CN105623215A - Flexible circuit conductive composition and 3D (three dimensional) printing based flexible circuit construction method - Google Patents
Flexible circuit conductive composition and 3D (three dimensional) printing based flexible circuit construction method Download PDFInfo
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- 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
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- 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
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention belongs to the field of high polymer materials and relates to a flexible circuit conductive composition and a 3D (three dimensional) printing based flexible circuit construction method. A thermoplastic substrate and conductive filler are subjected to solution premixing, melt blending, and melting extrusion to obtain the flexible circuit conductive composition, and the flexible circuit conductive composition is printed onto the substrate by means of 3D printing. An obtained flexible circuit guarantees integral high conductivity and has excellent mechanical properties and high flexibility.
Description
Technical field:
The present invention relates to a kind of flexible circuit conductive compositions and print the method building flexible circuit based on 3D. Belong to polymeric material field.
Background technology:
Along with developing rapidly of 21 century computer industry, the update speed of electronic devices and components is also accelerated therewith. Electronic equipment, electronic devices and components become the core that the fields such as traffic, national defence, communication, space flight are run. Electronic equipment and components and parts thereof towards less, faster, direction portable, low cost develops. In this context, the manufacturing process of circuit and method are also needed badly and are updated, and adapt to new demand proposed after electronic equipment updates with this. Flexible circuit, in view of it is portable, the feature of low cost, is one of the dominant direction of novel circuit development all the time.
The manufacture of flexible circuit is most commonly used that the method by printing and realizes: layers of copper and flexible base layer being fit together, interlayer adhesive is bonded together. Then circuit pattern is obtained by the method for conventional etch. Also flexible substrates can be placed between two layers of copper, after etching, form double-sided PCB, connect by boring a hole between two conductive layers. Patent CN101460020, CN101203095 disclose a kind of method manufacturing multi-layer flexible circuit version, and its main technique is the stacking of monolayer circuit version, and the method for patterning remains as conventional etch. In this stage, the method for conventional etch considerably increases the manufacturing cost of flexible PCB, the use of conductive bodies copper so that reduces weight of equipment and becomes problem, therefore becomes portable major obstacle. On the other hand, this kind of method, only substrate material is flexible material, and the metallic copper that conductive bodies is hard does not change, and so there is no the flexible circuit realized truly.
In recent years, silk screen printing and nanometer embossing became the mainstream technology improving conventional flex circuits board fabrication method. These two kinds of methods have the advantages such as technique is simple, cost is low, product flexibility is good. But the conductive material conductivity replacing copper at present is on the low side, it does not have reaching conductor or the conductive extensions of high conductor, therefore its actual application value is inconsiderable. Patent CN104527247A discloses the method for printing screen after a kind of improvement, it is manufactured that the fuel cell microcircuit that electric conductivity is good, stability is high, but owing to its conductive bodies is silver slurry, its cost beyond major part printing technology cost, does not therefore possess actual application value.
Meanwhile, inkjet printing also becomes one of main stream approach of existing flexible circuit manufacture. Its cardinal principle, for conductive bodies being dissolved in or being dispersed in ink-jet ink, regulates and controls its viscosity by regulating and controlling its solvent and other additive levels, it is thus possible to print on flexible parent metal from business printer smoothly. The preparation method that patent CN103619128A discloses a kind of flexible PCB based on inkjet printing, has prepared the flexible circuit pattern that quality is higher. But, inkjet printing and actual industrialization have three major obstacles between producing, and first, the conductive bodies of inkjet printing is generally metal dust or metal nanoparticle, such as gold, silver, copper, the powder of nickel or its nanoparticle. The cost of this kind of metallic product is too high so that puts into practical application and becomes unrealistic. Second, the ink used by inkjet printing, because to adapt to the ink-jet printer of business, therefore to control its viscosity by various allotments in preparation process, and its technique is excessively complicated, brings the rising of cost and the reduction of efficiency to actual production. 3rd, the conductive bodies of inkjet printing is powder, and after therefore solvent volatilization treated by the flexible circuit of its printing, though adhesion can form conductive path between powder, but the slight stretching of external force or bending are all likely to make its adhesion interrupt, so that its open circuit. Defect in mechanical property makes it be difficult to flexibility truly.
