CN115028989B - Nylon composite powder, preparation method thereof and application thereof in laser sintering - Google Patents
Nylon composite powder, preparation method thereof and application thereof in laser sintering Download PDFInfo
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- CN115028989B CN115028989B CN202210734888.6A CN202210734888A CN115028989B CN 115028989 B CN115028989 B CN 115028989B CN 202210734888 A CN202210734888 A CN 202210734888A CN 115028989 B CN115028989 B CN 115028989B
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- 239000000843 powder Substances 0.000 title claims abstract description 156
- 239000004677 Nylon Substances 0.000 title claims abstract description 148
- 229920001778 nylon Polymers 0.000 title claims abstract description 148
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000149 argon plasma sintering Methods 0.000 title description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229960000892 attapulgite Drugs 0.000 claims abstract description 34
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 34
- 239000011259 mixed solution Substances 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002019 doping agent Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 23
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 8
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 2
- 230000007480 spreading Effects 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 239000002121 nanofiber Substances 0.000 claims 1
- 239000000463 material Substances 0.000 description 31
- 239000011246 composite particle Substances 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000000110 selective laser sintering Methods 0.000 description 14
- 239000008187 granular material Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 238000007873 sieving Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 238000010146 3D printing Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- -1 ethanol dilauryl amide Chemical compound 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920000767 polyaniline Polymers 0.000 description 3
- DHGARFOQTPTLET-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)(=O)N.C(CCCCCCCCCCCCCCCCC)(=O)N.C(C)O Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)N.C(CCCCCCCCCCCCCCCCC)(=O)N.C(C)O DHGARFOQTPTLET-UHFFFAOYSA-N 0.000 description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- WMLQMUZIKADTHR-UHFFFAOYSA-N C(CCCCCCCCCCC)(=O)N.C(CCCCCCCCCCC)(=O)N.C(C)O Chemical compound C(CCCCCCCCCCC)(=O)N.C(CCCCCCCCCCC)(=O)N.C(C)O WMLQMUZIKADTHR-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- 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
- B29C64/141—Processes of additive manufacturing using only solid materials
- B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
-
- 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
- B29C64/386—Data acquisition or data processing for additive manufacturing
- B29C64/393—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
-
- 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
- B33Y50/00—Data acquisition or data processing for additive manufacturing
- B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
-
- 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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- 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
- C08K2201/001—Conductive additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
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Abstract
The invention discloses a preparation method of nylon composite powder, which comprises the steps of mixing attapulgite, aniline monomer, oxidant, doping agent and deionized water for reaction to obtain fibrous conductive powder; mixing nylon, an anti-sticking agent and an organic solvent to obtain a nylon mixed solution; and heating the fibrous conductive powder and the nylon mixed solution for reaction, decompressing, cooling to room temperature, and performing aftertreatment to obtain the nylon composite powder. The invention also provides the nylon composite powder prepared by the preparation method of the nylon composite powder and application of the nylon composite powder in laser scanning forming. The formed part formed by laser scanning has higher mechanical property and dimensional precision, and also has higher electric conduction, heat conduction and flame retardance functions.
Description
Technical Field
The invention belongs to the field of additive manufacturing, and particularly relates to nylon composite powder, a preparation method thereof and application thereof in laser sintering.
Background
Additive manufacturing (additive manufacturing, AM), also known as 3D printing, belongs to one of the rapid prototyping (rapid prototyping, RP) techniques, and is a method for directly manufacturing three-dimensional physical entities in a layer-by-layer stacking manner based on a computer three-dimensional CAD model. The additive manufacturing technology is not limited by the shape of a formed geometric entity, the three-dimensional model processing is directly changed into plane processing, and parts with any complex shape and structure can be rapidly and precisely manufactured on one piece of equipment, so that free manufacturing is realized. As a prospective and strategic technology, the engineering application is very strong, the field span is large, and the technology is very important to the development of future manufacturing industry, especially high-end manufacturing. The composite material has wide application prospect in the fields of automobile parts, aerospace parts, medical devices and the like.
Selective Laser Sintering (SLS), also known as selective laser sintering, has emerged in the 80 s of the last century as a 3D printing technology based on additive manufacturing. The principle of the method is that a layer of powder material is paved on a workbench in advance, and laser is controlled by a computer to sinter solid part powder according to interface contour information, and then the powder is continuously circulated and stacked layer by layer for forming. The technology requires that the powder material has uniform particle size distribution and good fluidity, which is beneficial to powder bed powder. The forming method has the characteristics of simple manufacturing process, high flexibility, high material utilization rate, high forming speed and the like.
