and a block copolymer thermoplastic resin having a glass transition temperature (Tg) of not more than 50 C. The low T. of the block copolymer permits a relatively low temperature laser sintering process that, according to U.S. Patent No.
The particulate material in areas that have not been sintered b,y the laser remains unfused and in place, and acts as a natural support for the article being manufactured. Accordingly, no need exists for support structures during manufacture of the article. Figures 1 and 2 are schematics illus-trating the laStr-sintering process for the manufac-ture of an article having a complex shape. Clausen et al. U.S. Patent No. 6,110,411 provides a detailed description of the selective layer sintering process, and also discloses laser-sinterable thermoplastic compositions for use in the process.
In particular, U.S. Patent No. 6,110,411 is directed to thermoplastic compositions having a glass transition temperature (Tg) of not more than 50 C that are useful in a selective laser sintering process. U.S.. Patent No. 6,110, 411 particularly teaches a laser-sinterable composition containing a flow agent and a block copolymer thermoplastic resin having a glass transition temperature (Tg) of not more than 50 C. The low T. of the block copolymer permits a relatively low temperature laser sintering process that, according to U.S. Patent No.
6,110,411, overcomes,the problems of temperature control, distortion of the formed article, article inflexibility, and long cooling times associated with prior compositions, e.g., nylon-based composi-tions, that had to be heated to 170 C to 190 C prior to laser sintering. Such high process temperatures are considered disadvantageous because of poor sintering performance, especially poor temperature control, which leads to parts having poor physical properties and failing to meet specifications. U.S, Patent No. 6,110,411 teaches compositions that are laser sinterable below 170 C to 190 C, i.e., from room temperature to a temperature less than 150 C.
However, the compositions-of U.S. Patent No. 6,110,411 also have disadvantages. First, reso-lution of the article after manu'facture'is substan-dard; with the article lacking crisp sharp features, such as edges. Second, the durability of articles manufactured from the low Tg and low melting point block copolymer often is poor. The property of the compositions disclosed in U.S. Patent No. 6,110,411 that allows a low process temperature and imparts enhanced flexibility to the articles, therefore also detracts from the long-term durability of the article.
Third, the density of the article typi-cally is low. In particular, articles prepared by laser sintering a composition of U.S. Patent No.
6,110,411 have a relatively high void volume, and, consequently, a relatively low volume density. Such ~ -. 4 -articles typically have a volume density that is about 60% to about 80% of theoretical density.
Therefore, the strength of the articles, especially thin articles, is low.
To improve the density and strength of an article of manufacture prepared using a low Tg and low melting point block copolymer of U.S. Patent'No.
6,110,411, the article is subjected'to an "infiltra-tion" step wherein a liquid polymer, such as a poly-urethane oligomer, is introduced into the voids of the article, then crosslinked. This infiltration step decreases the void volume of the article, increases article density, and strengthens the article, but adds an expensive and time-consuming step to the manufacturing process.
The present invention is directed to thermoplastic compositions that are laser sinterable-and overcome the disadvantages associated with the compositions of U.S. Pa,tent No. 6,110,411 and other laser sinterable thermoplastic compositions.
I
BACKGROUND OF THE INVENTION
The present invention is directed to thermoplastic compositions useful in laser sintering processes. More particularly, the present invention is directed to a thermoplastic composition compris-ing a block copolymer having a relatively high melt-ing point, and, in preferred embodiments, a high heat of fusion.
Accordingly, one aspect of the present in-vention is to provide a thermoplastic composition that can be laser sintered to yield flexible arti-cles of manufacture having excellent resolution, durability, and strength.
Another aspect of the present invention is to provide a laser sinterable thermoplastic composi-tion comprising a mixture of (a) one or more partic-ulate thermoplastic block copolymer having a melting point of about 180 C to about 210 C, and, in pre-ferred embodiments, a high heat of fusion (AHf), and (b) an optional particulate flow agent. In pre-ferred embodiments, the block copolymer has a re-crystallization temperature that is about 40 C to about 60 C below its,melting point.
A block copolymer included in the present composition contains a multiplicity-of recurring segments characterized as soft (amorphous) and hard (crystalline) segments. These s'egments'are joined head,to tail randomly to form the block copolymer.
The soft segment is selected from the group consist-ing of ether and ester monomer units, and the hard segment is selected from the group consisting of ester, amide, and urethane monomer units.
Still another aspect of the present inven-tion is to provide a method of manufacturing an article of manufacture using laser sintering com-prising the steps of (a) depositing a quantity of a thermo-plastic composition of the present invention on a support surface;
(b) leveling the composition to form a smooth layer of the composition on the support sur-face;
(c) then directing an energy beam over a predetermined target area on the support surface causing the composition to form an integral layer;
and I
(d) repeating steps (a) to (c) to form additional layers that are integrally bonded to adjacent layers to form,a three-dimensional article.
Yet another aspect of the present inven-tion is to manufacture an article by a laser sinter-ing process having a sufficient volume density such that an infiltration step to increase article den-sity and strength can be omitted. ,, These and other novel aspe'cts and advan-tages of the present invention will become more apparent from the following detailed description of the preferred embodimeiits taken in conjunction with the figures.
BRIEF DESCRIPTION OF THE FIGURES
Figs. 1 and 2 are schematics illustrating the laser sintering process.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A thermoplastic composition of the present invention comprises a thermoplastic block copolymer having a melting point of about 180 C to 210 C.
More particularly, a thermoplastic composition of
However, the compositions-of U.S. Patent No. 6,110,411 also have disadvantages. First, reso-lution of the article after manu'facture'is substan-dard; with the article lacking crisp sharp features, such as edges. Second, the durability of articles manufactured from the low Tg and low melting point block copolymer often is poor. The property of the compositions disclosed in U.S. Patent No. 6,110,411 that allows a low process temperature and imparts enhanced flexibility to the articles, therefore also detracts from the long-term durability of the article.
Third, the density of the article typi-cally is low. In particular, articles prepared by laser sintering a composition of U.S. Patent No.
6,110,411 have a relatively high void volume, and, consequently, a relatively low volume density. Such ~ -. 4 -articles typically have a volume density that is about 60% to about 80% of theoretical density.
Therefore, the strength of the articles, especially thin articles, is low.
To improve the density and strength of an article of manufacture prepared using a low Tg and low melting point block copolymer of U.S. Patent'No.
6,110,411, the article is subjected'to an "infiltra-tion" step wherein a liquid polymer, such as a poly-urethane oligomer, is introduced into the voids of the article, then crosslinked. This infiltration step decreases the void volume of the article, increases article density, and strengthens the article, but adds an expensive and time-consuming step to the manufacturing process.