Conductive carbon material, if Graphene, CNT etc. are because its electrical conductivity is high, quality is little, excellent in mechanical performance is widely used gradually. Patent CN102212304A disclose a kind of with modified carbon nano-tube be conductive bodies, the flexible circuit preparation flow that is preparation method with silk screen printing. Prepared flexible PCB not only conductivity is high, and excellent in mechanical performance, step major step towards industrial applications. But its manufacturing process need further optimization, to improve efficiency. On the other hand, the method can only be confined to two-dimensional circuit, it is impossible to realizes three-dimensional circuit or the structure of curved surface circuit.
And up-to-date flexible circuit preparation method is the laser orientation sintering process based on Graphene. Patent CN102501701A discloses a kind of flexible circuit preparation method based on Graphene laser ablation, graphene oxide is made thin film and is layered on resistant to elevated temperatures base material or on CD by the method, is oriented burning with the laser head of DVD or the laser head that is connected with computer and carves. Graphene oxide is by the scanned part of thin beam laser, and due to high temperature, graphene oxide is reduced, and forms the Graphene of high connductivity, thus forming the pattern of high connductivity. Although flexible circuit electrical conductivity height prepared by this kind of method, but similar with method before, however it remains the problem in some mechanical properties. After graphene oxide is reduced by laser orientation, structure forms spongy body state, more frangible. It addition, the mechanical property of graphene oxide film own is bad, does not have the holder of flexible parent metal to serve as a contrast in addition, become insecure.
Summary of the invention:
It is desirable to provide a kind of flexible circuit conductive compositions and the method based on 3D printing structure flexible circuit, by thermoplastic matrix with conductive filler through solution premixing, then through melt blending, through melt extruding prepared flexible circuit conductive compositions after, by the 3D mode printed, flexible circuit conductive compositions is printed on flexible substrate to flexible circuit not only ensure that the high conductivity of entirety but also there is the mechanical property of excellence and flexible preferably.
A kind of flexible circuit conductive compositions provided by the invention, is made up of thermoplastic matrix and conductive filler, and thermoplastic matrix and conductive filler mass ratio be: 9-200:1, it is preferred to 20-50:1.
Described thermoplastic matrix is thermoplastic or thermoplastic elastomer (TPE), it is preferable that from: polylactic acid (PLA), cellulose acetate, polyethylene (PE), polrvinyl chloride (PVC), polypropylene (PP), styrene-butadiene-acrylonitrile terpolymer (ABS), polystyrene (PS), Merlon (PC), nylon 6, thermoplastic polyurethane (TPU).
Described conductive filler is selected from: CNT, Graphene, chopped carbon fiber, nanometer silver or micron silver, Nanometer Copper or micron copper.
Any in the following material of above-mentioned CNT or their mixture: CNT that common CNT, oxide/carbon nanometer tube, nano metal particles are modified (as: the CNT that CNT that CNT that the CNT of decorated by nano-gold, nanometer silver are modified, nanometer silver nickel are modified, nano nickel are modified).
The preparation method of above-mentioned oxide/carbon nanometer tube is: CNT adds the dense H of 98wt% that volume ratio is 3:12SO4HNO dense with 62-63wt%3Mixed solution in, ultrasonic resonance 2-6 hour. Its handlability of CNT after oxidized and degree of orientation in the base can be greatly increased.
The preparation method of the CNT that nano metal particles is modified is: by oxide/carbon nanometer tube ultrasonic resonance 1-3 hour in the solution of dodecylbenzene sodium sulfonate (SDBS) and polyvinyl pyrrolidone (PVP); Then polyhydric alcohol (polyhydric alcohol of unimolecule hydroxyl quantity 2-6) and metal strong acid aqueous solution (AgNO are added3��NiSO4��HAuCI4), ultrasonic resonance 2-6 hour at 50-70 DEG C.
Any in the following material of above-mentioned Graphene or their mixture: electronation Graphene, thermal reduction Graphene, high-performance mechanical peel off single-layer graphene, graphene nanometer sheet, chemistry-thermal reduction Graphene.
