CN104109343A - High-flowability plastic composite powder material and preparation method thereof - Google Patents
High-flowability plastic composite powder material and preparation method thereof Download PDFInfo
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- CN104109343A CN104109343A CN201410376493.9A CN201410376493A CN104109343A CN 104109343 A CN104109343 A CN 104109343A CN 201410376493 A CN201410376493 A CN 201410376493A CN 104109343 A CN104109343 A CN 104109343A
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Abstract
The invention discloses a high-flowability plastic composite powder material and a preparation method thereof. The composite powder material comprises a plastic matrix material and a fiber-reinforced component, wherein the plastic matrix material is one or more selected from polypropylene (PP), ABS (Acrylonitrile Butadiene Styrene), polyamide, polyimide, poly(aryl ether ketone), polyether sulfone, polyphenylene sulfide and polytetrafluoroethylene; the fiber-reinforced component is one or more selected from glass fiber, carbon fiber, carbon fiber powder, mineral fiber powder, aramid fiber, ceramic fiber and boron fiber; the additive amount of the fiber-reinforced component is 0.01-30%, and the volume fraction of the fiber-reinforced component is 0-40%. According to the preparation method, firstly, the fiber-reinforced component is subjected to coupling modification, and then, the modified fiber-reinforced component is mixed with a plastic powder matrix to obtain the composite powder material, so that the flowability of the plastic powder is enhanced, the laser energy absorption efficiency of the plastic powder is improved, the powder packing density is also increased, and the mechanical performance and heat stability of a sintered material are enhanced. The high-flowability plastic composite powder material is wide in material source, simple in preparation process and very remarkable in effect.
Description
Technical field
The invention belongs to plastics composite field, relate to a kind of high workability plastics composite powder material and preparation method thereof.
Background technology
Increasing fast material manufacturing technology and be called again " 3D printing technique ", is current coming of new technology of being shown great attention to, and is called as the gordian technique that promotes the Industrial Revolution for the third time together with robot technology, artificial intelligence etc.Selective laser sintering (SLS) is a very important technology during 3D prints.SLS technique is a kind ofly based on discrete/stack shaping principle, to integrate the new technologies such as computer, numerical control, laser and novel material, selectively metal or nonmetallic powder material is carried out to sintering preparing product fast.The restriction that the required laser power of polymkeric substance SLS technology sintering is little, be not subject to part shape complexity, accurate fast restore design concept, directly the nearly fine and close part of machine-shaping, function test part, broken through the restriction of traditional manufacturing technology completely, obtains fast-developing in recent years.In SLS technique, realize high sintering precision, require polymer materials can be made into the spherical powder material of median size between 10-250um, such material flowability is good, and loose density is high.
The plastic shaping energy used is CO2 laser, in moulding process, utilize the laser high energy light velocity to scan selectively material, the laser energy that powdered material absorbs collides mutually by the basic energy particle of laser photon and powdered material inside, after making absorbed luminous energy, temperature raises, and energy is converted within extremely short moment to heat energy also gradually to internal delivery; The laser beam rapid heating material surface with enough power densities, reaches it and thinks temperature fusing, and after melting, heat transmits in powder; But material internal keeps the state of cooling substantially, this is mainly can not by plastic material, be absorbed completely due to energy that laser beam sends, also has part luminous energy to be reflected away by material surface, and the laser power density that causes being radiated material surface is lower.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of powder flowbility is strong, laser energy absorption efficiency is high plastics composite powder material and preparation method thereof.
For achieving the above object, the invention provides following technical scheme: a kind of high workability plastics composite powder material, this composite powder material comprises plastic matrix material and fiber reinforcement component; Described plastic matrix material is one or more in polypropylene PP, ABS, polymeric amide, polyimide, polyaryletherketone, polyethersulfone, polyphenylene sulfide and tetrafluoroethylene, and the size of plastic matrix material is 10～250 μ m; Described fiber reinforcement component is one or more in glass fibre, carbon fiber, mineral fibre, aramid fiber, ceramic fiber and boron fibre; The addition of described fiber reinforcement component is 0.01～30%, and volume fraction is 0～40%.
