WO2007133912A2 - Use of fluoropolymers in laser sintering - Google Patents
Use of fluoropolymers in laser sintering Download PDFInfo
- Publication number
- WO2007133912A2 WO2007133912A2 PCT/US2007/067454 US2007067454W WO2007133912A2 WO 2007133912 A2 WO2007133912 A2 WO 2007133912A2 US 2007067454 W US2007067454 W US 2007067454W WO 2007133912 A2 WO2007133912 A2 WO 2007133912A2
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- WO
- WIPO (PCT)
- Prior art keywords
- powder
- fluoropolymer
- polymer
- polyvinylidene fluoride
- copolymers
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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
- 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
- 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
- B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
- B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
- B29K2027/18—PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
Definitions
- the invention relates to the use of fluoropolymers, and in particular polyvinylidene fluoride and its copolymers, or polychlorotrifluoroethylene and its copolymers, in a laser sintering process.
- Fluoropolymer powder provides many advantages over polymers currently used in that it intrinsically possesses flame- retardancy, as well as excellent chemical resistance and thermal resistance.
- the technology of sintering polymer powders under a laser beam is used for the manufacture of objects in three dimensions, such as prototypes and models.
- the selective laser sintering process is described in US Patent Number 4,863,568.
- a fine layer of polymer powder is deposited on a horizontal plate held in a chamber heated to a temperature lying between the crystallization temperature Tc and the melting point Tm of the polyamide powder.
- the laser sinters powder particles at various points of the powder layer according to a geometry corresponding to the object, for example using a computer which has the shape of the object in its memory and which reconstructs it in the form of slices.
- the horizontal plate is subsequently lowered by a value corresponding to the thickness of a layer of powder (for example, between 0.05 and 2 mm and generally of the order of 0.1 mm) and then a new layer of powder is deposited and the laser sinters powder particles according to a geometry corresponding to this new slice of the object.
- the procedure is repeated until the complete object has been manufactured.
- a block of powder consisting of polymer powder and melt is obtained within which the object is present.
- the parts that have not been sintered have thus remained in the powder state.
- the combination is gently cooled and the object solidifies as soon as its temperature falls below the crystallization temperature Tc. After cooling is complete, the object is separated from the powder, which can be recycled and used in another sintering operation.
- the powder it is recommended for the powder to have a difference Tm - Tc that is as large as possible in order to avoid deformation (or curling) phenomena during manufacture. This is because, at time to immediately after the action of the laser beam, the temperature of the sample is greater than the crystallization temperature (Tc) of the powder but the introduction of a new colder powder layer causes the temperature of the component to rapidly fall below Tc and results in deformations.
- Tc crystallization temperature
- an enthalpy of fusion which is as high as possible is required in order to obtain good geometrical definition of the components manufactured. This is because, if the enthalpy of fusion is too low, the energy supplied by the laser is sufficient to cake, by thermal conduction, the powder particles close to the walls being constructed, and thus the geometrical precision of the component is no longer satisfactory.
- US 6,245,281 discloses the use of polyamide-12 (PA 12) powders in the technology of the sintering of powders under a laser beam. These powders are such that their Tm is between 185 and 189°C, their Tc is between 138 and 143 0 C and their ⁇ Hf has a value of 112 ⁇ 17 J/g. These powders are manufactured according to the process disclosed in Patent US 4 334 056.
- US-2005-0197446 Describes a polyamide 12 designed specifically for a laser sintering operation.
- US20050003189 describes the use of a blend of a thermoplastic powder
- 3D printing uses an inkjet printer rather than a laser to produce prototype articles.
- fluoropolymers and copolymers can be used in a laser and infra-red (IR) sintering process, providing material properties to the formed article that are much better than those of currently used materials, such as flame retardency, chemical resistance and thermal resistance.
- the invention relates to a process for forming a three-dimensional object comprising the steps of: a) applying a layer of a fluoropolymer or co-polymer powder at a target surface; b) directing energy at selected locations of said polymer powder layer to sinter said powder at those selected points; c) repeating steps a) and b) over multiple layers to form an object; d) removing the unsintered powder from said object.
- the invention relates to the use of fluoropolymer and copolymers in a laser sintering process or other means of achieving a layer-by-layer construction, such as by IR sintering.
