US10385478B2 - Process for forming a consumable filament - Google Patents
Process for forming a consumable filament Download PDFInfo
- Publication number
- US10385478B2 US10385478B2 US16/094,647 US201716094647A US10385478B2 US 10385478 B2 US10385478 B2 US 10385478B2 US 201716094647 A US201716094647 A US 201716094647A US 10385478 B2 US10385478 B2 US 10385478B2
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- filament
- propylene
- ethylene copolymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
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- 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
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
-
- 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
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/12—Melt flow index or melt flow ratio
Definitions
- the present disclosure relates to the field of chemistry. More specifically, the present disclosure relates to polymer chemistry. In particular, the present disclosure relates to a filament made from or containing a propylene ethylene copolymer, for use in an extrusion-based 3D printer.
- An extrusion-based 3D printer is used to build a 3D model from a digital representation of the 3D model in a layer-by-layer manner by extruding a flowable modeling material.
- a filament of the modeling material is extruded through an extrusion tip carried by an extrusion head, and is deposited as a sequence of roads on a substrate in an x-y plane.
- the extruded modeling material fuses to deposited modeling material, and solidifies upon a drop in temperature.
- the position of the extrusion head relative to the substrate is then incremented along a z-axis (perpendicular to the x-y plane), and the process is then repeated to form a 3D model resembling the digital representation.
- Movement of the extrusion head is performed under computer control, in accordance with build data that represents the 3D model.
- the build data is obtained by slicing the digital representation of the 3D model into multiple horizontally sliced layers. Then, for each sliced layer, the host computer generates a build path for depositing roads of modeling material to form the 3D model.
- the filament changes the material of the filament, thereby changing the final mechanical and aesthetic properties of the finished object.
- PVA polylactic acid
- ABS acrylonitrile, butadiene, styrene
- polyamides are used for filaments.
- the filament it is desirable for the filament to have a constant diameter (in some instances, 1.75 mm or 3 mm); otherwise, finely tuning the amount of material in the printed object is challenging. It is difficult to achieve a constant diameter for the filament, which is believed to depend on the characteristics of the polymer.
- the filament be printable, which, as the term “printable” is used herein, means the filament achieves appropriate adhesion with the plate and among the layers.
- the present disclosure provides a filament for use in an extrusion-based additive manufacturing system made from or containing a propylene ethylene copolymer having:
- ethylene derived units content ranging from about 3.0 wt % to about 12.0 wt %, based upon the weight of the propylene ethylene copolymer;
- MFR L Melt Flow Rate according to ISO 1133, condition L, at 230° C. and 2.16 kg load
- xylene solubles measured at 25° C. from about 3 wt % to about 30 wt %, based upon the weight of the propylene ethylene copolymer.
- the FIGURE is a front view of a sample used in print tests.
- the units of measure are mm. As shown, the printed sample was 5 mm thick.
- the present disclosure provides a filament for use in an extrusion-based additive manufacturing system made from or containing a propylene ethylene copolymer having:
- ethylene derived units content ranging from about 3.0 wt % to about 12.0 wt %; alternatively from about 3.5 wt % to about 10.0 wt %; alternatively from about 3.8 wt % to about 8.0 wt %, based upon the weight of the propylene ethylene copolymer;
- MFR L Melt Flow Rate according to ISO 1133, condition L, at 230° C. and 2.16 kg load
- xylene solubles measured at 25° C. from about 3 wt % to about 30 wt %; alternatively from about 4 wt % to about 25 wt %, based upon the weight of the propylene ethylene copolymer.
- copolymer refers to polymer formed from only two monomers: propylene and ethylene.
- the propylene/ethylene copolymer is extruded in a filament having a constant diameter.
- the diameter of the filament is about 1.75 mm or about 3 mm. In some embodiments, other diameters are used. In some embodiments, the variation from the nominal diameter is +/ ⁇ 0.05 mm, alternatively +/ ⁇ 0.03 mm. In some embodiments, the diameter of the filament is about 1.75 mm+/ ⁇ 0.05 mm or about 3 mm+/ ⁇ 0.05 mm. In some embodiments, the diameter of the filament is about 1.75 mm+/ ⁇ 0.03 mm or about 3 mm+/ ⁇ 0.03 mm.
- the polymeric materials when amorphous polymeric materials are used, the polymeric materials have little or no ordered arrangements of their polymer chains in their solid states. It is believed that this lack of arrangements reduces the effects of curling and plastic deformation in the resulting 3D model or support structure.
- the amorphous polymeric materials are acrylonitrile-butadiene-styrene (ABS) resins or polycarbonate resins.
