CN106380806A - Conductive polylactic acid composite material composition for hot-melt 3D printing and preparation method thereof - Google Patents
Conductive polylactic acid composite material composition for hot-melt 3D printing and preparation method thereof Download PDFInfo
- Publication number
- CN106380806A CN106380806A CN201610862731.6A CN201610862731A CN106380806A CN 106380806 A CN106380806 A CN 106380806A CN 201610862731 A CN201610862731 A CN 201610862731A CN 106380806 A CN106380806 A CN 106380806A
- Authority
- CN
- China
- Prior art keywords
- composite material
- lactic acid
- conductive
- acid composite
- printing
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Abstract
The invention discloses a conductive polylactic acid composite material composition for hot-melt 3D printing and a preparation method thereof. The composition comprises the following components (in parts by mass): 90-75 parts of polylactic acid, 0.5-2 parts of silver nanowire, 0.01-0.05 part of coupling agent, 1-5 parts of compatilizer, 0.3-0.6 part of antioxidant, 1-5 parts of toughener, 0.5-2 parts of lubricant, 0.1-2 parts of nucleator and 0.5-2 parts of plasticizer. The preparation method comprises the following steps: dissolving the polylactic acid in dichloroethane, adding the silver nanowire, dispersing the silver nanowire in the polylactic acid solution under ultrasonic action, evaporating the dichloroethane, uniformly mixing the components through a double screw extruder, and extruding strips at an extrusion temperature of 140-190 DEG C. The prepared composite material has excellent flowability and low mold shrinkage rate, and is suitable for hot-melt 3D rapid printing forming; the notch impact strength can be up to 20 KJ/m<2> or above, and the volume resistivity is 200 ohm/cm or below; and the composite material can be used for high-toughness conductive 3D printing products.
Description
Technical field
The present invention relates to the field of high polymer composite material preparation of heat molten type 3D printing speed molding, more particularly to a kind of
Conductive lactic acid composite material compositionss for heat molten type 3D printing and preparation method thereof.
Background technology
In recent years, rapid shaping has obtained significant progress, and wherein three-dimensional (3D) printing technique is increasingly mature and industrialization,
In the gradually popularization and application of the fields such as biological engineering, Aero-Space, building, design.3D printing has several, is also the most simply minimum one-tenth
This is plastic hot melt deposition printing shaping, using plastic strip, heats, quickly plastic molten melt is become liquid at die cavity and shower nozzle
Body, then prints 3D product layer by layer.There are ABS, nylon, polylactic acid etc. using more plastics variety.
Polylactic acid is plastics that be polymerized by lactic acid, fully biodegradable, is completely green ecological biological plasticss, no
Consume fossil energy, applied in fields such as medicine, medical treatment, organizational projects.But, polylactic acid toughness itself is poor, knot
Brilliant speed is slower, and thermostability is relatively low, limits its application in some fields, thus normal needs are modified and are combined.With
The fast development of plastics industry, the modification of macromolecular material and complex technique are also increasingly mature, develop changing of multiple polylactic acid
Property and composite, but be applied to 3D printing have conductive characteristic lactic acid composite material report few, be therefore badly in need of into
Row exploitation and industrialization.
Content of the invention
Based on the problems of above-mentioned prior art, the present invention provides a kind of conduction for heat molten type 3D printing to gather breast
Sour composite and preparation method thereof, energy.