- fluoromonomer or the expression “fluorinated monomer” means a polymerizable alkene which contains at least one fluorine atom, fluoroalkyl group, or fluoroalkoxy group attached to the double bond of the alkene that undergoes polymerization.
- fluoropolymer means a polymer formed by the polymerization of at least one fluoromonomer, and it is inclusive of homopolymers, copolymers, terpolymers and higher polymers which are thermoplastic in their nature, meaning they are capable of being formed into useful pieces by flowing upon the application of heat, such as is done in molding and extrusion processes.
- the thermoplastic polymers typically exhibit a crystalline melting point.
- fluoropolymers for a laser sintering application include polymer and copolymers of polyvinylidene fluoride or polychlorotrifluoroethylene
- PVDF polyvinylidene fluoride
- copolymers and terpolymers include those containing at least 50 mole percent of vinylidene fluoride copolymerized with at least one comonomer selected from the group consisting of tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, hexafluoropropene, vinyl fluoride, pentafluoropropene, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether and any other monomer that would readily copolymerize with vinylidene fluoride.
- copolymers composed of from at least about 70 and up to 99 mole percent vinylidene fluoride, and correspondingly from 1 to 30 percent tetrafluoroethylene; and about 70 to 99 percent vinylidene fluoride and 1 to 30 percent hexafluoropropene (as described in U.S. Patent No. 3,178,399); and about 70 to 99 mole percent vinylidene fluoride and 1 to 30 mole percent trifluoroethylene.
- Terpolymers of vinylidene fluoride, hexafluoropropene and tetrafluoroethylene such as described in U.S. Patent No.
- 2,968,649 and terpolymers of vinylidene fluoride, trifluoroethylene and tetrafluoroethylene are also representatives of the class of vinylidene fluoride copolymers which can be used in the process embodied herein.
- a preferred PVDF copolymer for laser sintering would have a reasonable amount of crystalinity to present a distinct melt point, yet would have a small amount of non-crystallinity to reduce the brittleness of a formed article.
- An example of such a copolymer would be a random copolymer composed of 80-97 weight percent of vinylidene fluoride monomer units and 3-20 parts by weight of hexafluoropropane monomer units.
- the term "polychlorotrifluoroethylene”, as used herein includes both normally solid, high molecular weight homopolymers, copolymers and terpolymers.
- Such copolymers and terpolymers include those containing at least 50 mole percent of chlorotrifluoroethylene copolymerized with at least one comonomer selected from the group consisting of tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, hexafluoropropene, vinyl fluoride, pentafluoropropene, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether and any other monomer that would readily copolymerize with vinylidene fluoride.
- comonomer selected from the group consisting of tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, hexafluoropropene, vinyl fluoride, pentafluoropropene, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether and any other monomer that would readily copolymerize with vinylidene fluoride.
- the fluoropolymers useful for laser sintering could also include a blend of a fluoropolymers or copolymer with an acrylic or methacrylic polymer.
- the fluoropolymer powder may be blended with small amounts up to 10% by weight, based on the amount of polymer, of a reinforcing powder whose melting point is considerably higher than that of the polymer, or a glass powder. This blend forms a polyvinylidene fluoride laser sinterable composition.
- Fluoropolymer powders of the present invention can be directly formed into powders from emulsion or suspension polymerization through the use of spray drying, freeze-drying, and other methods of powder formation.
- the powder average particle size is less than 100 microns, typically in the range of 40 to 80 microns.
- Particle size can be adjusted and optimized for the laser sintering process by known means, such as by cryogenic grinding and by sieving and/or classifying.
- the polyvinylidene fluoride polymers and copolymers of the invention show melting and recrystallization characteristics with minimum overlap. They can be used in place of currently used powders in the laser sintering process.
- a homopolymer or copolymer of PVDF can be selected to match the physical properties desired in the laser sintering operation, and in the formed article.
- PVDF powders have intrinsic flame retardant properties, and PVDF show higher chemical and thermal resistance than polyamide. PVDF powders are far more flame retardant than polyamides any other materials currently used in a laser sintering operation.
- Sintered parts made of polyvinylidene fluoride powder can be used in aggressive chemical and thermal environments, and also whenever flame retardant properties are required. Additionally, parts made of VF 2 -VF 3 copolymers (80/20 to 60/40) can show piezoelectric properties.