Further, described fiber reinforcement component is through coupling agent modified fiber reinforcement component or does not pass through coupling agent modified fiber reinforcement component.
Further, described coupling agent is one or more in silane coupling agent, titanate coupling agent, chromium complex coupling agent and zirconium coupling agent.
Further, the volume fraction of described fiber reinforcement component is 10～20%.
Further, the addition of described fiber reinforcement component is 5～10%.
Further, the size of described composite powder material is 10～250 μ m.
Further, the size of described composite powder material is 40～100 μ m.
Further, the staple length in described composite powder material is 0.8～1.5 with the ratio of the particle diameter of composite powder material.
The present invention also provides a kind of method of preparing above-mentioned high workability plastics composite powder material, mainly comprise the following steps: (1) chooses fiber reinforcement component, carry out the coupling agent modified of fiber reinforcement component, modifying process is: fiber reinforcement component is dissolved in the ethanol and coupling agent mixed solution of 5～10 times, then heat 3～5 hours, remove mixed solution, dry, obtain the fiber reinforced material through modification; (2) utilize high-speed mixer that fiber reinforced material is mixed with plastic matrix material, obtain composite powder material.
Beneficial effect of the present invention is: the present invention prepares composite powder material by plastic powders matrix is added to fiber reinforcement component, mobility and the laser energy absorption efficiency of plastic powders have not only been increased, solved dexterously the poor problem of plastic powders material flowability, also improved the tap density of powder, strengthened mechanical property and the thermostability of agglomerated material, the shrinking percentage of material reduces, the dimensional stability of product improves, material source is extensive, and preparation process is simple, and effect is very remarkable.
Embodiment
To be described in detail the preferred embodiments of the present invention below.
High workability plastics composite powder material described in the present embodiment, this composite powder material comprises plastic matrix material and fiber reinforcement component; Described plastic matrix material is one or more in polypropylene PP, ABS, polymeric amide, polyimide, polyaryletherketone, polyethersulfone, polyphenylene sulfide and tetrafluoroethylene; Described fiber reinforcement component is one or more in glass fibre, carbon fiber, mineral fibre, aramid fiber, ceramic fiber and boron fibre; Wherein, the size of plastic matrix material is 10～250 μ m, and the size of composite powder material is 10～250 μ m, and the addition of fiber reinforcement component is 0.01～30%, and volume fraction is 0～40%.
Fiber reinforcement component in the present embodiment is the fiber reinforcement component through coupling agent modified, and the fiber reinforcement component after modification can improve the energy absorption efficiency of plastic matrix material, and raising ratio is 3%～10%.Wherein, coupling agent is one or more in silane coupling agent, titanate coupling agent, chromium complex coupling agent and zirconium coupling agent.
Preferably, the addition of described fiber reinforcement component is 5～10%, and volume fraction is 10～20%.
Preferably, the size of described composite powder material is 40～100 μ m.
Especially, the staple length in described composite powder material is 0.8～1.5 with the ratio of the particle diameter of composite powder material.
A kind of preparation method of high workability plastics composite powder material, mainly comprise that step (1) chooses fiber reinforcement component, carry out the coupling agent modified of fiber reinforcement component, modifying process is: fiber reinforcement component is dissolved in the ethanol and coupling agent mixed solution of 5～10 times, then heat 3～5 hours, remove mixed solution, dry, obtain the fiber reinforced material through modification; (2) utilize high-speed mixer blend fiber strongthener and plastic matrix material, fortifying fibre is embedded in the powder particle being comprised of plastic matrix material, obtain composite powder material.