For solving above-mentioned technical problem, the present invention provides a kind of conductive lactic acid composite material for heat molten type 3D printing
Compositionss are it is characterised in that said composition includes the following component measured in parts by mass：
The embodiment of the present invention provides a kind of preparation of the conductive lactic acid composite material compositionss for heat molten type 3D printing
Method, for preparing conduction lactic acid composite material compositionss of the present invention, comprises the following steps：
Obtain each component by conduction lactic acid composite material composite formula of the present invention；
First, polylactic acid is dissolved in the dichloroethanes that mass concentration is 5%, is subsequently adding nano silver wire, stirring is all
Even, add coupling agent, stir 30 minutes～1 hour under ul-trasonic irradiation, then evaporation of dichloroethane, by residue in vacuum
It is dried to the flake that thickness is not more than 5mm in drying baker, cools down after being dried, pulverize；By remaining component in formula, it is added to
In high-speed mixer, mixed at high speed adds mixture to melting mixing in screw extruder after 1 minute, and tank cools down, and pulls into
The strand of diameter of phi 1.75mm ± 0.2mm, uses for fusion sediment 3D printer；The screw slenderness ratio of used screw extruder
For 32～40, screw combinations are moderate shear rate combinations mode, and temperature is 140～190 DEG C.
Beneficial effects of the present invention are：The method by being combined nano silver wire with polylactic acid, then adds coupling agent, compatible
The lactic acid composite material of electric conductivity prepared by agent, nucleator, lubricant etc., this conductive lactic acid composite material compositionss tool
There are high fluidity, rapid crystallization and high tenacity, its shrinkage factor is low, printing precision is high it is adaptable to fusion sediment 3D beats
Print rapid shaping, extends the application of polylactic acid.
Brief description
In order to be illustrated more clearly that the technical scheme of the embodiment of the present invention, below will be to required use in embodiment description
Accompanying drawing be briefly described it should be apparent that, drawings in the following description are only some embodiments of the present invention, for this
For the those of ordinary skill in field, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings
Accompanying drawing.
Fig. 1 prepares, for the embodiment of the present invention, the twin screw integrated mode schematic diagram that conductive lactic acid composite material adopts.
Specific embodiment
Below the embodiment it is clear that described is clearly and completely described to the technical scheme in the embodiment of the present invention
It is only a part of embodiment of the present invention, rather than whole embodiments.Based on embodiments of the invention, ordinary skill
The every other embodiment that personnel are obtained under the premise of not making creative work, broadly falls into protection scope of the present invention.
The embodiment of the present invention provides a kind of conductive lactic acid composite material compositionss for heat molten type 3D printing, this combination
Thing includes the following component measured in parts by mass：
In said method, polylactic acid adopt high molecular poly-L-lactic acid (PLLA), this poly-L-lactic acid at 190 DEG C, 2.16kgf bar
Melt flow index (MI) under part is 5～40g/10min；Preferably employ the poly- L that melt flow index is 10～20g/10min
Lactic acid；Polylactic acid molecule amount is too high, and melting viscosity is big, and shower nozzle drippage is slow, affects print speed；Polylactic acid molecule amount is too low, system
Product mechanical property is bad.
Described coupling agent adopts silane coupler；Silane coupler adopt gamma-aminopropyl-triethoxy-silane (KH-550),
γ-glycydoxy trimethoxy silane (KH-560), γ-methacryloxypropyl trimethoxy silane
(KH-570) any one in；Dispersibility in polylactic acid for the CNT can be greatly improved using silane coupler.
Described antioxidant adopts the mixture of antioxidant 1010 and irgasfos 168, wherein antioxidant 1010 and irgasfos 168
Mass ratio be 1：1～1：5；Antioxidant 1010 is preferably 1 with the mass ratio of irgasfos 168：2.The application of this antioxidant
Avoid degraded in process.
In said method, a diameter of 5～50nm of nano silver wire that adopted, length is 100～200 μm.
In said method, Research of Grafting Malaic Anhydride Onto Polyethylene that described compatilizer is 1～4% using percent grafting, styrene-the third
Alkene nitrile-glycidyl methacrylate terpolymer and the mixture of ethylene butyl acrylate copolymer.Using with ring
The compatilizer of oxygen groups also has the effect to polylactic acid chain extension, thus improving the toughness of lactic acid composite material.