The nylon material is used as the first engineering plastic at present, most varieties are crystalline polymers, amide bonds are contained in macromolecular chains, hydrogen bonds can be formed, and the nylon material has the excellent characteristics of toughness, wear resistance, impact resistance, fatigue resistance, corrosion resistance and the like, and particularly has excellent wear resistance and self-lubricating property and small friction coefficient, so that nylon steadily and rapidly grows in strong competition with other engineering plastics, and is widely applied to manufacturing of parts such as automobile household appliances, sports equipment and the like. But the nylon material has low oxygen index and high combustion speed, and generates a large amount of dense smoke and molten drops in the combustion process, so that flame is easy to propagate, thereby greatly limiting the application of the nylon material in the special fields of aerospace, automobile manufacturing, electronic appliances and the like. The functional part with higher density and better mechanical property can be directly formed through an SLS process, and becomes one of the SLS forming materials which are most widely used at present.
The Chinese patent with the patent number of CN106426916A discloses a 3D printing method which comprises the following steps: mixing powdery material to be processed and powdery nylon material. The nylon material is melted using a selective laser sintering technique to bond the material to be processed to form a green body. The green body is heated to thermally degrease to volatilize the nylon material. Heating the green body to a sintering temperature of the material to be processed to sinter the green body. The ambient temperature of the green body was reduced to room temperature to obtain a dense part. The 3D printing method of the invention does not need to use high-intensity laser beams, has low temperature in the processing process, can not generate thermal strain and residual stress, avoids the problems of warping, cracking and/or delamination of parts, and ensures the mechanical property and dimensional accuracy of the parts. However, the mechanical properties of the pure nylon sample molded by the SLS technology are generally lower than those of the traditional injection molding sample, and the functions of electric conduction, heat conduction and flame retardance are lacking, so that the performance requirements of certain high-end application fields cannot be met.
Disclosure of Invention
The invention provides a preparation method of nylon composite powder, and a sample formed by the nylon composite powder prepared by the method after laser scanning forming has higher mechanical property and higher electric conduction, heat conduction and flame retardance.
A preparation method of nylon composite powder comprises the following steps:
mixing attapulgite, aniline monomer, oxidant and doping agent with deionized water for reaction for 5-8 hours to obtain fibrous conductive powder;
mixing nylon, an anti-sticking agent and an organic solvent to obtain a nylon mixed solution;
and heating the fibrous conductive powder and the nylon mixed solution for reaction, decompressing, cooling to room temperature, and performing aftertreatment to obtain the nylon composite powder.
The attapulgite has a length of 0.5-2um and a diameter of 20-50 nm.
The mass ratio of the attapulgite to the aniline monomer is 1:0.1-0.4. Further preferably, the mass ratio of the attapulgite to the aniline monomer is 1:0.2-0.3.
When the proportion of the aniline monomer is too low, polyaniline is difficult to be formed through in-situ polymerization to realize effective total coating of the attapulgite, and when the proportion of the aniline monomer is too high, independent polyaniline particles are formed to influence the dispersibility and uniformity of the powder, so that the mechanical property, the electric conduction, the heat conduction and the flame retardance of the composite material are influenced.
The oxidant is ammonium persulfate or ferric chloride.
The mass ratio of the aniline to the oxidant is 1:1.3-1.8, and more preferably, the mass ratio of the aniline to the oxidant is 1:1.5.
The doping agent is benzene sulfonic acid, hydrochloric acid or phosphoric acid.
The mass ratio of the fibrous conductive powder to the nylon mixed solution is 1:10-40.
The mass ratio of the aniline to the dopant is 1:1.1-1.5, and more preferably, the mass ratio of the attapulgite to the dopant is 1:1.3.
The mass ratio of the attapulgite to the deionized water is 1:20-30, and more preferably, the mass ratio of the attapulgite to the deionized water is 1:25.
The anti-sticking agent is at least one of oleamide, erucamide, ethanol bisstearamide and ethanol bislauramide.
The organic solvent is at least one of ethylene glycol, isopropanol, N-butanol and N, N-dimethylformamide.
The mass of the anti-sticking agent is 0.1-1% of that of nylon;
the mass percentage concentration of nylon in the mixed solution is 5-25%.
The heating temperature is 130-200deg.C, heating time is 0.5-2h, and further preferably, the heating temperature is 150-180deg.C.