Embodiment 1
1) choose the PEEK resin powder that 70 parts of median sizes are 100 μ m, 28 parts of median sizes are the carbon fiber powder of 150 μ m, and wherein PEEK resin powder adopts airflow pulverization method preparation, and carbon fiber powder adopts high energy ball mill method preparation;
2) 2.5 parts of silane coupling agents are dissolved in the ethanolic soln of 5～10 times, then by step 1) in carbon fiber powder sneak in mixing solutions, heat 3 hours, remove coupling agent and solvent, dry;
3) by step 1) selected PEEK resin powder, step 2) the carbon fiber powder of modification mixes by high-speed mixing equipment, obtains PEEK resin compounded powder body material;
4) adopt selective laser sintering method, sintering goes out standard dumb-bell shape experiment batten.
Embodiment 2
1) choose the PPS resin powder that 89 parts of median sizes are 130 μ m, 9 parts of median sizes are the glass fibre powder of 150 μ m, and wherein PPS resin powder adopts airflow pulverization method preparation, and glass fibre powder adopts high energy ball mill method preparation;
2) 2 parts of titanate coupling agents are dissolved in the ethanolic soln of 5～10 times, then by step 1) in glass fibre powder sneak in mixing solutions, heat 3 hours, remove coupling agent and solvent, dry;
3) by step 1) selected PPS resin powder, step 2) the glass fibre powder of modification mixes by high-speed mixing equipment, obtains PPS resin compounded powder body material;
4) adopt selective laser sintering method, sintering goes out standard dumb-bell shape experiment batten.
Embodiment 3
1) choose the PA12 resin powder that 60 parts of median sizes are 30 μ m, 38 parts of median sizes are the glass fibre powder of 50 μ m, and wherein PA12 resin powder adopts airflow pulverization method preparation, and glass fibre powder adopts high energy ball mill method preparation;
2) 2.5 parts of silane coupling agents are dissolved in the ethanolic soln of 5～10 times, then by step 1) in glass fibre powder sneak in mixing solutions, heat 3 hours, remove coupling agent and solvent, dry;
3) by step 1) selected PA12 resin powder, step 2) the glass fibre powder of modification mixes by high-speed mixing equipment, obtains PA12 resin compounded powder body material;
4) adopt selective laser sintering method, sintering goes out standard dumb-bell shape experiment batten;
Composite powder material and the contrast situation of unmodified resin powder aspect material property of utilizing above-mentioned three kinds of methods to obtain are as shown in the table:
| ? | PEEK | PEEK+ carbon fiber | PPS | PPS+ glass fibre | PA12 | PA12+ glass dimension |
| Powder flowbility BFE (mJ) | 39.5 | 30 | 44 | 32 | 35 | 29 |
| Laser energy absorption rate % | 80％ | 85％ | 70％ | 75％ | 78％ | 82％ |
| Powder accumulation density | 0.5 | 0.65 | 0.45 | 0.5 | 0.4 | 0.55 |
| Tensile strength (MPa) | 100 | 180 | 80 | 120 | 90 | 130 |
| Tensile modulus (GPa) | 2.7 | 5 | 2.9 | 4 | 3 | 3.5 |
| Td 5(℃) | 450 | 500 | 410 | 430 | 350 | 380 |
| Material contracts rate (%) | 0.6 | 0.2 | 0.7 | 0.4 | 0.9 | 0.7 |
As can be seen from the above table, the toner that has added filamentary material flows obvious decline, laser energy absorption efficiency, powder accumulation density, tensile strength, tensile modulus and Td when property and material contracts rate are not added
5also have rising, wherein the ascending amount of tensile strength is especially obvious, and the premises all has direct impact to the surface quality of workpiece and workpiece performance; The present invention, by plastic powders matrix is added to mobility and the laser energy absorption efficiency that fiber reinforcement component improves plastic powders, makes it be more suitable for SLS sintering.
Above-described embodiment has only been chosen partly plastic powder, filamentary material and coupling agent, but applicable too for plastic powders, filamentary material and the coupling agent of other kinds.