In said method, described toughener adopts transparent butylbenzene anti-impact resin (also known as K-Resin, K- resin), melt flow
Dynamic index M I is 8～15g/10min.
In said method, described lubricant adopts ethylene bis stearamide (EBS), OPE (OPE), cohune
One of palmitic acid wax or arbitrarily several mixture.3D printing can be made more smooth using this specific mixed lubrication agent, with
When product surface bright, attractive in appearance.
In said method, described nucleator adopts the mixture of decanedioic acid dibenzoyl hydrazine and nano silicon；Add
This specific nucleator can improve crystallization rate and the crystallization integrity of polylactic acid, thus improving printing speed efficiency and product
Performance.Nano silicon can be also both reinforcing agent as nucleator, can improve the intensity of lactic acid composite material and resistance to
Hot.
Described plasticizer adopts the polyethylene glycol oxide (PEO) of molecular weight 100000～500000, the addition of this plasticizer
Improve the mobility of polylactic acid, be suitable to rapid shaping.
The embodiment of the present invention provides a kind of preparation of the conductive lactic acid composite material compositionss for heat molten type 3D printing
Method, for above-mentioned conductive lactic acid composite material compositionss, comprises the following steps：
Obtain each component by above-mentioned conductive lactic acid composite material composite formula；
First, polylactic acid is dissolved in the dichloroethanes that mass concentration is 5%, is subsequently adding nano silver wire, stirring is all
Even, add coupling agent, stir 30 minutes～1 hour under ul-trasonic irradiation, then evaporation of dichloroethane, by residue in vacuum
It is dried to the flake that thickness is not more than 5mm in drying baker, cools down after being dried, pulverize；By remaining component in formula, it is added to
In high-speed mixer, mixed at high speed adds mixture to melting mixing in screw extruder after 1 minute, and tank cools down, and pulls into
The strand of diameter of phi 1.75mm ± 0.2mm, uses for fusion sediment 3D printer；Screw extruder adopts peg type single screw rod to squeeze
Go out machine, double screw extruder, any one in reciprocating single-bolt extruder, it is preferred to use double screw extruder is (as Fig. 1 institute
Show), the screw slenderness ratio of used screw extruder is 32～40, and screw combinations are moderate shear rate combinations mode, temperature
For 140～190 DEG C.
With reference to specific embodiment, compositionss of the present invention and preparation method thereof are described further.
Using SZ-900/NB injector injection moulding standard specimen, molding technological condition：Injection temperature (charge door) 170/
180/185/180 DEG C (nozzle)；Injection pressure 30MPa, dwell time 8s；Cool time 20s；
Performance test methods are as follows：
Melt flow rate (MFR) (MI)：Carry out according to GB/T 3682-2000 standard；
Tensile strength and elongation at break：Carry out according to GB/T 1040-2006 standard；
Bending strength and bending moduluses：Carry out according to GB/T 9341-2008 standard；
Single beam notched impact properties：Carry out according to GB/T1043-2008 standard；
Heat distortion temperature：Carry out according to GB/T1634-2004 standard；Maximum deflection direct stress 0.46MPa, programming rate：2
℃/min；
Specific insulation：Carry out according to GB/T1410-2006 standard；
Molding shrinkage：Carry out by GB/T 15585-1995 standard.