The present invention is directed to thermoplastic compositions that are laser sinterable-and overcome the disadvantages associated with the compositions of U.S. Pa,tent No. 6,110,411 and other laser sinterable thermoplastic compositions.
I
BACKGROUND OF THE INVENTION
The present invention is directed to thermoplastic compositions useful in laser sintering processes. More particularly, the present invention is directed to a thermoplastic composition compris-ing a block copolymer having a relatively high melt-ing point, and, in preferred embodiments, a high heat of fusion.
Accordingly, one aspect of the present in-vention is to provide a thermoplastic composition that can be laser sintered to yield flexible arti-cles of manufacture having excellent resolution, durability, and strength.
Another aspect of the present invention is to provide a laser sinterable thermoplastic composi-tion comprising a mixture of (a) one or more partic-ulate thermoplastic block copolymer having a melting point of about 180 C to about 210 C, and, in pre-ferred embodiments, a high heat of fusion (AHf), and (b) an optional particulate flow agent. In pre-ferred embodiments, the block copolymer has a re-crystallization temperature that is about 40 C to about 60 C below its,melting point.
A block copolymer included in the present composition contains a multiplicity-of recurring segments characterized as soft (amorphous) and hard (crystalline) segments. These s'egments'are joined head,to tail randomly to form the block copolymer.
The soft segment is selected from the group consist-ing of ether and ester monomer units, and the hard segment is selected from the group consisting of ester, amide, and urethane monomer units.
Still another aspect of the present inven-tion is to provide a method of manufacturing an article of manufacture using laser sintering com-prising the steps of (a) depositing a quantity of a thermo-plastic composition of the present invention on a support surface;
(b) leveling the composition to form a smooth layer of the composition on the support sur-face;
(c) then directing an energy beam over a predetermined target area on the support surface causing the composition to form an integral layer;
and I
(d) repeating steps (a) to (c) to form additional layers that are integrally bonded to adjacent layers to form,a three-dimensional article.
Yet another aspect of the present inven-tion is to manufacture an article by a laser sinter-ing process having a sufficient volume density such that an infiltration step to increase article den-sity and strength can be omitted. ,, These and other novel aspe'cts and advan-tages of the present invention will become more apparent from the following detailed description of the preferred embodimeiits taken in conjunction with the figures.
BRIEF DESCRIPTION OF THE FIGURES
Figs. 1 and 2 are schematics illustrating the laser sintering process.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A thermoplastic composition of the present invention comprises a thermoplastic block copolymer having a melting point of about 180 C to 210 C.
More particularly, a thermoplastic composition of
- 7 -the present invention comprises: (a) about 90% to 100%, by weight, of a particulate thermoplastic block copolymer having a melting point of about 180 C to about 210 C, and, in preferred embodiments, a high heat of fusion, and (b) about 0% to about 5%, by weight, of a particulate flow agent. The thermo-pla,~tic compositions also can comprise other op-tional ingredients, such as a coloring agent or a second modifying polymer, that do not adversely affect the thermoplastic composition or an article of manufacture prepared from the composition.
The major component of the thermoplastic composition is a particulate thermoplastic copolymer in an amount of about 90% to about 100%, and pref-erably about 95% to about 99.950; by weight of the composition. To achieve the full advantage of the present invention, the thermopla'stic coinposition contains about 97% to about 99.95%, by weight, of the thermoplastic block copolymer.
The particulate thermoplastic block co-polymer contains discrete segments along the polymer chain characterized as soft and hard segments.
These segments are bonded one to another, randomly, by condensation polymerization such that the head of one segment is joined to the tail of another seg-ment.
The soft segment can be an ether or an ester, and is amorphous. The hard segment can be an ester, an amide, or a urethane, and is crystalline.
The block copolymers useful in the present invention are represented by the following, nonlimiting, com-- :8 -.binati.ons with the soft segment,listed first:
ether-ester, ester-ester, ether-amide,' ester-amide, ether-urethane, ester-urethane, or mixtures of these combinations. The structures of these block copoly-mers are disclosed in U.S. Patent No.s. 6,110,411;
3,561,014; 3,763,109; 3,766,146; 4,205,158;
4, 544, 734; 4, 556, 688; 3, 784, 52:0; and 3, 044, 987.
A particulate thermoplastic block copoly-mer used in the present,invention can be a single block copolymer or a mixture of block copolymers.
Howev;er, each copolymer has a melting point of about 1180 C to about 210 C, and, preferably, a high OHt.
In such a mixture of block copolyrners, it is pre-f erred that 'ths. melting points of the block copoly-mers are within 10C , and more p.refetably 5C ,' of one another.
Regardless of the chemical identity of the thermoplastic block copplymer, the copolymer has a melting pointof about 180 C to about 210 C, and preferably about 185 C to about 205 C=. To achieve the full advantage of the present invention, the thermoplastic block copolymer has a melting point of about 190 C to about 200 C.
Preferably, the thermoplastic block co-polymer also has a high heat of fusiori (LHf) of about 15 to about 35, and more preferably about 17 to about 33, J/g {Joules/gram). To achieve the full advantage of the present invention, the block co-polymer has a AHf of about 20 to about 30 J/g.
The heat of fusion is the quantity of heat required to change'one gram of a solid to a liquid, without a temperature change, at the melting point of the solid. A high LHf allows the block copolymer to remain in the crystalline state when heated near its softening point prior to laser sintering. The particles of the block copolymer, therefore, resist softening and clumping, and do not fuse prematurely prior to laser sintering. As a result, the laser sintering process is facilitated and the resolution of the articles of manufacture is improved.
As discussed in more detail hereafter, a high melting thermoplastic block copolymer used in the present method provides a strong, durable arti-cle of manufacture having excellent-resolution.
These improvements are attributed, in part, to pro-viding a more dense article of m~nufacture.
I Examples of thermoplastic block copolymers that can be used in the present invention include copolymers sold under the tradenames HYTREL (E.I.
duPont), SANIFLEX (Wilden), ECDEL (Eastman Chem-icals), GAFLEX (Celanese), LOMOD (General Electric), ARNITEL (Dutch State Mines), PEBAX (Atochem), ESTANE
(B.F. Goodrich), ESTAMID (Dow), RITEFLEX (Ticona GmbH), PELLATHANE (Dow Chemical), Q-THANE (K.J.