Finally explanation is, above preferred embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is described in detail by above preferred embodiment, but those skilled in the art are to be understood that, can to it, make various changes in the form and details, and not depart from the claims in the present invention book limited range.
Claims (9)
1. a high workability plastics composite powder material, is characterized in that: this composite powder material comprises plastic matrix material and fiber reinforcement component; Described plastic matrix material is one or more in polypropylene PP, ABS, polymeric amide, polyimide, polyaryletherketone, polyethersulfone, polyphenylene sulfide and tetrafluoroethylene, and the size of plastic matrix material is 10～250 μ m; Described fiber reinforcement component is one or more in glass fibre, carbon fiber, mineral fibre, aramid fiber, ceramic fiber and boron fibre; The addition of described fiber reinforcement component is 0.01～30%, and volume fraction is 0～40%.
2. high workability plastics composite powder material according to claim 1, is characterized in that: described fiber reinforcement component is for the fiber reinforcement component through coupling agent modified or do not pass through coupling agent modified fiber reinforcement component.
3. high workability plastics composite powder material according to claim 2, is characterized in that: described coupling agent is one or more in silane coupling agent, titanate coupling agent, chromium complex coupling agent and zirconium coupling agent.
4. high workability plastics composite powder material according to claim 1, is characterized in that: the volume fraction of described fiber reinforcement component is 10～20%.
5. high workability plastics composite powder material according to claim 1, is characterized in that: the addition of described fiber reinforcement component is 5～10%.
6. high workability plastics composite powder material according to claim 1, is characterized in that: the size of described composite powder material is 10～250 μ m.
7. high workability plastics composite powder material according to claim 6, is characterized in that: the size of described composite powder material is 40～100 μ m.
8. high workability plastics composite powder material according to claim 1, is characterized in that: the staple length in described composite powder material is 0.8～1.5 with the ratio of the particle diameter of composite powder material.
9. a method of preparing the high workability plastics composite powder material as described in claim 1-8 any one, it is characterized in that mainly comprising the following steps: (1) chooses fiber reinforcement component, carry out the coupling agent modified of fiber reinforcement component, modifying process is: fiber reinforcement component is dissolved in the ethanol and coupling agent mixed solution of 5～10 times, then heat 3～5 hours, remove mixed solution, dry, obtain the fiber reinforced material through modification; (2) utilize high-speed mixer that fiber reinforced material is mixed with plastic matrix material, obtain composite powder material.
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| CN105670280A (en) * | 2016-04-01 | 2016-06-15 | 青岛国恩科技股份有限公司 | Glass-fiber-reinforced polyamide 6 (PA6) material for vehicle lights and preparation method thereof |
| CN105860521A (en) * | 2016-04-13 | 2016-08-17 | 万达集团股份有限公司 | Selective laser sintering-based polyimide powder material and preparation method thereof |
| CN106380610A (en) * | 2016-09-23 | 2017-02-08 | 江西师范大学 | Method for preparing polyether sulfone powder consumable item for 3D printing of laser sintering and molding |
| CN106554619A (en) * | 2016-12-02 | 2017-04-05 | 江苏新瑞贝科技股份有限公司 | A kind of printing masterbatch of the manual imitation synthetic fabrics suitable for printing shaping technology |
