CN110091499A - A kind of 3D printing method based on polytetrafluoroethylene (PTFE) - Google Patents
A kind of 3D printing method based on polytetrafluoroethylene (PTFE) Download PDFInfo
- Publication number
- CN110091499A CN110091499A CN201910230169.9A CN201910230169A CN110091499A CN 110091499 A CN110091499 A CN 110091499A CN 201910230169 A CN201910230169 A CN 201910230169A CN 110091499 A CN110091499 A CN 110091499A
- Authority
- CN
- China
- Prior art keywords
- ptfe
- polytetrafluoroethylene
- carbon dioxide
- extruder
- supercritical carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 105
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 105
- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000010146 3D printing Methods 0.000 title claims abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 40
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 40
- 230000000694 effects Effects 0.000 claims abstract description 15
- 238000001125 extrusion Methods 0.000 claims abstract description 10
- 230000009477 glass transition Effects 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 238000007789 sealing Methods 0.000 claims abstract description 7
- 230000008961 swelling Effects 0.000 claims abstract description 7
- 230000008859 change Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims 1
- 239000011800 void material Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 6
- 230000002522 swelling effect Effects 0.000 abstract 1
- 238000003856 thermoforming Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 206010000269 abscess Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- 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
-
- 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
- B29C64/30—Auxiliary operations or equipment
- B29C64/307—Handling of material to be used in additive manufacturing
-
- 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
- B33Y10/00—Processes of additive manufacturing
-
- 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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Optics & Photonics (AREA)
Abstract
The 3D printing method based on polytetrafluoroethylene (PTFE) that the invention discloses a kind of, it is to mix the polytetrafluoroethylene (PTFE) of molten condition in extruder with supercritical carbon dioxide gas, carbon dioxide is absorbed by polytetrafluoroethylene polymer strand, reduce molecular entanglement, increase free volume, carbon dioxide serves as intermolecular lubricant simultaneously, both effects reduce the viscosity of molten mass, the glass transition temperature for the polytetrafluoroethylene (PTFE) being swollen by supercritical carbon dioxide reduces 40~60 DEG C, the pressure rise in extruder under the action of its swelling, also container both ends is made to form pressure difference while reaching self sealing effect, realize the continuous extrusion of polytetrafluoroethylene (PTFE), complete 3D printing；The method of the present invention has swelling action to polymer using supercritical carbon dioxide, and the glass transition temperature of polymer can be greatly lowered, and reduces the harm decomposed during PTFE thermoforming, realizes the 3D printing molding of PTFE.
Description
Technical field
The invention belongs to 3D printing and field shaping techniques, and in particular to one kind is molding based on polytetrafluoroethylene (PTFE) 3D printing
Method.
Background technique
3D printing forming technique is one kind of quick forming fabri-cation and increasing material manufacturing, is connection under the control of the computer or solid
Change material to generate the process of three-dimension object, be generally fused together using fluid molecule or powder particle and successively add up final
Construct object.Currently, the molding technology of 3D printing generally has: fusion sediment method, such as using thermoplastic, eutectic system gold
Belong to material, shaping speed is slow, and the mobility of material molten will be got well；Direct metal sintering process, such as using titanium alloy powder,
Powder of stainless steel, aluminium powder etc. are directly sintered, although metallic article can directly be made, because the reason of being sintered technique itself leads
Cause article surface coarse；Photocuring processes, using the light source direct irradiation of light-hardening resin specific wavelength want molding path come,
Its is with high costs, and workable material category is few, can only use photosensitive resin, and material needs are protected from light protection；Jet printing method, makes
Solidify after being sprayed with materials such as gypsum to pallet, finished product product intensity is lower.
Polytetrafluoroethylene (PTFE) has the characteristics that antiacid alkali resistant, resists various organic solvents, is practically insoluble in all solvents, together
When, polytetrafluoroethylene (PTFE) has the characteristics that resistant to high temperature, its coefficient of friction is extremely low.Therefore it is commonly used in container and pipe-line system
For reactivity and eroding chemical.Though polytetrafluoroethylene (PTFE) is thermoplastic, its melt viscosity is big, shear-sensitive, big
Shrinkage creep properties and low friction factor, it is difficult to processed with the forming method of ordinary thermoplastics；And by poly- four
Technology of the vinyl fluoride for 3D printing raw material is fewer, and rarely has research.
Summary of the invention
In view of the shortcomings of the prior art, the present invention provides it is a kind of it is stable, formed precision is higher is based on polytetrafluoroethyl-ne
The molding method of alkene 3D printing, this method are to mix the polytetrafluoroethylene (PTFE) of molten condition and supercritical carbon dioxide in extruder
It closes, so that the mass percent of supercritical carbon dioxide is 4~10% in polytetrafluoroethylene (PTFE), carbon dioxide is gathered by polytetrafluoroethylene (PTFE)
Adduct molecule chain absorbs, and reduces molecular entanglement, increases free volume, while carbon dioxide serves as intermolecular lubricant, this
Two kinds of effects reduce the viscosity of molten mass, and the glass transition temperature for the polytetrafluoroethylene (PTFE) being swollen by supercritical carbon dioxide reduces
40~60 DEG C, under the action of its swelling pressure rise in extruder, also makes container two while reaching self sealing effect
End forms pressure difference, realizes the continuous extrusion of polytetrafluoroethylene (PTFE), completes 3D printing.