Quinn), and TEXIN (Mobay). HYTREL and RITEFLEX, for example, are polyether-ester elastomers; ARNITEL is a polyester-ester elastomer, PEBAX is a polyether-amide elastomer, ESTANE is a polyether-urethane * elastomer, ESTAMID is a polyester-amide; and TEXIN
is a polyester-urethane.
i -110 -Specific block copolymers, useful in the present invention include, but are not limited to, HYTREL Types 4069, 4556, 5526, 4059FG, G4778, G4774, 5555HS, and 6359FG, and RITEFLEX Type 663. Espe-cially preferred block copolymers useful in the present invention are HYTREL 4068FG and RITEFLEX
640. 1 HYTREL 4068Fd has a melting point of 193 C, a recrystallization,point of about 140 C, and a AHf of 25,J/g. HYTREL 4068FG is a thermoplastic block copolymer having a hard (i.e., crystalline) segment of polybutylene phthalate and a soft (i.e., amorphous) segment based on a long chain polyalkyl-enether glycol.
In a,ccordance with -an important featur,e of the present invention, the particles'of the thermo-plastic block copolymer have a median particle size of about 40 to about 60 pm, a particle size range of about 1 to about 150 pm, and a particle size distri-bution (d90) of about 90 to about 100 pm. The term "d90 of about 9'0 to about 100 m" is defined as 90%
of the particles being smaller than about 90 to about 100 pm, and about 10% of the particles being greater than about 90 to about 100 pm. This small uniform particle size allows a more efficient fusion of block copolymer particles during laser sintering, and provides a more dense and stronger article of manufacture.
A thermoplastic composition of the present invention optionally contains a flow agent. In particular, a thermoplastic composition of the pres-ent invention contains 0%, preferably 0.05%, to about 5%, and more'preferably about 0.075% to about 1%, by weight of a particulate flow agent. To achieve the full advantage of the present invention, the thermoplastic composition contains about 0.1% to about 0.25%, by weight, of the flow,agent.
The optional flow agent included in the thermoplastic composition is a particulate inorganic material having a median particle size of 10 microns or less, and is selected from the group consisting of a hydrated silica, amorphous alumina, a glassy silica, a glassy phosphate, a glassy borate, a glassy oxide, titani~i, talc, mica, a fumed silica, kaolin, attapulgite, calcium silicate, alumina, and magnesium silicate. The=flow agent-preferably is present in an amountsufficient to allow the thermoplastic block copolymer to, flow and levelon the build surface of the laser sintering device.
The preferred flow agent is a fumed silica.
A present thermoplastic composition also can contain other optional ingredients. These optional ingredients are particulate materials and include organic and inorganic materials, such as fillers and coloring agents. An optional ingredient is present in a sufficient amount to perform its intended function, without adversely affecting the thermoplastic composition or an article prepared therefrom. Optional ingredients have a particle size in the range of the particle sizes of the block copolymer and/or optional flow agent. Each optional ingredient is milled,iif necessary, to the desired median particle size and particle size distribution.
Each individual optional ingredient, if present at all, typically is present.in the thermo-plastic composition in an amount of about 0.1% to about 30%, by weight, of the composition. The total amount of optional ingredients in the thermoplastic composition ranges from'O% up to about 30%, by weight.
It is not necessary for an optional ingre-dient to melt during the laser sintering process.
However, each optional ingredient must be compatible with the block copolymer in order to provide a strong and durable article of manufacture. The optional ingredient, therefore, can be inorganic, filler that imparts additional strength to the article of manufacture.
One optional ingredient is a coloring agent, for example a pigment or a dye, like carbon black, to impart a desired color to the article of manufacture. The coloring agent is not limited, as long as the coloring agent does not adversely affect the composition or an article prepared therefrom, and is sufficiently stable to retain its color under conditions of the laser sintering process and during exposure to the laser.
The optional ingredient also can be a second polymer that modifies the properties of the thermoplastic block copolymer. One useful second polymer is a nylon, such as nylon 6, nylon 66, nylon 11, nylon 610, nylon 12, nylon 612, copolymerized nylons, and mixtures thereof. Such nylon materials typically are laser sintered after heating to about 170 C to about 190 C. Accordingly, the nylons melt near the range of a block copolymer included in a present composition, and the laser sintering process is facilitated. One nonlimiting example of a nylon that can be included in a thermoplastic composition of the present invention is the ELVAMIDE line of nylon resins, available from DuPont Co., Wilmington, DE, for example, ELVAMIDE 8061, a polyamide terpoly-mer of nylon 6, nylon 66, and nylon 610. 0 The present thermoplastic compositions are sinterable at relatiyely high temperatures, e.g., at a temperature slightly below the melting point of the block copolymer. Because of the relative high melting point of the block copolymer, and, prefer-ably, the high AHf, thermal degradation'of the block copolymer is essentially eliminated. Accordingly, a thermoplastic composition of the present invention can be laser sintered at a temperature of about 160 C to about 210 C, depending upon the melting point of the block copolymers present in the thermo-plastic composition. In preferred embodiments, a high AHf of the block copolymer helps ensure that the copolymer particles do not soften, flow, and/or fuse prior to laser sintering.
Each ingredient of the thermoplastic com-position is dry, i.e., contains a minimal amount of moisture, typically 2%, by weight, or less. All composition ingredients are milled or ground, if necessary, to provide the desired particle size.
The composition ingredients then are blended, in any order, but typically by adding ingredients to the block copolymer, and admixed until a uniform com-position containing discrete particles of each ingredient results. After admixture, the resulting composition is sieved to provide a desired particle size and particle size distribution.
The thermoplastic compositions of the present invention preferably are elastomeric and provide flexible articles of manufacture. However, because of the high melting point of the block co-polymers present in the thermoplastic composition, and because of the particle size of the ingredients in the composition, the articles of manufacture resulting from',.the laser sintering process exhilpit a durability and strength that substan'tially exceed the durability and strength of articles prepared using an elastomeric composition of the prior art, for example, an elastomeric composition disclosed in U.S. Patent No. 6,110,411.
It is theorized, but not relied upon here-in, that the relatively high melting point block copolymer utilized in the present invention, assis-ted by the particle size of the block copolymer particles, and, preferably, high block copolymer OHf, provides a more stable thermoplastic composition after heating near its melting point prior to laser sintering. The heated composition remains crystal-line, and melts and fuses after being subjected to laser sintering. These features are believed to improve the resolution, durability, and strength of the manufactured art~cle.
Accordingly, an article of manufacture prepared by laser sintering a thermoplastic composi-tion of the present invention has a volume density that is substantially equal to an article manufac-tur(~!d isotropically, e.g., molded, from the iden-tical composition. As defined herein, the term "volume density substantially equal to" is defined as a density that is 80% to 95%, and preferably greater than 90%, of the volume density of an arti-, cle manufactured isotropically using an identical composition.