- crystalline or semicrystalline polymer can exhibit superior mechanical properties than amorphous polymers
- crystalline or semicrystalline polymers show undesirable shrinkage effects both when the extruded road is deposited to form a portion of a layer of a 3D model and when the road is cooled.
- the shrinkage effects renders the crystalline or semicrystalline polymers unsuitable for building 3D objects in an extrusion-based additive manufacturing process.
- the present disclosure provides a semi-crystalline propylene ethylene copolymer suitable for building a 3D model.
- propylene ethylene copolymer examples include (a) RP220M sold by LyondellBasell, (b) BOREALIS RD204 CF, and (c) LyondellBasell CLYRELL RC 1908.
- the filament is made from or contains additionally additives such as antioxidants, slipping agents, process stabilizers, antiacid and nucleants.
- the filament is made from or contains additionally fillers such as talc, calcium carbonate, wollastonite, glass fibers, glass spheres and carbon derived grades.
- the filament is made from or contains additionally wood powder, metallic powder, marble powder and similar materials.
- the Xylene Soluble fraction was measured according to ISO 16152, 2005, but with the following deviations (between parentheses).
- the solution volume was 250 ml (200 ml).
- the final drying step was done under vacuum at 70° C. (100° C.).
- the content of the xylene-soluble fraction was expressed as a percentage of the original 2.5 grams and then, by difference (complementary to 100), the xylene unsoluble %.
- the peak of the S ⁇ carbon was used as internal reference at 29.9 ppm.
- the nomenclature was according to C. J. Carman, R. A. Harrington and C. E. Wilkes, “Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by 13C NMR. 3. Use of Reaction Probability Mode,” 10 Macromolecules 536 (1977).
- the samples were dissolved in 1,1,2,2-tetrachloroethane-d2 at 120° C. with a 8% wt/v concentration. Each spectrum was acquired with a 90° pulse, 15 seconds of delay between pulses and CPD to remove 1H-13C coupling. 512 transients were stored in 32K data points using a spectral window of 9000 Hz.
- E ⁇ ⁇ % ⁇ ⁇ wt . 100 * E ⁇ ⁇ % ⁇ ⁇ mol * M ⁇ ⁇ W E E ⁇ ⁇ % ⁇ ⁇ mol * M ⁇ ⁇ W E + P ⁇ ⁇ % ⁇ ⁇ mol * M ⁇ ⁇ W P
- the product of reactivity ratio r 1 r 2 was calculated according to Carman (C. J. Carman, R. A. Harrington and C. E. Wilkes, 10 Macromolecules 536 (1977)) as:
- the tacticity of Propylene sequences was calculated as mm content from the ratio of the PPP mmT ⁇ (28.90-29.65 ppm) and the whole Tpp (29.80-28.37 ppm)
- the melt flow rate MFR of the polymer was determined according to ISO 1133 (230° C., 2.16 Kg).
- Propylene homopolymer having a MFR of 6.5 and a fraction soluble in xylene at 25° C. of ⁇ 4 wt %, based upon the weight of the propylene homopolymer.
- Propylene ethylene copolymer sold under the tradename MOPLEN RP220M being a random propylene ethylene copolymer having an ethylene content of 4 wt %, based upon the weight of the random propylene ethylene copolymer, an MFR of 7, and a fraction soluble in xylene at 25° C. of 7%, based upon the weight of the random propylene ethylene copolymer.
- Polymers PP1 and PP3 were extruded to form a filament having 1.75 mm of diameter. To extrude PP1, 10 wt % of talc, based upon the total weight of the composition, was added.
- the printer was a 3D Rostock delta printer.
- the printer conditions were the followings:
- the printed sample is shown in FIG. 1 .