Supercritical carbon dioxide gas volumetric concentration > 99.9%.
The heating temperature of the extruder is 230~260 DEG C.
The incorporation time of the supercritical carbon dioxide gas and polytetrafluoroethylene (PTFE) in extruder is greater than 2min.
The beneficial effects of the present invention are:
(1) problem that PTFE is excessive applied to 3D printer Shi Yinqi melt viscosity and extrusion is difficult is improved；
(2) supercritical carbon dioxide auxiliary squeezes out PTFE and forms the extrusion temperature and extrusion pressure reduced, avoids traditional heat
Process medium temperature spends the problem of height causes PTFE to decompose；
(3) under supercritical carbon dioxide effect auxiliary, there are abscess and crazings in molding PTFE architecture, so that
The toughness and shock resistance of PTFE greatly improves.
Specific embodiment
The present invention is described in detail With reference to embodiment, but the scope of the present invention be not limited to it is described
Content.
Embodiment 1: the 3D printing method based on polytetrafluoroethylene (PTFE) be by the polytetrafluoroethylene (PTFE) of molten condition with it is overcritical
Carbon dioxide gas (99.92%) mixes 5min in extruder so that in polytetrafluoroethylene (PTFE) supercritical carbon dioxide quality hundred
Divide than being 5%, carbon dioxide is absorbed by polytetrafluoroethylene polymer strand, reduces molecular entanglement, increases free volume, together
When carbon dioxide serve as intermolecular lubricant, both effect reduce molten masses viscosity, it is molten by supercritical carbon dioxide
The glass transition temperature of swollen polytetrafluoroethylene (PTFE) reduces, and heats temperature using Repetier-Host software set PTFE extruder
Degree is 230 DEG C, and pressure rise in extruder, also makes container both ends under the action of its swelling while reaching self sealing effect
Pressure difference is formed, realizes the continuous extrusion of polytetrafluoroethylene (PTFE), a rectangular body Model is imported and is calculated, moulded dimension is 10 × 5
× 1cm, setting compactedness be 50%, it is contemplated that the print time be 43 points 26 seconds, complete 3D printing.
Embodiment 2: the 3D printing method based on polytetrafluoroethylene (PTFE) be by the polytetrafluoroethylene (PTFE) of molten condition with it is overcritical
Carbon dioxide gas (99.95%) mixes 6min in extruder so that in polytetrafluoroethylene (PTFE) supercritical carbon dioxide quality hundred
Divide than being 8%, carbon dioxide is absorbed by polytetrafluoroethylene polymer strand, reduces molecular entanglement, increases free volume, together
When carbon dioxide serve as intermolecular lubricant, both effect reduce molten masses viscosity, it is molten by supercritical carbon dioxide
The glass transition temperature of swollen polytetrafluoroethylene (PTFE) reduces, and heats temperature using Repetier-Host software set PTFE extruder
Degree is 250 DEG C, and pressure rise in extruder, also makes container both ends under the action of its swelling while reaching self sealing effect
Pressure difference is formed, realizes the continuous extrusion of polytetrafluoroethylene (PTFE), a rectangular body Model is imported and is calculated, moulded dimension is 10 × 5
× 1cm, setting compactedness be 50%, it is contemplated that the print time be 43 points 26 seconds, complete 3D printing.
Embodiment 3: the 3D printing method based on polytetrafluoroethylene (PTFE) be by the polytetrafluoroethylene (PTFE) of molten condition with it is overcritical
Carbon dioxide gas (99.94%) mixes 8min in extruder so that in polytetrafluoroethylene (PTFE) supercritical carbon dioxide quality hundred
Divide than being 10%, carbon dioxide is absorbed by polytetrafluoroethylene polymer strand, reduces molecular entanglement, increases free volume, together
When carbon dioxide serve as intermolecular lubricant, both effect reduce molten masses viscosity, it is molten by supercritical carbon dioxide
The glass transition temperature of swollen polytetrafluoroethylene (PTFE) reduces, and heats temperature using Repetier-Host software set PTFE extruder
Degree is 260 DEG C, and pressure rise in extruder, also makes container both ends under the action of its swelling while reaching self sealing effect
Pressure difference is formed, realizes the continuous extrusion of polytetrafluoroethylene (PTFE), a rectangular body Model is imported and is calculated, moulded dimension is 10 × 5
× 1cm, setting compactedness be 50%, it is contemplated that the print time be 43 points 26 seconds, complete 3D printing.