| CN106589941A (en) * | 2016-03-16 | 2017-04-26 | 东北林业大学 | Glass-fiber-reinforced walnut shell composite powder material for laser sintering 3D printing technology |
| CN108368275A (en) * | 2016-01-20 | 2018-08-03 | 东丽株式会社 | Polyarylene sulfide resin bulk material and its manufacturing method |
| CN108519402A (en) * | 2018-03-28 | 2018-09-11 | 北京工业大学 | The device and method that laser method measures ultra-thin glass reheating linear shrinkage ratio |
| CN108530757A (en) * | 2018-04-27 | 2018-09-14 | 常州凌风超智科技信息咨询有限公司 | A kind of preparation method of washing machine lifting rib modified polypropylene material |
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| CN112537921A (en) * | 2020-12-17 | 2021-03-23 | 中国科学院上海硅酸盐研究所 | Phenolic resin coated chopped carbon fiber composite powder for laser 3D printing and preparation method thereof |
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| CN103951971A (en) * | 2014-05-12 | 2014-07-30 | 湖南华曙高科技有限责任公司 | Carbon fiber reinforced resin powder material for selective laser sintering |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103951971A (en) * | 2014-05-12 | 2014-07-30 | 湖南华曙高科技有限责任公司 | Carbon fiber reinforced resin powder material for selective laser sintering |
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| CN108368275A (en) * | 2016-01-20 | 2018-08-03 | 东丽株式会社 | Polyarylene sulfide resin bulk material and its manufacturing method |
| CN108368275B (en) * | 2016-01-20 | 2019-06-21 | 东丽株式会社 | Polyarylene sulfide resin bulk material and its manufacturing method |
| CN106589941B (en) * | 2016-03-16 | 2018-12-25 | 东北林业大学 | Laser sintered 3D printing technique fiberglass reinforced walnut shell composite powder material |
| CN106589941A (en) * | 2016-03-16 | 2017-04-26 | 东北林业大学 | Glass-fiber-reinforced walnut shell composite powder material for laser sintering 3D printing technology |
| CN105670280A (en) * | 2016-04-01 | 2016-06-15 | 青岛国恩科技股份有限公司 | Glass-fiber-reinforced polyamide 6 (PA6) material for vehicle lights and preparation method thereof |
| CN105860521A (en) * | 2016-04-13 | 2016-08-17 | 万达集团股份有限公司 | Selective laser sintering-based polyimide powder material and preparation method thereof |
| CN106380610A (en) * | 2016-09-23 | 2017-02-08 | 江西师范大学 | Method for preparing polyether sulfone powder consumable item for 3D printing of laser sintering and molding |
| CN106380610B (en) * | 2016-09-23 | 2018-08-21 | 江西师范大学 | The preparation method of laser sintering (SLS) 3D printing polyether sulfone powder supplies |
| CN106554619A (en) * | 2016-12-02 | 2017-04-05 | 江苏新瑞贝科技股份有限公司 | A kind of printing masterbatch of the manual imitation synthetic fabrics suitable for printing shaping technology |
| CN108519402B (en) * | 2018-03-28 | 2020-12-22 | 北京工业大学 | Device and method for measuring re-heating wire shrinkage rate of ultrathin glass by laser method |
| CN108519402A (en) * | 2018-03-28 | 2018-09-11 | 北京工业大学 | The device and method that laser method measures ultra-thin glass reheating linear shrinkage ratio |
| CN108530757A (en) * | 2018-04-27 | 2018-09-14 | 常州凌风超智科技信息咨询有限公司 | A kind of preparation method of washing machine lifting rib modified polypropylene material |
| CN109912967A (en) * | 2019-01-18 | 2019-06-21 | 常州先风三维科技有限公司 | A kind of nylon carbon fiber composite powder and preparation method thereof of the reduction material anisotropy for selective laser sintering |
| CN112537921A (en) * | 2020-12-17 | 2021-03-23 | 中国科学院上海硅酸盐研究所 | Phenolic resin coated chopped carbon fiber composite powder for laser 3D printing and preparation method thereof |
| CN112537921B (en) * | 2020-12-17 | 2021-11-02 | 中国科学院上海硅酸盐研究所 | Phenolic resin coated chopped carbon fiber composite powder for laser 3D printing and preparation method thereof |
| CN113121242A (en) * | 2021-03-05 | 2021-07-16 | 中国科学院上海硅酸盐研究所 | Short carbon fiber toughened silicon carbide composite material and preparation method thereof |
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