Due to the high volume density and low void density of an article prepared-by laser sintering a composition of the present invention, the strength of the article is sufficient such that an infiltration step can be eliminated. Articles made by laser sintering a composition of U.S. Patent No. 6,110,411 have a relatively low volume density, and, accordingly, a relatively high void density.
The relatively porous article therefore lacks strength, and an infiltration step is necessary to fill the voids and impart strength to the article.
The present composition overcomes the need of an infiltration step.
The thermoplastic compositions of the present invention are laser sintered by heating a layer of the composition present on the build sur-face of a process chamber to a temperature slightly below the softening point (Ts) of the block copoly--'16 -mer, e.g., within about 10C of~the softening point of the block copolymer. By directing a laser at a predetermined portion of the build surface, the .
thermoplastic composition is heated above the melt-ing point of the block copolymer, the particles of the thermoplastic composition in the layer then fuse together, and the layer fuses to an adjacent, pre-viously fused layer. After a layer-by-layer manu-facture of an article of manufacture, the article exhibits excellent resolution, durability, and strength.
The following examples illustrate the un-expected benefits provided by laser sintering a thermoplastic composition of the present invention.
All tests were,',.performed using the composition of Example 1.
Example 1 HYTREL 4068FG, a polyether-ester elasto-mer, available from E.I. duPoint de Nemours, Inc. of Wilmington, DE, as quarter-inch diameter, cylindri-cal pellets, was milled under liquid nitrogen in an attrition mill and screened to a particle size having a d90 of 94 microns.
The milled HYTREL 4068FG was admixed with fumed silica, e.g., Cab-o-Sil PS 530 fumed silica (flow agent), available from Cabot Corporation, Inc., Tuscola, IL, to provide a thermoplastic compo-sition containing 99.9%, by weight, HYTREL 4068FG
and 0.1%, by weight, fumed silica.
This thermoplastic composition was applied to a build surface 'of a selective laser sintering apparatus, i.e., a VANGUARDTI" HS selective laser sintering system, from 3D Systems, Valencia, CA.
The layer of the thermoplastic composition had a thickness of about 100 to about 200 microns.
After the thermoplastic composition was leveled to form a smooth surface, the composition was heated to about 180 C to about 190 C (i.e., slightly below the softening point of the block co-polymer), then exposed to radiation from a 25 watt carbon dioxide laser. The laser beam was controlled by computer such that laser beam movement scanned an area of about 6.45 square centimeters.
The energy of the laser was held constant at 25 watts, but the intensity of,the exposure was controlled by varying the scan rate from between 1 m/sec to 2 m/sec. Before each pass of the laser, a layer of powdered polymer was deposited over the build surface such that the new layer of thermo-plastic composition was about 150 microns. The laser line spacing was 0.20 mm. Each pass of the laser caused the thermoplastic composition to fuse and produce a solid layer. With successive passes of the laser beam, the newly formed layer is fused to the layer formed during the previous pass. After ten such passes, a rectangular solid article was formed having a thickness of about 0.15 cm and faces of 6.45 cm2. The formed article then was cooled.
The article was flexible and could be deformed by pressure supplied by hand. Once the pressure was relaxed, the article returned to its original shape.
Any residual powdered polymer clinging-to the surface of the article was removed by shaking the article or brushing its surface. The thermo-plastic composition was fused into articles using a wide range of laser interisities, and in all cases the articles had good physical integrity and could not be divided into separate layers by pulling or other types of deformations with force applied directly by hand.
Example 2 The thermoplastic composition of Example 1 also was used~to manufacture complex articles o~' manufacture using the VANGUARDT" HS system. The com-position of Example 1 provided flexible articles having excellent strength and hardness. In this test, the thermoplastic composition of Example 1 was heated to about, 100 C to about 120 C prior to laser sintering. The part bed temperature and feed tem-perature settings were varied as illustrated in the following table. The first article of manufacture, i.e., hearing aid shells, provided articles of excellent resolution. In additional tests, the part bed temperature setting was reduced by about 5C , which resulted in improved articles.
Process Parameter First Run Second Run Roller speed 3 inch/second 12 inch/second Part bed temp. setting 120 C 100 C
Feed bed temp. setting 100 C 100 C
Laser fill scans 1 2 Part bed ramp 0 C/inch 5 C/inch Warm-up height 0.5 inch 0.1 inch Cool, down time Overnight As fast as possible During the first run, the buildability of the composition was good. Composition rollout (i.e., leveling) was good, but slightly clumpy in front of the roller. The increased roller speed in the second run eliminated clumping.
The laser power during one pass causes the composition to smoke, which indicates that the laser power is sufficiently high. Increasing the number of laser scans did not-adversely,'affect,the article, and helped eliminate delamination of layers.
Melt flow data was collected for the com-position of Example 1 using the latest melt flow procedure of drying and using a heavy weight. The melt flow index was about 38 grams/minute for a composition subjected to laser sintering one time.
The strength of the manufactured articles was tested on a durometer and exhibited a strength of about 54 Shore A.
Overall, the composition of Example 1 was easy to process, and the composition outside of the sintering zone had good recyclability. The un-sintered composition was completely broken up by hand, resifted, and reused without noticeable ad-verse effects. A number of different articles of manufacture were constructed successfully, including hearing aids, tubes, bellows, and a spider.
The thermoplastic composition of Example 1 also was compared to a commercial composition incorporating a low melting point block copolymer and flow agent, as disciosed in U.S., Patent No.
6,110,411. The following,table shows that a compo-sition of Example 1 has,an improved tear strength and elongation at break, and a comparable Shore A
Hardness, for both uninfiltrated and infiltrated sintered articles. The infiltrant in both cases was a polyurethane.
Surprisingly, the data shows that the,un-infiltrated article prepared from-a composition of the present invention had a greater tear strength and greater elongation at break than an infiltrated article prepared from the same composition. Accord-ingly, an articie of manufacture prepared from a composition of the present invention by laser sintering does not require an infiltration step to improve the properties of the articles. In pre-ferred embodiments of the present invention, an infiltration step is avoided.
Example 1 Comparative Composition Uninfiltrated Infiltrated Uninfiltrated Infiltrated Tear strength 2.71 N/mm 2 2.43 N/mm2 1.02 N/mmZ 1.15 N/mm2 Elongation at 170% 155%
b break 115% 60%
Shore A 55-65 55-75 75 75 Hardness
The major component of the thermoplastic composition is a particulate thermoplastic copolymer in an amount of about 90% to about 100%, and pref-erably about 95% to about 99.950; by weight of the composition. To achieve the full advantage of the present invention, the thermopla'stic coinposition contains about 97% to about 99.95%, by weight, of the thermoplastic block copolymer.