- a three-dimensional object is formed by a) applying a layer of a fluoropolymer or co-polymer powder at a target surface, then b) directing energy at selected locations of said polymer powder layer to sinter said powder at those selected points, and then repeating steps a) and b) over multiple layers to form an object.
- the unsintered powder form said object.
Abstract
The invention relates to the use of a fluoropolymer and its copolymers in a laser sintering process. Fluoropolymer powder provides many advantages over polymers currently used in that it intrinsically possesses flame-retardancy, as well as excellent chemical resistance and thermal resistance.
Description
USE OF FLUOROPOLYMERS IN LASER SINTERING
Field of the Invention
The invention relates to the use of fluoropolymers, and in particular polyvinylidene fluoride and its copolymers, or polychlorotrifluoroethylene and its copolymers, in a laser sintering process. Fluoropolymer powder provides many advantages over polymers currently used in that it intrinsically possesses flame- retardancy, as well as excellent chemical resistance and thermal resistance.
Background of the Invention
The technology of sintering polymer powders under a laser beam is used for the manufacture of objects in three dimensions, such as prototypes and models. The selective laser sintering process is described in US Patent Number 4,863,568. In the process, a fine layer of polymer powder is deposited on a horizontal plate held in a chamber heated to a temperature lying between the crystallization temperature Tc and the melting point Tm of the polyamide powder. The laser sinters powder particles at various points of the powder layer according to a geometry corresponding to the object, for example using a computer which has the shape of the object in its memory and which reconstructs it in the form of slices. The horizontal plate is subsequently lowered by a value corresponding to the thickness of a layer of powder (for example, between 0.05 and 2 mm and generally of the order of 0.1 mm) and then a new layer of powder is deposited and the laser sinters powder particles according to a geometry corresponding to this new slice of the object. The procedure is repeated until the complete object has been manufactured. A block of powder consisting of polymer powder and melt is obtained within which the object is present. The parts that have not been sintered have thus remained in the powder state. Subsequently, the combination is gently cooled and the object solidifies as soon as its temperature falls below the crystallization temperature Tc. After cooling is complete, the object is separated from the powder, which can be recycled and used in another sintering operation.
It is recommended for the powder to have a difference Tm - Tc that is as large as possible in order to avoid deformation (or curling) phenomena during manufacture. This is because, at time to immediately after the action of the laser beam, the
temperature of the sample is greater than the crystallization temperature (Tc) of the powder but the introduction of a new colder powder layer causes the temperature of the component to rapidly fall below Tc and results in deformations. The greater the difference between Tm and Tc, the smaller the amount of shrinkage upon solidification.
Furthermore, an enthalpy of fusion (ΔHf) which is as high as possible is required in order to obtain good geometrical definition of the components manufactured. This is because, if the enthalpy of fusion is too low, the energy supplied by the laser is sufficient to cake, by thermal conduction, the powder particles close to the walls being constructed, and thus the geometrical precision of the component is no longer satisfactory.
US 6,245,281 discloses the use of polyamide-12 (PA 12) powders in the technology of the sintering of powders under a laser beam. These powders are such that their Tm is between 185 and 189°C, their Tc is between 138 and 1430C and their ΔHf has a value of 112 ± 17 J/g. These powders are manufactured according to the process disclosed in Patent US 4 334 056.
Many different materials have been used in the laser sintering process: US 6,245 ,281 describes polyamide-11 and polyamide-12 as preferred powders, with other useful polymers being nylons, polyacetals, polypropylene, polyethylene, ionomers, polycarbonates and polystyrene. US 5,304,329 mentions semi-crystalline polymers useful in a selective laser sintering machine to also include polybutylene terephthlate.
US-2005-0197446: Describes a polyamide 12 designed specifically for a laser sintering operation. US20050003189 describes the use of a blend of a thermoplastic powder
(included polyvinylidene fluoride) with an adhesive particulate material for 3D printing. 3D printing uses an inkjet printer rather than a laser to produce prototype articles.
It has now surprisingly been found that fluoropolymers and copolymers can be used in a laser and infra-red (IR) sintering process, providing material properties to the formed article that are much better than those of currently used materials, such as flame retardency, chemical resistance and thermal resistance.