The formula of comparative example and embodiment 1～3 is shown in Table 1：
Table 1 comparative example and the conductive lactic acid composite material composite formula table of embodiment 1～3
Preparation method：First, polylactic acid is dissolved in the dichloroethanes that mass concentration is 5% (50 DEG C of solution temperature, stirs
Mix), it is subsequently adding nano silver wire, stirs, add coupling agent, stirring 30 minutes～1 hour under ul-trasonic irradiation, then
Dichloroethanes are evaporated by evacuation again, residue are dried in vacuum drying oven laminar (thickness is not more than 5mm), are dried
After cool down, pulverize；Weigh remaining component each by formula proportion, be added in high-speed mixer, mixed at high speed will mix after 1 minute
Thing is added to melting mixing in screw extruder, and tank cools down, and pulls into the strand of diameter of phi 1.75mm ± 0.2mm, heavy for melting
Long-pending 3D printer uses.It is characterized in that, the screw extruder being used is peg type single screw extrusion machine, twin-screw extrusion
Machine, reciprocating single-bolt extruder, preferably double screw extruder, its screw slenderness ratio is 32～40, and screw combinations are medium cutting
Cutting speed rate compound mode is (see accompanying drawing 1, in Fig. 1：A is vacuum exhaust；B is aerofluxuss；C is kneading block；D is family's hopper；E is
Plus thread element), temperature (process conditions are shown in Table 2) between 150～190 DEG C.
The conductive lactic acid composite material preparation technology parameter of table 2 embodiment 1～3
The performance of comparative example and embodiment 1～3 is shown in Table 3.
The performance of the conductive lactic acid composite material of table 3
From table 3 it can be seen that after adding carbon nano silver wire and compatilizer, toughener in polylactic acid, the leading of composite
Electrically greatly improve with impact flexibility, molding shrinkage is decreased obviously, the melt flow rate (MFR) of composite is higher than pure PLA simultaneously
Melt flow rate (MFR), and still substantially maintain the bending strength of composite, bending moduluses and heat distortion temperature and decline.
In a word, the combination property of the composite of present invention preparation greatly improves, and the dimensional stability of obtained product increases, and is conducive to
Improve the precision printing product.It is of special importance that the electric conductivity of composite increases substantially, go for wanting to conductive
Seek higher 3D printing product, effectively expand the application of polylactic acid.The notch impact strength of this composite
Up to 20kJ/m2More than, specific insulation is 200 Ω/below cm, can be used for requirement high tenacity, conductive 3D printing product.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any those familiar with the art in the technical scope of present disclosure, the change or replacement that can readily occur in,
All should be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Enclose and be defined.
Claims (10)
1. a kind of conductive lactic acid composite material compositionss for heat molten type 3D printing are it is characterised in that said composition includes
The following component measured in parts by mass：
2. the conductive lactic acid composite material compositionss for heat molten type 3D printing according to claim 1, its feature exists
Adopt high molecular poly-L-lactic acid (PLLA) in, described polylactic acid, this poly-L-lactic acid at 190 DEG C, the melt flow under the conditions of 2.16kgf
Dynamic index (MI) is 5～40g/10min；
Described coupling agent adopts silane coupler；
Described antioxidant adopts the matter of the mixture of antioxidant 1010 and irgasfos 168, wherein antioxidant 1010 and irgasfos 168
Amount ratio is 1：1～1：5.
3. the conductive lactic acid composite material compositionss for heat molten type 3D printing according to claim 2, its feature exists
In,
Described poly-L-lactic acid preferably employs the poly-L-lactic acid that melt flow index is 10～20g/10min；
Described silane coupler adopts gamma-aminopropyl-triethoxy-silane (KH-550), γ-glycydoxy front three
Any one in TMOS (KH-560), γ-methacryloxypropyl trimethoxy silane (KH-570)；
Described antioxidant 1010 is preferably 1 with the mass ratio of irgasfos 168：2.
4. the conductive lactic acid composite material compositionss for heat molten type 3D printing according to claim 1, its feature exists
In, a diameter of 5～50nm of the nano silver wire being adopted, length is 100～200 μm.
5. the conductive lactic acid composite material compositionss for heat molten type 3D printing according to claim 1, its feature exists
In Research of Grafting Malaic Anhydride Onto Polyethylene that described compatilizer is 1～4% using percent grafting, styrene-acrylonitrile-methacrylic acid
Ethylene oxidic ester terpolymer and the mixture of ethylene butyl acrylate copolymer.