The particulate thermoplastic block co-polymer contains discrete segments along the polymer chain characterized as soft and hard segments.
These segments are bonded one to another, randomly, by condensation polymerization such that the head of one segment is joined to the tail of another seg-ment.
The soft segment can be an ether or an ester, and is amorphous. The hard segment can be an ester, an amide, or a urethane, and is crystalline.
The block copolymers useful in the present invention are represented by the following, nonlimiting, com-- :8 -.binati.ons with the soft segment,listed first:
ether-ester, ester-ester, ether-amide,' ester-amide, ether-urethane, ester-urethane, or mixtures of these combinations. The structures of these block copoly-mers are disclosed in U.S. Patent No.s. 6,110,411;
3,561,014; 3,763,109; 3,766,146; 4,205,158;
4, 544, 734; 4, 556, 688; 3, 784, 52:0; and 3, 044, 987.
A particulate thermoplastic block copoly-mer used in the present,invention can be a single block copolymer or a mixture of block copolymers.
Howev;er, each copolymer has a melting point of about 1180 C to about 210 C, and, preferably, a high OHt.
In such a mixture of block copolyrners, it is pre-f erred that 'ths. melting points of the block copoly-mers are within 10C , and more p.refetably 5C ,' of one another.
Regardless of the chemical identity of the thermoplastic block copplymer, the copolymer has a melting pointof about 180 C to about 210 C, and preferably about 185 C to about 205 C=. To achieve the full advantage of the present invention, the thermoplastic block copolymer has a melting point of about 190 C to about 200 C.
Preferably, the thermoplastic block co-polymer also has a high heat of fusiori (LHf) of about 15 to about 35, and more preferably about 17 to about 33, J/g {Joules/gram). To achieve the full advantage of the present invention, the block co-polymer has a AHf of about 20 to about 30 J/g.
The heat of fusion is the quantity of heat required to change'one gram of a solid to a liquid, without a temperature change, at the melting point of the solid. A high LHf allows the block copolymer to remain in the crystalline state when heated near its softening point prior to laser sintering. The particles of the block copolymer, therefore, resist softening and clumping, and do not fuse prematurely prior to laser sintering. As a result, the laser sintering process is facilitated and the resolution of the articles of manufacture is improved.
As discussed in more detail hereafter, a high melting thermoplastic block copolymer used in the present method provides a strong, durable arti-cle of manufacture having excellent-resolution.
These improvements are attributed, in part, to pro-viding a more dense article of m~nufacture.
I Examples of thermoplastic block copolymers that can be used in the present invention include copolymers sold under the tradenames HYTREL (E.I.
duPont), SANIFLEX (Wilden), ECDEL (Eastman Chem-icals), GAFLEX (Celanese), LOMOD (General Electric), ARNITEL (Dutch State Mines), PEBAX (Atochem), ESTANE
(B.F. Goodrich), ESTAMID (Dow), RITEFLEX (Ticona GmbH), PELLATHANE (Dow Chemical), Q-THANE (K.J.
Quinn), and TEXIN (Mobay). HYTREL and RITEFLEX, for example, are polyether-ester elastomers; ARNITEL is a polyester-ester elastomer, PEBAX is a polyether-amide elastomer, ESTANE is a polyether-urethane * elastomer, ESTAMID is a polyester-amide; and TEXIN
is a polyester-urethane.
i -110 -Specific block copolymers, useful in the present invention include, but are not limited to, HYTREL Types 4069, 4556, 5526, 4059FG, G4778, G4774, 5555HS, and 6359FG, and RITEFLEX Type 663. Espe-cially preferred block copolymers useful in the present invention are HYTREL 4068FG and RITEFLEX
640. 1 HYTREL 4068Fd has a melting point of 193 C, a recrystallization,point of about 140 C, and a AHf of 25,J/g. HYTREL 4068FG is a thermoplastic block copolymer having a hard (i.e., crystalline) segment of polybutylene phthalate and a soft (i.e., amorphous) segment based on a long chain polyalkyl-enether glycol.
In a,ccordance with -an important featur,e of the present invention, the particles'of the thermo-plastic block copolymer have a median particle size of about 40 to about 60 pm, a particle size range of about 1 to about 150 pm, and a particle size distri-bution (d90) of about 90 to about 100 pm. The term "d90 of about 9'0 to about 100 m" is defined as 90%
of the particles being smaller than about 90 to about 100 pm, and about 10% of the particles being greater than about 90 to about 100 pm. This small uniform particle size allows a more efficient fusion of block copolymer particles during laser sintering, and provides a more dense and stronger article of manufacture.
A thermoplastic composition of the present invention optionally contains a flow agent. In particular, a thermoplastic composition of the pres-ent invention contains 0%, preferably 0.05%, to about 5%, and more'preferably about 0.075% to about 1%, by weight of a particulate flow agent. To achieve the full advantage of the present invention, the thermoplastic composition contains about 0.1% to about 0.25%, by weight, of the flow,agent.
The optional flow agent included in the thermoplastic composition is a particulate inorganic material having a median particle size of 10 microns or less, and is selected from the group consisting of a hydrated silica, amorphous alumina, a glassy silica, a glassy phosphate, a glassy borate, a glassy oxide, titani~i, talc, mica, a fumed silica, kaolin, attapulgite, calcium silicate, alumina, and magnesium silicate. The=flow agent-preferably is present in an amountsufficient to allow the thermoplastic block copolymer to, flow and levelon the build surface of the laser sintering device.
The preferred flow agent is a fumed silica.
A present thermoplastic composition also can contain other optional ingredients. These optional ingredients are particulate materials and include organic and inorganic materials, such as fillers and coloring agents. An optional ingredient is present in a sufficient amount to perform its intended function, without adversely affecting the thermoplastic composition or an article prepared therefrom. Optional ingredients have a particle size in the range of the particle sizes of the block copolymer and/or optional flow agent. Each optional ingredient is milled,iif necessary, to the desired median particle size and particle size distribution.
Each individual optional ingredient, if present at all, typically is present.in the thermo-plastic composition in an amount of about 0.1% to about 30%, by weight, of the composition. The total amount of optional ingredients in the thermoplastic composition ranges from'O% up to about 30%, by weight.
It is not necessary for an optional ingre-dient to melt during the laser sintering process.
However, each optional ingredient must be compatible with the block copolymer in order to provide a strong and durable article of manufacture. The optional ingredient, therefore, can be inorganic, filler that imparts additional strength to the article of manufacture.
One optional ingredient is a coloring agent, for example a pigment or a dye, like carbon black, to impart a desired color to the article of manufacture. The coloring agent is not limited, as long as the coloring agent does not adversely affect the composition or an article prepared therefrom, and is sufficiently stable to retain its color under conditions of the laser sintering process and during exposure to the laser.