In order to keep good flexibility, reduce the addition of conductive filler as far as possible, improve the electrical conductivity of circuit, it is preferable that high-performance mechanical peels off single-layer graphene or chemistry-thermal reduction Graphene.
The preparation method of above-mentioned chemistry-thermal reduction Graphene is: native graphite Hummers method is prepared into graphene oxide (GO). Ultrasonic resonance after graphene oxide is reduced with strong reductant so that it is fully peel off. It is then placed in tube furnace nitrogen protection and is heated to 800-1200 DEG C of insulation 1-2h.
Above-mentioned nanometer silver or micron silver are selected from: nano silver wire, Nano silver grain, Nano silver piece or silver micropowder.
Above-mentioned Nanometer Copper or micron copper are selected from: copper nano-wire, copper nano-particle, copper nanometer sheet or copper micropowder.
The nano wire that above-mentioned silver, copper nano-wire are metal salt back method or polyol process growth method is prepared, radial dimension is 30-60nm, and line length is 1-5 ��m. Above-mentioned copper, Nano silver grain particle diameter are between 5-50nm. Above-mentioned copper, Nano silver piece lateral dimension between 100-800nm. Above-mentioned copper, silver micropowder particle size between 10-40 ��m.
Provided by the invention a kind of based on the 3D method printing structure flexible circuit:
(1) first conductive filler is added in thermoplastic matrix's liquid solution and carry out solution premixing, in banbury, carry out melt blending, then pass through extruder and melt extrude into conductive filament material.
(2) by conductive filament material, insert in 3D printer, regulate and control suitable head temperature, according to the circuit pattern of computer software (CAD, SolidWork, 3DMax etc.) Aided Design, print to flexible substrates, make flexible circuit. The printing of two dimension, three-dimensional and curve flexibility circuit can be realized.
In above-mentioned steps (1), the solvent used by solution premixing is selected from: dichloromethane, chloroform, acetonitrile, oxolane, N, dinethylformamide, N, N-dimethyl acetylamide, Isosorbide-5-Nitrae-dioxane, toluene, dimethylbenzene or dimethyl sulfoxide. The concentration of the thermoplastic matrix's liquid solution prepared by solution premixing is preferably controlled within 0.1g/ml-0.25g/ml scope, can be sufficiently mixed after being stirred together for guarantee and conductive filler.
Controlling banbury screw speed in melt blending process of the present invention is 60-100r/min, screw temperature set is for exceeding thermoplastic matrix's bulk melting point 10-15 degree Celsius (DEG C), under this condition, blended effect is optimum, is conducive to being formed in thermoplastic matrix's body continuous conduction path.
In above-mentioned steps (2), in 3D print procedure, printer head temperature is set as: exceed thermoplastic matrix's bulk melting point 50-60 degree Celsius (DEG C), to ensure that melted conductive material can be got smoothly from the vestibule of 400 ��m.
Flexible substrates of the present invention is selected from: polyimide film (PI), polyethylene terephthalate film (PET), polychloroethylene film (PVC), polypropylene screen (PP), polyurethane film (PU), paper or aluminum stannum thin slice.
For making to have good adhesion between flexible substrates and electric conductor, and avoid lubricating substance in 3D print procedure, flexible substrates can be carried out surface plasma etching processing.
The preferred polyimide film of flexible substrates (PI) or polyethylene terephthalate film (PET), for making to have between PI or PET film and electric conductor better adhesion, and preferably at the dense H of the 98wt% that volume ratio is 3:1 before avoiding lubricating substance in 3D print procedure, PI or PET film to use2SO4And 36%H2O2Solution soaks 1-3h.
The method adopting 3D printing to prepare flexible circuit provided by the invention. Preparation process is simple to operation, and stability is high, the cycle is short. Prepared flexible circuit is excellent compared to traditional method electrical conductivity height, excellent in mechanical performance, flexibility. Meanwhile, in preparation process, raw materials is cheap, can be mass-produced, and can put in commercial production and use.
Accompanying drawing illustrates:
Fig. 1 is the two-dimension flexible circuit that the embodiment of the present invention 1 prints
Fig. 2 is the three-dimension flexible circuit that the embodiment of the present invention 6 prints
Detailed description of the invention:
Below in conjunction with embodiment, the present invention will be further described: the part described in embodiment refers both to mass parts.