- 5 printer tests were carried out. The print was stopped when one side of the object was detached from the plane, thereby preventing the print of the object. The results are reported in Table 1.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
Description
PPP=100T ββ S PPE=100T βδ S EPE=100T δδ S
PEP=100S ββ S PEE=100S βδ S EEE=100(0.25S γδ+0.5S δδ)/S
S=T ββ +T βδ +T δδ +S ββ +S βδ+0.25S γδ+0.5S δδ
The molar percentage of ethylene content was evaluated using the following equation:
E % mol=100*[PEP+PEE+EEE]
The weight percentage of ethylene content was evaluated using the following equation:
Filament diameter | mm | 1.75 ± 0.03 | ||
Nozzle diameter | mm | 0.4 | ||
Temperature first layer | ° C. | 245 | ||
Temperature other layers | ° C. | 245 | ||
1 | ||||
Layer high | mm | 0.2 | ||
Temperature plate | ° C. | 100 | ||
Support material to | vinylic glue | |||
adhere on the plate | ||||
Plate material. | | |||
Infill | ||||
100% | ||||
printer speed | mm/min | 3600 | ||
Speed first layer | 60% | |||
Speed |
100% | |||
Speed infill | mm/min | 4.000 | ||
TABLE 1 | |||
height before detach | |||
(Z) (mm) (average | |||
material | measure) | ||
PP1* | 0.8 | ||
PP2* | 1.2 | ||
PP3 | full (5 mm) | ||
*comparative |
Claims (11)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16166589 | 2016-04-22 | ||
EP16166589.8 | 2016-04-22 | ||
EP16166589 | 2016-04-22 | ||
PCT/EP2017/056495 WO2017182209A1 (en) | 2016-04-22 | 2017-03-20 | Propylene based filament for 3d printer |
Publications (2)
Publication Number | Publication Date |
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US20190112732A1 US20190112732A1 (en) | 2019-04-18 |
US10385478B2 true US10385478B2 (en) | 2019-08-20 |
Family
ID=55808987
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US16/094,647 Active US10385478B2 (en) | 2016-04-22 | 2017-03-20 | Process for forming a consumable filament |
Country Status (7)
Country | Link |
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US (1) | US10385478B2 (en) |
EP (1) | EP3445793B1 (en) |
JP (1) | JP6626991B2 (en) |
KR (1) | KR102009615B1 (en) |
CN (1) | CN109071723B (en) |
BR (1) | BR112018070035B1 (en) |
WO (1) | WO2017182209A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11964437B1 (en) | 2022-03-29 | 2024-04-23 | Mark Lamoncha | Additive manufacturing by solvent melding of build material |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2020106172A1 (en) * | 2018-11-21 | 2020-05-28 | Public Joint Stock Company "Sibur Holding" | Transparent, tasily flow able high-impact polypropylene composition |
EP4038136A1 (en) * | 2019-10-01 | 2022-08-10 | Basell Polyolefine GmbH | Propylene based filament for 3d printer |
JP7351493B2 (en) * | 2019-10-07 | 2023-09-27 | バーゼル・ポリオレフィン・ゲーエムベーハー | Polypropylene for extrusion additive manufacturing |
EP4351866A1 (en) * | 2021-06-10 | 2024-04-17 | W. R. Grace & Co.-Conn | Polypropylene random copolymer for three-dimensional printing and filament made therefrom |
DE102022001070A1 (en) | 2022-03-29 | 2023-10-05 | Technische Universität Bergakademie Freiberg, Körperschaft des öffentlichen Rechts | Thermoplastic binder system and process for the 3D production of ceramic components, metallic components or components based on metal-ceramic composite materials or material composites |
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EP1270628A1 (en) | 2001-06-27 | 2003-01-02 | Borealis Technology Oy | Propylene random copolymer and process for the production thereof |
EP1484345A1 (en) | 2003-06-06 | 2004-12-08 | Borealis Technology Oy | Process for the production of polypropylene using a Ziegler-Natta catalyst |
US20160297103A1 (en) | 2013-11-04 | 2016-10-13 | Fine Chemical Co., Ltd. | Polymer composition for three-dimensional printer |
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2017
- 2017-03-20 US US16/094,647 patent/US10385478B2/en active Active
- 2017-03-20 BR BR112018070035-5A patent/BR112018070035B1/en active IP Right Grant
- 2017-03-20 KR KR1020187032402A patent/KR102009615B1/en active IP Right Grant
- 2017-03-20 CN CN201780023163.3A patent/CN109071723B/en active Active
- 2017-03-20 EP EP17711219.0A patent/EP3445793B1/en active Active
- 2017-03-20 JP JP2018552801A patent/JP6626991B2/en active Active
- 2017-03-20 WO PCT/EP2017/056495 patent/WO2017182209A1/en active Application Filing
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JPH1161556A (en) | 1997-08-12 | 1999-03-05 | Mitsui Chem Inc | Monofilament |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11964437B1 (en) | 2022-03-29 | 2024-04-23 | Mark Lamoncha | Additive manufacturing by solvent melding of build material |
Also Published As
Publication number | Publication date |
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WO2017182209A1 (en) | 2017-10-26 |
EP3445793B1 (en) | 2020-01-01 |
US20190112732A1 (en) | 2019-04-18 |
BR112018070035A2 (en) | 2019-02-05 |
CN109071723A (en) | 2018-12-21 |
KR102009615B1 (en) | 2019-08-09 |
JP2019513913A (en) | 2019-05-30 |
EP3445793A1 (en) | 2019-02-27 |
BR112018070035B1 (en) | 2022-08-09 |
CN109071723B (en) | 2020-12-29 |
JP6626991B2 (en) | 2019-12-25 |
KR20180127500A (en) | 2018-11-28 |
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