The optional ingredient also can be a second polymer that modifies the properties of the thermoplastic block copolymer. One useful second polymer is a nylon, such as nylon 6, nylon 66, nylon 11, nylon 610, nylon 12, nylon 612, copolymerized nylons, and mixtures thereof. Such nylon materials typically are laser sintered after heating to about 170 C to about 190 C. Accordingly, the nylons melt near the range of a block copolymer included in a present composition, and the laser sintering process is facilitated. One nonlimiting example of a nylon that can be included in a thermoplastic composition of the present invention is the ELVAMIDE line of nylon resins, available from DuPont Co., Wilmington, DE, for example, ELVAMIDE 8061, a polyamide terpoly-mer of nylon 6, nylon 66, and nylon 610. 0 The present thermoplastic compositions are sinterable at relatiyely high temperatures, e.g., at a temperature slightly below the melting point of the block copolymer. Because of the relative high melting point of the block copolymer, and, prefer-ably, the high AHf, thermal degradation'of the block copolymer is essentially eliminated. Accordingly, a thermoplastic composition of the present invention can be laser sintered at a temperature of about 160 C to about 210 C, depending upon the melting point of the block copolymers present in the thermo-plastic composition. In preferred embodiments, a high AHf of the block copolymer helps ensure that the copolymer particles do not soften, flow, and/or fuse prior to laser sintering.
Each ingredient of the thermoplastic com-position is dry, i.e., contains a minimal amount of moisture, typically 2%, by weight, or less. All composition ingredients are milled or ground, if necessary, to provide the desired particle size.
The composition ingredients then are blended, in any order, but typically by adding ingredients to the block copolymer, and admixed until a uniform com-position containing discrete particles of each ingredient results. After admixture, the resulting composition is sieved to provide a desired particle size and particle size distribution.
The thermoplastic compositions of the present invention preferably are elastomeric and provide flexible articles of manufacture. However, because of the high melting point of the block co-polymers present in the thermoplastic composition, and because of the particle size of the ingredients in the composition, the articles of manufacture resulting from',.the laser sintering process exhilpit a durability and strength that substan'tially exceed the durability and strength of articles prepared using an elastomeric composition of the prior art, for example, an elastomeric composition disclosed in U.S. Patent No. 6,110,411.
It is theorized, but not relied upon here-in, that the relatively high melting point block copolymer utilized in the present invention, assis-ted by the particle size of the block copolymer particles, and, preferably, high block copolymer OHf, provides a more stable thermoplastic composition after heating near its melting point prior to laser sintering. The heated composition remains crystal-line, and melts and fuses after being subjected to laser sintering. These features are believed to improve the resolution, durability, and strength of the manufactured art~cle.
Accordingly, an article of manufacture prepared by laser sintering a thermoplastic composi-tion of the present invention has a volume density that is substantially equal to an article manufac-tur(~!d isotropically, e.g., molded, from the iden-tical composition. As defined herein, the term "volume density substantially equal to" is defined as a density that is 80% to 95%, and preferably greater than 90%, of the volume density of an arti-, cle manufactured isotropically using an identical composition.
Due to the high volume density and low void density of an article prepared-by laser sintering a composition of the present invention, the strength of the article is sufficient such that an infiltration step can be eliminated. Articles made by laser sintering a composition of U.S. Patent No. 6,110,411 have a relatively low volume density, and, accordingly, a relatively high void density.
The relatively porous article therefore lacks strength, and an infiltration step is necessary to fill the voids and impart strength to the article.
The present composition overcomes the need of an infiltration step.
The thermoplastic compositions of the present invention are laser sintered by heating a layer of the composition present on the build sur-face of a process chamber to a temperature slightly below the softening point (Ts) of the block copoly--'16 -mer, e.g., within about 10C of~the softening point of the block copolymer. By directing a laser at a predetermined portion of the build surface, the .
thermoplastic composition is heated above the melt-ing point of the block copolymer, the particles of the thermoplastic composition in the layer then fuse together, and the layer fuses to an adjacent, pre-viously fused layer. After a layer-by-layer manu-facture of an article of manufacture, the article exhibits excellent resolution, durability, and strength.
The following examples illustrate the un-expected benefits provided by laser sintering a thermoplastic composition of the present invention.
All tests were,',.performed using the composition of Example 1.
Example 1 HYTREL 4068FG, a polyether-ester elasto-mer, available from E.I. duPoint de Nemours, Inc. of Wilmington, DE, as quarter-inch diameter, cylindri-cal pellets, was milled under liquid nitrogen in an attrition mill and screened to a particle size having a d90 of 94 microns.
The milled HYTREL 4068FG was admixed with fumed silica, e.g., Cab-o-Sil PS 530 fumed silica (flow agent), available from Cabot Corporation, Inc., Tuscola, IL, to provide a thermoplastic compo-sition containing 99.9%, by weight, HYTREL 4068FG
and 0.1%, by weight, fumed silica.
This thermoplastic composition was applied to a build surface 'of a selective laser sintering apparatus, i.e., a VANGUARDTI" HS selective laser sintering system, from 3D Systems, Valencia, CA.
The layer of the thermoplastic composition had a thickness of about 100 to about 200 microns.
After the thermoplastic composition was leveled to form a smooth surface, the composition was heated to about 180 C to about 190 C (i.e., slightly below the softening point of the block co-polymer), then exposed to radiation from a 25 watt carbon dioxide laser. The laser beam was controlled by computer such that laser beam movement scanned an area of about 6.45 square centimeters.
The energy of the laser was held constant at 25 watts, but the intensity of,the exposure was controlled by varying the scan rate from between 1 m/sec to 2 m/sec. Before each pass of the laser, a layer of powdered polymer was deposited over the build surface such that the new layer of thermo-plastic composition was about 150 microns. The laser line spacing was 0.20 mm. Each pass of the laser caused the thermoplastic composition to fuse and produce a solid layer. With successive passes of the laser beam, the newly formed layer is fused to the layer formed during the previous pass. After ten such passes, a rectangular solid article was formed having a thickness of about 0.15 cm and faces of 6.45 cm2. The formed article then was cooled.
The article was flexible and could be deformed by pressure supplied by hand. Once the pressure was relaxed, the article returned to its original shape.
Any residual powdered polymer clinging-to the surface of the article was removed by shaking the article or brushing its surface. The thermo-plastic composition was fused into articles using a wide range of laser interisities, and in all cases the articles had good physical integrity and could not be divided into separate layers by pulling or other types of deformations with force applied directly by hand.