Embodiment 4: the 3D printing method based on polytetrafluoroethylene (PTFE) be by the polytetrafluoroethylene (PTFE) of molten condition with it is overcritical
Carbon dioxide gas (99.99%) mixes 7min in extruder so that in polytetrafluoroethylene (PTFE) supercritical carbon dioxide quality hundred
Divide than being 10%, carbon dioxide is absorbed by polytetrafluoroethylene polymer strand, reduces molecular entanglement, increases free volume, together
When carbon dioxide serve as intermolecular lubricant, both effect reduce molten masses viscosity, it is molten by supercritical carbon dioxide
The glass transition temperature of swollen polytetrafluoroethylene (PTFE) reduces, and heats temperature using Repetier-Host software set PTFE extruder
Degree is 240 DEG C, and pressure rise in extruder, also makes container both ends under the action of its swelling while reaching self sealing effect
Pressure difference is formed, realizes the continuous extrusion of polytetrafluoroethylene (PTFE), a rectangular body Model is imported and is calculated, moulded dimension is 10 × 5
× 1cm, setting compactedness be 70%, it is contemplated that the print time be 1 hour 03 point 47 seconds, complete 3D printing.
1 ~ 4 example of the invention is subjected to impact strength measurement according to according to GB/T 1843-2008, as a result such as following table
。
Claims (4)
1. a kind of 3D printing method based on polytetrafluoroethylene (PTFE), it is characterised in that: face the polytetrafluoroethylene (PTFE) of molten condition with super
Boundary's carbon dioxide gas mixes in extruder so that in polytetrafluoroethylene (PTFE) supercritical carbon dioxide mass percent be 4~
10%, carbon dioxide is absorbed by polytetrafluoroethylene polymer strand, reduces molecular entanglement, increases free volume, while dioxy
Change carbon and serve as intermolecular lubricant, both effects reduce the viscosity of molten mass, are swollen by supercritical carbon dioxide poly-
The glass transition temperature of tetrafluoroethene reduces 40~60 DEG C, the pressure rise in extruder under the action of its swelling, reaches certainly
Also so that container both ends is formed pressure difference while my sealing effect, realize the continuous extrusion of polytetrafluoroethylene (PTFE), complete 3D printing.
2. the 3D printing method according to claim 1 based on polytetrafluoroethylene (PTFE), it is characterised in that: the heating temperature of extruder
Degree is 230~260 DEG C.
3. the 3D printing method according to claim 1 based on polytetrafluoroethylene (PTFE), it is characterised in that: supercritical carbon dioxide
Void fraction is greater than 99.9%.
4. the 3D printing method according to claim 1 based on polytetrafluoroethylene (PTFE), it is characterised in that: supercritical carbon dioxide
The incorporation time of gas and polytetrafluoroethylene (PTFE) in extruder is greater than 2min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910230169.9A CN110091499A (en) | 2019-03-26 | 2019-03-26 | A kind of 3D printing method based on polytetrafluoroethylene (PTFE) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910230169.9A CN110091499A (en) | 2019-03-26 | 2019-03-26 | A kind of 3D printing method based on polytetrafluoroethylene (PTFE) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110091499A true CN110091499A (en) | 2019-08-06 |
Family
ID=67443098
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910230169.9A Pending CN110091499A (en) | 2019-03-26 | 2019-03-26 | A kind of 3D printing method based on polytetrafluoroethylene (PTFE) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110091499A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112403121A (en) * | 2020-11-21 | 2021-02-26 | 西安热工研究院有限公司 | Fused deposition modeling 3D printing dioxin removal bag cage and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030230834A1 (en) * | 2001-10-25 | 2003-12-18 | Kenneth Wynne | Fluoropolymer-carbon dioxide compositions and methods of processing fluoropolymers |
| CN106696295A (en) * | 2015-08-21 | 2017-05-24 | 研能科技股份有限公司 | Liquid spraying device |
| CN109278282A (en) * | 2018-11-28 | 2019-01-29 | 共享智能铸造产业创新中心有限公司 | 3D printing head and the printer and Method of printing for being provided with the print head |
-
2019
- 2019-03-26 CN CN201910230169.9A patent/CN110091499A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030230834A1 (en) * | 2001-10-25 | 2003-12-18 | Kenneth Wynne | Fluoropolymer-carbon dioxide compositions and methods of processing fluoropolymers |
| CN106696295A (en) * | 2015-08-21 | 2017-05-24 | 研能科技股份有限公司 | Liquid spraying device |
| CN109278282A (en) * | 2018-11-28 | 2019-01-29 | 共享智能铸造产业创新中心有限公司 | 3D printing head and the printer and Method of printing for being provided with the print head |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112403121A (en) * | 2020-11-21 | 2021-02-26 | 西安热工研究院有限公司 | Fused deposition modeling 3D printing dioxin removal bag cage and preparation method thereof |
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Application publication date: 20190806 |