6. the conductive lactic acid composite material compositionss for heat molten type 3D printing according to claim 1, its feature exists
In described toughener adopts transparent butylbenzene anti-impact resin, and melt flow index MI is 8～15g/10min.
7. the conductive lactic acid composite material compositionss for heat molten type 3D printing according to claim 1, its feature exists
In described lubricant adopts one of ethylene bis stearamide (EBS), OPE (OPE), Brazil wax or appoints
Several mixture of meaning.
8. the conductive lactic acid composite material compositionss for heat molten type 3D printing according to claim 1, its feature exists
In described nucleator adopts the mixture of decanedioic acid dibenzoyl hydrazine and nano silicon；
Described plasticizer adopts the polyethylene glycol oxide (PEO) of molecular weight 100000～500000.
9. a kind of preparation method of the conductive lactic acid composite material compositionss for heat molten type 3D printing is it is characterised in that use
In the conductive lactic acid composite material compositionss described in preparation any one of claim 1 to 8, comprise the following steps：
Conductive lactic acid composite material composite formula as described in any one of claim 1 to 8 obtains each component；
First, polylactic acid is dissolved in the dichloroethanes that mass concentration is 5%, is subsequently adding nano silver wire, stirs, plus
Enter coupling agent, stir 30 minutes～1 hour under ul-trasonic irradiation, then evaporation of dichloroethane, by residue in vacuum drying
It is dried to the flake that thickness is not more than 5mm in case, cools down after being dried, pulverize；By remaining component in formula, it is added at a high speed
In mixer, mixed at high speed adds mixture to melting mixing in screw extruder after 1 minute, and tank cools down, and pulls into diameter
The strand of Φ 1.75mm ± 0.2mm, uses for fusion sediment 3D printer；The screw slenderness ratio of used screw extruder is 32
～40, screw combinations are moderate shear rate combinations mode, and temperature is 140～190 DEG C.
10. the preparation side of the conductive lactic acid composite material compositionss for heat molten type 3D printing according to claim 1
Method is it is characterised in that described screw extruder adopts peg type single screw extrusion machine, double screw extruder, reciprocating single screw rod
Any one in extruder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610862731.6A CN106380806A (en) | 2016-09-28 | 2016-09-28 | Conductive polylactic acid composite material composition for hot-melt 3D printing and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610862731.6A CN106380806A (en) | 2016-09-28 | 2016-09-28 | Conductive polylactic acid composite material composition for hot-melt 3D printing and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106380806A true CN106380806A (en) | 2017-02-08 |
Family
ID=57936071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610862731.6A Pending CN106380806A (en) | 2016-09-28 | 2016-09-28 | Conductive polylactic acid composite material composition for hot-melt 3D printing and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106380806A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107033294A (en) * | 2017-04-21 | 2017-08-11 | 北京石油化工学院 | It is a kind of for conductive UV-cured resin composite of laser 3D printing and preparation method thereof |
| CN107286609A (en) * | 2017-06-20 | 2017-10-24 | 广东波斯科技股份有限公司 | A kind of low-density thermal conductivity PLA 3D printing material and its preparation method and application |
| WO2020049211A1 (en) * | 2018-09-06 | 2020-03-12 | Arctic Biomaterials Oy | Composite filament |
| CN113527765A (en) * | 2021-06-25 | 2021-10-22 | 浙江兴越材料技术有限公司 | Polylactic acid composition and additive composition thereof, plastic product and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607656A (en) * | 2015-03-06 | 2015-05-13 | 中国科学院上海硅酸盐研究所 | Super-long silver nanowire and preparation method thereof |
| CN105111703A (en) * | 2015-09-15 | 2015-12-02 | 北京石油化工学院 | Preparation method of conductive polylactic acid composite for thermal fusion 3D printing |