Example 2 The thermoplastic composition of Example 1 also was used~to manufacture complex articles o~' manufacture using the VANGUARDT" HS system. The com-position of Example 1 provided flexible articles having excellent strength and hardness. In this test, the thermoplastic composition of Example 1 was heated to about, 100 C to about 120 C prior to laser sintering. The part bed temperature and feed tem-perature settings were varied as illustrated in the following table. The first article of manufacture, i.e., hearing aid shells, provided articles of excellent resolution. In additional tests, the part bed temperature setting was reduced by about 5C , which resulted in improved articles.
Process Parameter First Run Second Run Roller speed 3 inch/second 12 inch/second Part bed temp. setting 120 C 100 C
Feed bed temp. setting 100 C 100 C
Laser fill scans 1 2 Part bed ramp 0 C/inch 5 C/inch Warm-up height 0.5 inch 0.1 inch Cool, down time Overnight As fast as possible During the first run, the buildability of the composition was good. Composition rollout (i.e., leveling) was good, but slightly clumpy in front of the roller. The increased roller speed in the second run eliminated clumping.
The laser power during one pass causes the composition to smoke, which indicates that the laser power is sufficiently high. Increasing the number of laser scans did not-adversely,'affect,the article, and helped eliminate delamination of layers.
Melt flow data was collected for the com-position of Example 1 using the latest melt flow procedure of drying and using a heavy weight. The melt flow index was about 38 grams/minute for a composition subjected to laser sintering one time.
The strength of the manufactured articles was tested on a durometer and exhibited a strength of about 54 Shore A.
Overall, the composition of Example 1 was easy to process, and the composition outside of the sintering zone had good recyclability. The un-sintered composition was completely broken up by hand, resifted, and reused without noticeable ad-verse effects. A number of different articles of manufacture were constructed successfully, including hearing aids, tubes, bellows, and a spider.
The thermoplastic composition of Example 1 also was compared to a commercial composition incorporating a low melting point block copolymer and flow agent, as disciosed in U.S., Patent No.
6,110,411. The following,table shows that a compo-sition of Example 1 has,an improved tear strength and elongation at break, and a comparable Shore A
Hardness, for both uninfiltrated and infiltrated sintered articles. The infiltrant in both cases was a polyurethane.
Surprisingly, the data shows that the,un-infiltrated article prepared from-a composition of the present invention had a greater tear strength and greater elongation at break than an infiltrated article prepared from the same composition. Accord-ingly, an articie of manufacture prepared from a composition of the present invention by laser sintering does not require an infiltration step to improve the properties of the articles. In pre-ferred embodiments of the present invention, an infiltration step is avoided.
Example 1 Comparative Composition Uninfiltrated Infiltrated Uninfiltrated Infiltrated Tear strength 2.71 N/mm 2 2.43 N/mm2 1.02 N/mmZ 1.15 N/mm2 Elongation at 170% 155%
b break 115% 60%
Shore A 55-65 55-75 75 75 Hardness
Claims (25)
1. A method of manufacturing an article comprising laser sintering a thermoplastic composition comprising a thermoplastic block copolymer having a melting point of about 180°C to about 210°C, wherein the block copolymer comprises soft and hard segments, the soft segment comprising an ether or an ester.
2. The method of claim 1, wherein the thermoplastic coating composition comprises at least 90%, by weight, of the thermoplastic copolymer.
3. The method of claim 1, wherein the thermoplastic coating composition comprises at least 97%, by weight, of the thermoplastic copolymer.
4. The method of claim 1, wherein the thermoplastic coating composition comprises at least 95%, by weight, of the thermoplastic copolymer.
5. The method of any one of claims 1 to 4, wherein the hard segment comprises an ester, amide, or urethane.
6. The method of any one of claims 1 to 5, wherein the block copolymer has a melting point of about 185°C to about 205°C.
7. The method of any one of claims 1 to 5, wherein the block copolymer has a melting point of about 190°C to about 200°C.
8. The method of any one of claims 1 to 7, wherein the block copolymer has a d90 of about 90 to about 100 µm.
9. The method of claim 8, wherein the block copolymer has a median particle size of about 40 to about 60 µm.
10. The method of claim 9, wherein the block copolymer has a particle size range of about 1 to about 150 µm.
11. The method of any one of claims 1 to 10, wherein the block copolymer has a heat of fusion of about 15 to about 35 Joules/gram.
12. The method of any one of claims 1 to 11, wherein the block copolymer comprises a polyether-ester elastomer.
13. The method of claim 12, wherein the polyether elastomer comprises polybutylene phthalate segments and long-chain polyalkylenether glycol segments.
14. The method of any one of claims 1 to 13, wherein thermoplastic composition further comprises a flow agent in an amount of about 0.05% to about 5%, by weight, of the composition.
15. The method of claim 14, wherein the flow agent has a median particle size of about 10 microns or less.
16. The method of claim 14 or 15, wherein the flow agent is selected from the group consisting of hydrated silica, amorphous alumina, a glassy silica, a glassy phosphate, a glassy borate, a glassy oxide, titania, talc, mica, a fumed silica, kaolin, attapulgite, calcium silicate, alumina, magnesium silicate, and mixtures thereof.
17. The method of claim 14 or 15, wherein the flow agent comprises a fumed silica.
18. The method of any one of claims 1 to 17, wherein the thermoplastic composition comprises about 0.1% to about 30%, by weight, in total, of an optional ingredient selected from the group consisting of a coloring agent, a filler, a second modifying polymer, and mixtures thereof.
19. The method of claim 18, wherein the coloring agent comprises carbon black.
20. The method of claim 18, wherein the second modifying polymer comprises a polyamide.
21. The method of claim 20, wherein the polyamide is selected from the group consisting of nylon 6, nylon 66, nylon 11, nylon 610, nylon 12, nylon 612, a copolymerized nylon, and mixtures thereof.
22. The method of claim 14, wherein the thermoplastic block copolymer comprises a polyetherester elastomer and the flow agent comprises a fumed silica.
23. The method of claim 22, wherein the thermoplastic composition further comprises about 0.1% to about 30%, by weight, of a polyamide.
24. A method of manufacturing an article comprising the steps of (a) depositing a quantity of a thermoplastic composition on a support surface;
(b) leveling the composition to form a smooth layer of the composition on the support surface;
(c) then directing an energy beam over a predetermined target area on the support surface causing the composition to form an integral layer; and (d) repeating steps (a) to (c) to form additional layers that are integrally bonded to adjacent layers to form a three-dimensional article, wherein the thermoplastic composition comprises a thermoplastic composition comprising a thermoplastic block copolymer having a melting point of about 180°C to about 210°C, wherein the block copolymer comprises soft and hard segments, the soft segment comprising an ether or an ester.