Summary of the Invention
The invention relates to a process for forming a three-dimensional object comprising the steps of: a) applying a layer of a fluoropolymer or co-polymer powder at a target surface; b) directing energy at selected locations of said polymer powder layer to sinter said powder at those selected points; c) repeating steps a) and b) over multiple layers to form an object; d) removing the unsintered powder from said object.
Detailed description of the Invention
The invention relates to the use of fluoropolymer and copolymers in a laser sintering process or other means of achieving a layer-by-layer construction, such as by IR sintering. The term "fluoromonomer" or the expression "fluorinated monomer" means a polymerizable alkene which contains at least one fluorine atom, fluoroalkyl group, or fluoroalkoxy group attached to the double bond of the alkene that undergoes polymerization. The term "fluoropolymer" means a polymer formed by the polymerization of at least one fluoromonomer, and it is inclusive of homopolymers, copolymers, terpolymers and higher polymers which are thermoplastic in their nature, meaning they are capable of being formed into useful pieces by flowing upon the application of heat, such as is done in molding and extrusion processes. The thermoplastic polymers typically exhibit a crystalline melting point. Especially preferred fluoropolymers for a laser sintering application include polymer and copolymers of polyvinylidene fluoride or polychlorotrifluoroethylene
The term "polyvinylidene fluoride" (PVDF) as used herein includes both normally solid, high molecular weight homopolymers, copolymers and terpolymers. Such copolymers and terpolymers include those containing at least 50 mole percent of vinylidene fluoride copolymerized with at least one comonomer selected from the group consisting of tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, hexafluoropropene, vinyl fluoride, pentafluoropropene, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether and any other monomer that would readily copolymerize with vinylidene fluoride. Particularly preferred are copolymers composed of from at least about 70 and up to 99 mole percent vinylidene fluoride, and correspondingly
from 1 to 30 percent tetrafluoroethylene; and about 70 to 99 percent vinylidene fluoride and 1 to 30 percent hexafluoropropene (as described in U.S. Patent No. 3,178,399); and about 70 to 99 mole percent vinylidene fluoride and 1 to 30 mole percent trifluoroethylene. Terpolymers of vinylidene fluoride, hexafluoropropene and tetrafluoroethylene such as described in U.S. Patent No. 2,968,649 and terpolymers of vinylidene fluoride, trifluoroethylene and tetrafluoroethylene are also representatives of the class of vinylidene fluoride copolymers which can be used in the process embodied herein.
A preferred PVDF copolymer for laser sintering would have a reasonable amount of crystalinity to present a distinct melt point, yet would have a small amount of non-crystallinity to reduce the brittleness of a formed article. An example of such a copolymer would be a random copolymer composed of 80-97 weight percent of vinylidene fluoride monomer units and 3-20 parts by weight of hexafluoropropane monomer units. The term "polychlorotrifluoroethylene", as used herein includes both normally solid, high molecular weight homopolymers, copolymers and terpolymers. Such copolymers and terpolymers include those containing at least 50 mole percent of chlorotrifluoroethylene copolymerized with at least one comonomer selected from the group consisting of tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, hexafluoropropene, vinyl fluoride, pentafluoropropene, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether and any other monomer that would readily copolymerize with vinylidene fluoride.
The fluoropolymers useful for laser sintering could also include a blend of a fluoropolymers or copolymer with an acrylic or methacrylic polymer. The fluoropolymer powder may be blended with small amounts up to 10% by weight, based on the amount of polymer, of a reinforcing powder whose melting point is considerably higher than that of the polymer, or a glass powder. This blend forms a polyvinylidene fluoride laser sinterable composition.
Fluoropolymer powders of the present invention can be directly formed into powders from emulsion or suspension polymerization through the use of spray drying, freeze-drying, and other methods of powder formation. The powder average particle size is less than 100 microns, typically in the range of 40 to 80 microns. Particle size can be adjusted and optimized for the laser sintering process by known means, such as by cryogenic grinding and by sieving and/or classifying.
The polyvinylidene fluoride polymers and copolymers of the invention show melting and recrystallization characteristics with minimum overlap. They can be used in place of currently used powders in the laser sintering process. A homopolymer or copolymer of PVDF can be selected to match the physical properties desired in the laser sintering operation, and in the formed article.