| CN105623215A (en) * | 2016-02-02 | 2016-06-01 | 北京化工大学 | Flexible circuit conductive composition and 3D (three dimensional) printing based flexible circuit construction method |
-
2016
- 2016-09-28 CN CN201610862731.6A patent/CN106380806A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607656A (en) * | 2015-03-06 | 2015-05-13 | 中国科学院上海硅酸盐研究所 | Super-long silver nanowire and preparation method thereof |
| CN105111703A (en) * | 2015-09-15 | 2015-12-02 | 北京石油化工学院 | Preparation method of conductive polylactic acid composite for thermal fusion 3D printing |
| CN105623215A (en) * | 2016-02-02 | 2016-06-01 | 北京化工大学 | Flexible circuit conductive composition and 3D (three dimensional) printing based flexible circuit construction method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107033294A (en) * | 2017-04-21 | 2017-08-11 | 北京石油化工学院 | It is a kind of for conductive UV-cured resin composite of laser 3D printing and preparation method thereof |
| CN107286609A (en) * | 2017-06-20 | 2017-10-24 | 广东波斯科技股份有限公司 | A kind of low-density thermal conductivity PLA 3D printing material and its preparation method and application |
| WO2020049211A1 (en) * | 2018-09-06 | 2020-03-12 | Arctic Biomaterials Oy | Composite filament |
| CN113527765A (en) * | 2021-06-25 | 2021-10-22 | 浙江兴越材料技术有限公司 | Polylactic acid composition and additive composition thereof, plastic product and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103342858B (en) | A kind of short glass fiber reinforced polypropylene compound material and its preparation method and application | |
| CN106380806A (en) | Conductive polylactic acid composite material composition for hot-melt 3D printing and preparation method thereof | |
| CN104479205B (en) | A kind of injection molding forming method of graphene modified poly ethylene high-strength composite thin products | |
| CN104725802A (en) | Preparation method of polylactic acid composite material for hot-melt 3D printing | |
| JP2003534955A (en) | Oriented nanofibers embedded in a polymer matrix | |
| JP2009534226A5 (en) | ||
| CN106633363A (en) | Polypropylene composition for 3D printing, and preparation method thereof | |
| CN107083030A (en) | A kind of low warpage high-strength glass fiber enhanced PBT/ASA alloy materials and preparation method thereof | |
| CN105111703A (en) | Preparation method of conductive polylactic acid composite for thermal fusion 3D printing | |
| CN109824979B (en) | Needle-shaped color master batch, preparation method thereof and plastic product | |
| CN107141699A (en) | One kind is used for 3D printing ABS composite material and preparation method thereof | |
| CN106751379A (en) | Product prepared by a kind of fused glass pellet technique and preparation method thereof | |
| CN106995596A (en) | A kind of high crystalline PLA material of 3D printing and preparation method thereof | |
| CN112126243B (en) | Liquid crystal polymer composition | |
| CN104592730A (en) | Polylactic acid/polyester alloy and preparation method thereof | |
| CN104194123B (en) | The preparation method of polyacrylonitrile fibre/high-density polyethylene composite material | |
| CN105017765A (en) | Basic magnesium sulfate whisker/PA610T composite material and preparation method thereof | |
| CN104672847A (en) | Glass fiber reinforced polycarbonate (PC) composite material and preparation method thereof | |
| CN101870807B (en) | Polycarbonate/polyethylene alloy conductive composite material and preparation method thereof | |
| CN103753727A (en) | Method for preparing polymer/inorganic filler composite material | |
| CN105440679A (en) | PPS composite conductive reinforced material and preparation method therefor | |
| CN103289197B (en) | Polypropylene composite material of containing potassium titanate whisker and glass fibre and preparation method thereof | |
| CN109054189A (en) | A kind of plant composite fibre filling polypropylene composite material and preparation method thereof | |
| CN108117744A (en) | It is a kind of for nylon material of increasing material manufacturing and preparation method thereof | |
| CN104693800A (en) | Impact-resistant conductive PPS/LCP composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170208 |