(b) leveling the composition to form a smooth layer of the composition on the support surface;
(c) then directing an energy beam over a predetermined target area on the support surface causing the composition to form an integral layer; and (d) repeating steps (a) to (c) to form additional layers that are integrally bonded to adjacent layers to form a three-dimensional article, wherein the thermoplastic composition comprises a thermoplastic composition comprising a thermoplastic block copolymer having a melting point of about 180°C to about 210°C, wherein the block copolymer comprises soft and hard segments, the soft segment comprising an ether or an ester.
25. The method of claim 24 wherein the article is free of an infiltration step performed after step (d).
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| PCT/US2004/027350 WO2005025839A1 (en) | 2003-09-08 | 2004-08-20 | Laser sintering processes using thermoplastic compositions |
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| CA2537749C true CA2537749C (en) | 2009-12-08 |
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| US8247492B2 (en) | 2006-11-09 | 2012-08-21 | Valspar Sourcing, Inc. | Polyester powder compositions, methods and articles |
| US8501863B2 (en) * | 2007-06-28 | 2013-08-06 | James Hardie Technology Limited | Paint |
| CA2697184C (en) * | 2007-06-29 | 2015-10-27 | James Hardie Technology Limited | Multifunctional primers |
| US9572402B2 (en) * | 2007-10-23 | 2017-02-21 | Nike, Inc. | Articles and methods of manufacturing articles |
| US8373092B2 (en) * | 2008-04-09 | 2013-02-12 | The Boeing Company | Purge and sealant cap for selective laser sintering build frame |
| FR2939075B1 (en) * | 2008-12-01 | 2010-12-17 | Rhodia Operations | REALIZATION OF ARTICLE BY SELECTIVE FUSION OF POLYMER POWDER LAYERS |
| CN102325645B (en) * | 2008-12-22 | 2015-07-15 | 3D系统公司 | Polyester powder compositions, methods and articles |
| WO2010095987A1 (en) * | 2009-02-18 | 2010-08-26 | Arcam Ab | Apparatus for producing a three-dimensional object |
| FR2955330B1 (en) * | 2010-01-19 | 2012-01-20 | Arkema France | THERMOPLASTIC POWDER COMPOSITION AND THREE-DIMENSIONAL ARTICLES MADE BY SINKING SUCH A COMPOSITION |
| DE102011079518A1 (en) * | 2011-07-21 | 2013-01-24 | Evonik Degussa Gmbh | Improved component properties through optimized process control in laser sintering |
| US9193111B2 (en) * | 2012-07-02 | 2015-11-24 | United Technologies Corporation | Super polish masking of integrally bladed rotor |
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| TWI666227B (en) | 2014-01-17 | 2019-07-21 | 美商盧伯利索先進材料有限公司 | Methods of using thermoplastic polyurethanes in selective laser sintering and systems and articles thereof |
| US20170087775A1 (en) | 2014-05-29 | 2017-03-30 | The Nippon Synthetic Chemical Industry Co., Ltd. | Support material for laminate shaping, product laminate-shaped by using the same, and laminate-shaped product production method |
| ES2690840T3 (en) * | 2014-06-23 | 2018-11-22 | Covestro Deutschland Ag | Use of thermoplastic polyurethane powders |
| EP3189959B1 (en) * | 2014-09-05 | 2019-05-01 | MCPP Innovation LLC | Filament for 3d printing and method for producing crystalline soft resin molded article |
| JP6669756B2 (en) * | 2014-12-23 | 2020-03-18 | ダウ グローバル テクノロジーズ エルエルシー | Method for producing additive using molecular self-assembly material and microfiller |
| US10799952B2 (en) | 2015-06-04 | 2020-10-13 | The Regents Of The University Of California | Selective laser sintering using functional inclusions dispersed in the matrix material being created |
| TWI705981B (en) * | 2015-07-17 | 2020-10-01 | 美商盧伯利索先進材料有限公司 | Thermoplastic polyurethane compositions for solid freeform fabrication, medical device, and method of fabricating the same |
| US20170145155A1 (en) * | 2015-11-19 | 2017-05-25 | Eastman Chemical Company | Compositions for the production of objects using additive manufacturing |
| EP3374162B1 (en) | 2015-12-21 | 2024-07-10 | SHPP Global Technologies B.V. | Enhanced powder flow and melt flow of polymers for additive manufacturing applications |
| KR20170089621A (en) * | 2016-01-27 | 2017-08-04 | 이철수 | Apparatus for printing 3-dimensonal object based on laser scanner for large area using on-the-fly |
| CN105885395B (en) * | 2016-04-27 | 2018-01-16 | 华南理工大学 | A kind of composition of copolymer nylon 6 for 3D printing and preparation method thereof |
| US11318670B2 (en) | 2016-05-29 | 2022-05-03 | Stratasys Ltd. | Additive manufacturing of rubber-like materials |
| KR102192803B1 (en) * | 2016-07-20 | 2020-12-18 | 휴렛-팩커드 디벨롭먼트 컴퍼니, 엘.피. | Formation of microstructures in 3D printing |
| DE102016009770A1 (en) | 2016-08-08 | 2018-02-08 | Sören Grießbach | Process for the treatment of waste powder from additive manufacturing processes |
| EP3545025B1 (en) * | 2016-11-25 | 2022-10-12 | Covestro Deutschland AG | Method for producing an at least partially coated object |
| TWI696429B (en) * | 2017-02-21 | 2020-06-21 | 荷蘭商耐克創新有限合夥公司 | Method of reinforcing footwear component and system of reinforcing footwear component |
| EP3765547B1 (en) | 2018-03-13 | 2025-08-13 | Eastman Chemical Company | Build materials for additive manufacturing applications |
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| DE4203307C1 (en) * | 1992-02-06 | 1992-12-03 | Fa. Carl Freudenberg, 6940 Weinheim, De | |
| US5342919A (en) * | 1992-11-23 | 1994-08-30 | Dtm Corporation | Sinterable semi-crystalline powder and near-fully dense article formed therewith |
| US5527877A (en) * | 1992-11-23 | 1996-06-18 | Dtm Corporation | Sinterable semi-crystalline powder and near-fully dense article formed therewith |
| US6110411A (en) * | 1997-03-18 | 2000-08-29 | Clausen; Christian Henning | Laser sinterable thermoplastic powder |
| DE19747309B4 (en) * | 1997-10-27 | 2007-11-15 | Degussa Gmbh | Use of a polyamide 12 for selective laser sintering |
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| US20070132158A1 (en) | 2007-06-14 |
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