The use of a fluoropolymer or copolymer in a laser sintering operation has several advantages over currently used materials, such as polyamides. PVDF powders have intrinsic flame retardant properties, and PVDF show higher chemical and thermal resistance than polyamide. PVDF powders are far more flame retardant than polyamides any other materials currently used in a laser sintering operation.
Sintered parts made of polyvinylidene fluoride powder can be used in aggressive chemical and thermal environments, and also whenever flame retardant properties are required. Additionally, parts made of VF2 -VF3 copolymers (80/20 to 60/40) can show piezoelectric properties.
Example
A three-dimensional object is formed by a) applying a layer of a fluoropolymer or co-polymer powder at a target surface, then b) directing energy at selected locations of said polymer powder layer to sinter said powder at those selected points, and then repeating steps a) and b) over multiple layers to form an object. The unsintered powder form said object.
Claims
1. A process for forming a three-dimensional object comprising the steps of: a) applying a layer of a fluoropolymer, co-polymer or terpolymer powder at a target surface; b) directing energy at selected locations of said polymer powder layer to sinter said powder at those selected points; c) repeating steps a) and b) over multiple layers to form an object; d) removing the unsintered powder from said object.
2. The process of claim 1, wherein said fluoropolymer or copolymer powder comprises a polyvinylidene fluoride or polychlorotrifluoroethylene.
3. The process of claim 1 , wherein said fluoropolymer or copolymer powder further comprises up to 10 percent of additives.
4. The process of claim 3, wherein said additive comprises small glass beads or glass powder.
5. The process of claim 2, wherein said polyvinylidene fluoride polymer comprises a copolymer having 80-97 weight percent of vinylidene fluoride monomer units and 3-20 weight percent of hexafluoropropane monomer units
6. The process of claim 1 , wherein said fluoropolymer polymer powder has an average particle size in the range from 40 to 80 microns.
7. The process of claim 2, wherein said polyvinylidene fluoride polymer is a VF2 -VF3 copolymers at a ratio in the range of 80/20 to 60/40.
8. The process of claim 7, wherein said object formed by the process has piezoelectric properties.
9. The process of claim 1, wherein said energy source is a laser.
10. The process of claim 1, wherein said energy source is an infra red energy source.
11. An object formed by a laser sintering process comprising at least 90 percent by weight of a fluoropolymer.
12. The obj ect of claim 11 , wherein said fluoropolymer or copolymer powder comprises a polyvinylidene fluoride or polychlorotrifluoroethylene.
13. The object of claim 12 wherein said object comprises as the polyvinylidene fluoride polymer a VF2 -VF3 copolymers at a ratio in the range of 80/20 to 60/40, and wherein said object has piezoelectric properties.
14. The object of claim 12, wherein said object is flame retardant, and has excellent chemical and thermal resistance.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79938606P | 2006-05-10 | 2006-05-10 | |
| US60/799,386 | 2006-05-10 |
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| Publication Number | Publication Date |
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| WO2007133912A2 true WO2007133912A2 (en) | 2007-11-22 |
| WO2007133912A3 WO2007133912A3 (en) | 2008-07-17 |
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| PCT/US2007/067454 WO2007133912A2 (en) | 2006-05-10 | 2007-04-26 | Use of fluoropolymers in laser sintering |
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| WO2018149757A1 (en) * | 2017-02-16 | 2018-08-23 | Solvay Specialty Polymers Italy S.P.A. | Perfluorinated thermoplastic elastomer |
| WO2018149758A1 (en) * | 2017-02-16 | 2018-08-23 | Solvay Specialty Polymers Italy S.P.A. | Method for manufacturing a three-dimensional object |
| WO2019016739A2 (en) | 2017-07-19 | 2019-01-24 | 3M Innovative Properties Company | Additive processing of fluoropolymers |
| WO2019016738A3 (en) * | 2017-07-19 | 2019-03-21 | 3M Innovative Properties Company | Method of making polymer articles and polymer composites by additive processing and polymer and composite articles |
| US20190127500A1 (en) * | 2016-04-01 | 2019-05-02 | Arkema Inc. | 3-d printed fluoropolymer structures |
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