Embodiment 1:
47.5 parts of polylactic acid (PLA) are joined in dichloromethane, is sufficiently stirred for until polylactic acid is dissolved completely in dichloromethane, form transparent PLA solution (solution concentration 0.15g/ml). Under agitation, 2.5 parts of chemistry-thermal reduction Graphene (after the graphene oxide strong reductant electronation prepare Hummers method, put in the tube furnace of argon shield 1000 DEG C and be incubated 1 hour) continuously stirred 20min it are slowly added to. PLA-graphene dispersing solution is poured in container, ventilates, after solvent volatilizees, carry out vacuum drying. Taking-up is ground into powder, puts in HAKKE banbury blended, and extruder temperature is 160 DEG C, and screw speed is 80r/min, and the blended time is 10min. Blended rear pelletizing is pulverized, and puts in single screw extrusion machine and melt extrudes, and extruder screw temperature is 213 DEG C, makes the silk material that diameter is 1.75mm. Being inserted by silk material in 3D printer (MakerbotReplicator2), according to the single-layer model circuit that CAD design goes out, by PI film substrate, (substrate is first at volume ratio is 3:1 98% dense H2SO4With 36%H2O2Mixed solution soaks 3h) it is fixed on print platform, head temperature controls, at 210 DEG C, to print flexible circuit.
Prepared flexible circuit electrical conductivity reaches 3.98S/cm, and Young's modulus reaches 12.1MPa. Elongation at break reaches 7.09%.
Embodiment 2:
20 parts of terpolymer ABS are joined in the mixed solution (volume ratio 1:1) of appropriate chloroform and toluene, be sufficiently stirred for until ABS is completely dissolved, form the ABS solution (solution concentration 0.15g/ml) of turbid white. In high-speed stirred, it is slowly added to the chloroform dispersion liquid containing 2 parts of nano silver wires continuously stirred 1h. ABS-nano silver wire dispersion liquid is poured in container, ventilates, after solvent volatilizees, carry out vacuum drying. Taking out ABS-nano silver wire and be ground into powder, put in single screw extrusion machine and melt extrude, extruder temperature is 237 DEG C, makes the silk material that diameter is 1.75mm. Being inserted in 3D printer by silk material, go out single-layer model circuit by CAD design, by PET film substrate, (substrate is first at volume ratio is 3:1 98% dense H2SO4With 36%H2O2Mixed solution soaks 3h) it is fixed on print platform, head temperature controls at 240 DEG C, prints flexible circuit.
Above-mentioned nano silver wire preparation method is: 3.34 parts of PVP and ethylene glycol are mixed to form the solution that concentration is 0.1g/ml, heats after 170 DEG C, is slowly added to containing 11 parts of AgNO after adding 2.5 parts of grindings broken AgCI, 3min immediately3Weak solution, post-heating to 170 DEG C keep 30min, separated prepared nano silver wire, radial dimension is 30-60nm, and line length is 1-5 ��m.
Prepared flexible circuit electrical conductivity reaches 2.01S/cm, and Young's modulus reaches 9.41MPa. Elongation at break reaches 8.70%.
Embodiment 3:
47 parts of polystyrene (PS) are joined in appropriate oxolane, is sufficiently stirred for until polystyrene is dissolved completely in oxolane, form transparent polystyrene solution (solution concentration 0.15g/ml). In high-speed stirred, add 3 parts of carbon nano-tube modified rear and continuously stirred 20min of nanometer silvers. PS-carbon nano-tube solution is poured in container, ventilates, after solvent volatilizees, carry out vacuum drying. Taking out PS-CNT and be ground into powder, put in HAKKE banbury blended, extruder temperature is 220 DEG C, and screw speed is 80r/min, and the blended time is 10min. Blended rear pelletizing is pulverized, and puts in single screw extrusion machine and melt extrudes, and extruder screw temperature is 240 DEG C, makes the silk material that diameter is 1.75mm. Being inserted in 3D printer by silk material, go out single-layer model circuit by CAD design, with paper for substrate, be fixed on print platform, head temperature controls at 240 DEG C, prints flexible circuit.
The preparation method of above-mentioned modified by silver CNT is: takes 2 parts of CNTs after peroxidating and joins the solution forming 0.1g/ml in ethylene glycol, more than ultrasonic disperse 15min, obtains solution A. Weigh 1 part of AgNO respectively3, 1 part of polyvinyl pyrrolidone (PVP) and 1 part of sodium dodecyl benzenylsulfonate (SDBS) join the solution forming 0.1g/ml in ethylene glycol, sonic oscillation 10min solution B derived above. Solution A is mixed with solution B and more than sonic oscillation 3h. After put in ultraviolet drying baker dry.
Prepared flexible circuit electrical conductivity reaches 4.10S/cm, and Young's modulus reaches 13.9MPa. Elongation at break reaches 6.82%.
Embodiment 4:
46 parts of cellulose acetate are joined in appropriate DMF (DMF), is sufficiently stirred for until cellulose acetate is dissolved completely in DMF, form transparent cellulose acetate solution (solution concentration 0.15g/ml). In high-speed stirred, add 4 parts of commercially available chopped carbon fibers continuously stirred 20min. Cellulose acetate-carbon fiber solution is poured in container, ventilates, after solvent volatilizees, carry out vacuum drying. Taking out cellulose acetate-carbon fiber powder and be broken into powder, put in HAKKE banbury blended, extruder temperature is 227 DEG C, and screw speed is 80r/min, and the blended time is 10min. Blended rear pelletizing is pulverized, and puts in single screw extrusion machine and melt extrudes, and extruder screw temperature is 233 DEG C, makes the silk material that diameter is 1.75mm. Being inserted in 3D printer by silk material, go out single-layer model circuit by CAD design, be fixed on print platform by aluminum stannum platelet substrate, head temperature controls at 240 DEG C, prints flexible circuit.
Prepared flexible circuit electrical conductivity reaches 3.87S/cm, but owing to printing after extrusion through 3D printer, carbon fiber generation orientation, therefore prepared circuit local conductivity is up to 100S/cm. Young's modulus reaches 16.77MPa. Elongation at break reaches 7.24%.
Embodiment 5:
47 parts of thermoplastic polyurethanes (TPU) are joined in appropriate DMF, is sufficiently stirred for until TPU is dissolved completely in DMF, form thermoplastic polyurethane solution (solution concentration 0.19g/ml). In high-speed stirred, add 3 parts of chemistry-thermal reduction Graphenes (with preparation method in example 1) continuously stirred 20min. TPU-graphene solution is poured in container, ventilates, after solvent volatilizees, carry out vacuum drying. Taking out TPU-Graphene and be ground into powder, put in HAKKE banbury blended, extruder temperature is 200 DEG C, and screw speed is 80r/min, and the blended time is 10min. Blended rear pelletizing is pulverized, and puts in the feed well of 3D printer, goes out single-layer model circuit by CAD design, and by PET film substrate, (substrate must first at 98% dense H2SO4With 36%H2O2Mixed solution soaks 3h) it is fixed on print platform, head temperature controls at 230 DEG C, prints flexible circuit.
Prepared flexible circuit electrical conductivity reaches 2.24S/cm, and Young's modulus reaches 8.89MPa. Elongation at break reaches 10.07%. Owing to matrix used in the method is thermoplastic elastomer (TPE), therefore prepared circuit is except having good flexibility, also has good elasticity and pliability.
Embodiment 6:
47 parts of thermoplastic polyurethanes (TPU) are joined in 300mlDMF, is sufficiently stirred for until TPU is dissolved completely in DMF, form thermoplastic polyurethane solution (solution concentration 0.19g/ml). In high-speed stirred, add 3 parts of carbon nano-tube modified (with preparation methoies in example 3) of nanometer silver continuously stirred 20min. TPU-carbon nano-tube solution is poured in container, ventilates, after solvent volatilizees, carry out vacuum drying. Taking out TPU-CNT and be ground into powder, put in HAKKE banbury blended, extruder temperature is 200 DEG C, and screw speed is 80r/min, and the blended time is 10min. Blended rear pelletizing is pulverized, and puts in the feed well of 3D printer, goes out single-layer model circuit by CAD design, and by PI film substrate, (substrate must first at 98% dense H2SO4With 36%H2O2Mixed solution soaks 3h) it is fixed on print platform, head temperature controls at 230 DEG C, prints flexible circuit.
Prepared flexible circuit electrical conductivity reaches 2.67S/cm, and Young's modulus reaches 8.13MPa. Elongation at break reaches 11.20%. Owing to matrix used in example 5 and example 6 method is thermoplastic elastomer (TPE), therefore prepared circuit is except having good flexibility, also has good elasticity and pliability.
Claims (10)
1. a flexible circuit conductive compositions, is made up of thermoplastic matrix and conductive filler, and thermoplastic matrix and conductive filler mass ratio be: 9-200:1;
Described thermoplastic matrix is thermoplastic or thermoplastic elastomer (TPE), is selected from: polylactic acid, cellulose acetate, polyethylene, polrvinyl chloride, polypropylene, styrene-butadiene-acrylonitrile terpolymer, polystyrene, Merlon, nylon 6 or thermoplastic polyurethane;
Described conductive filler is selected from: CNT, Graphene, chopped carbon fiber, nanometer silver or micron silver, Nanometer Copper or micron copper.
2. flexible circuit conductive compositions according to claim 1, is characterized in that: thermoplastic matrix and conductive filler mass ratio be: 20-50:1.
3. flexible circuit conductive compositions according to claim 1, is characterized in that: any in the following material of CNT or their mixture: the CNT that CNT, oxide/carbon nanometer tube, nano metal particles are modified.
4. flexible circuit conductive compositions according to claim 1, is characterized in that: any in the following material of Graphene or their mixture: electronation Graphene, thermal reduction Graphene, high-performance mechanical peel off single-layer graphene, graphene nanometer sheet, chemistry-thermal reduction Graphene.
5. the flexible circuit conductive compositions according to claim 1 or 4, is characterized in that: Graphene peels off single-layer graphene or chemistry-thermal reduction Graphene selected from high-performance mechanical.
6. flexible circuit conductive compositions according to claim 1, is characterized in that: nanometer silver or micron silver are selected from: nano silver wire, Nano silver grain, Nano silver piece or silver micropowder; Nanometer Copper or micron copper are selected from: copper nano-wire, copper nano-particle, copper nanometer sheet or copper micropowder.
7. flexible circuit conductive compositions according to claim 6, is characterized in that: silver, copper nano-wire radial dimension are 30-60nm, and line length is 1-5 ��m; Copper, Nano silver grain particle diameter are between 5-50nm; Copper, Nano silver piece lateral dimension between 100-800nm; Copper, silver micropowder particle size between 10-40 ��m.
8. one kind prints the method building flexible circuit based on 3D:
(1) adopt the flexible circuit conductive compositions described in claim 1, first conductive filler is added in thermoplastic matrix's liquid solution and carry out solution premixing, in banbury, carry out melt blending, then pass through extruder and melt extrude into conductive filament material;
(2) by conductive filament material, insert in 3D printer, regulate and control suitable head temperature, according to the circuit pattern of computer software Aided Design, print to flexible substrates, make flexible circuit.
9. method according to claim 8, it is characterized in that: in step (1), the solvent used by solution premixing is selected from: dichloromethane, chloroform, acetonitrile, oxolane, N, dinethylformamide, N, N-dimethyl acetylamide, Isosorbide-5-Nitrae-dioxane, toluene, dimethylbenzene or dimethyl sulfoxide.
10. method according to claim 8, is characterized in that: in step (1), the concentration of thermoplastic matrix's liquid solution prepared by solution premixing controls within 0.1g/ml-0.25g/ml scope.
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| CN106336632A (en) * | 2016-08-05 | 2017-01-18 | 南京工业职业技术学院 | Antistatic 3D printing material and production method thereof |
| CN106380806A (en) * | 2016-09-28 | 2017-02-08 | 北京石油化工学院 | Conductive polylactic acid composite material composition for hot-melt 3D printing and preparation method thereof |
| CN106496983A (en) * | 2016-11-17 | 2017-03-15 | 南宁梦幻三体环保科技有限公司 | A kind of graphene composite material of 3D printing |
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