The cooling rate is 2-5 ℃/min, and in order to make the particle size distribution more uniform, the cooling rate is more preferably 4 ℃/min.
The post-treatment is filtering, drying and sieving. The agglomerated large particles are removed by sieving.
The invention also provides the nylon composite powder prepared by the preparation method of the nylon composite powder.
The invention also provides application of the nylon composite powder in laser sintering forming, which comprises the following steps:
(1) Uniformly spreading the nylon composite powder on a processing platform, heating the processing platform to a processing temperature, and carrying out laser scanning based on a set two-dimensional sheet layer;
(2) After the laser scanning is finished, shifting down one powder layer thickness, and repeating the step (1);
(3) Repeating the steps (1) and (2) until a laser sintered part is obtained; the laser power is 30-80w, the laser scanning speed is 4-6m/s, the thickness of each powder layer is 0.08-0.95mm, and the processing temperature is 170-185 ℃.
The laser scanning mode is that scanning is performed from inside to outside.
Further, the thickness of each powder layer is 0.10-0.11mm.
Further, the processing temperature was 180 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, polyaniline is guided to be uniformly coated on the surface of the attapulgite through in-situ polymerization of an aniline monomer loaded on the attapulgite to form fibrous conductive powder, and nylon (also called polyamide) is guided to be tightly combined with the fibrous conductive powder in the hot-melting-cooling precipitation process through interaction of a large number of aniline groups and amide groups existing on the surface of the fibrous conductive powder, so that uniform dispersion and efficient interface fusion of the fibrous conductive powder in a nylon matrix are realized, a stable network structure is formed, and a sample obtained through laser sintering has good mechanical property and electric conduction, heat conduction and flame retardance.
(2) The fibrous attapulgite material is introduced into the nylon composite powder, the attapulgite is an inorganic rigid nano material, has a low thermal expansion coefficient, and the uniform distribution of the attapulgite in the nylon matrix can effectively reduce the thermal expansion coefficient of the nylon composite powder, so that the nylon composite powder is not easy to warp and deform in the laser sintering forming process, and the dimensional accuracy of a formed sample is improved.
Drawings
FIG. 1 is an SEM photograph of a nylon composite powder material prepared in example 1
FIG. 2 is an SEM photograph of a pure nylon powder material prepared in comparative example 1
FIG. 3 is an SEM photograph of the pure attapulgite/nylon composite powder material prepared in comparative example 2.
Detailed Description
The present invention will be further described in detail with reference to the following examples for further elucidation of the objects, technical solutions and advantages of the present invention, but without thereby limiting the scope of the present invention.
Example 1
(1) 1000g of nylon granules, 200g of attapulgite powder, 60g of aniline monomer, 80g of oxidant ammonium persulfate and 75g of dopant benzenesulfonic acid are weighed;
(2) Adding the attapulgite, aniline monomer, ammonium persulfate and benzenesulfonic acid into 5000g of deionized water, stirring and ultrasonically oscillating for 6 hours to obtain fibrous powder;
(3) Adding the nylon granules and the ethanol dilauryl amide anti-sticking agent into N, N-dimethylformamide according to the mass ratio of 1:0.005 to prepare a mixed solution with the mass concentration of nylon of 15 percent;
(4) Placing the fibrous powder prepared in the step (2) and the nylon mixed solution prepared in the step (3) into a high-pressure reaction kettle, introducing nitrogen to pressurize to 1MPa, and stirring at a high speed (630 rpm); raising the temperature to 175 ℃, and preserving the heat for 1.5 hours until the nylon is completely dissolved; after complete dissolution, the high pressure is released, and the temperature is reduced to room temperature at the speed of 4 ℃/min, so as to obtain nylon composite particle suspension;
(5) Carrying out vacuum drying treatment on the nylon composite particles prepared in the step (4), and sieving the nylon composite particles with a 200-mesh sieve to obtain a nylon composite powder material; as shown in an electron microscope SEM photograph of the nylon composite powder material as shown in figure 1, the conductive fibers in the nylon composite powder material are uniformly dispersed in a nylon matrix, so that the nylon composite powder material plays a good role in reinforcing and modifying.
(6) Adding the prepared nylon composite powder into a powder supply bin of selective laser sintering forming equipment, uniformly paving the nylon composite powder on a processing platform by a powder paving scraper, emitting laser by a laser, paving the powder for 6mm, setting the processing temperature to 185 ℃, setting the processing platform temperature to 130 ℃, and pre-baking the powder for 2 hours; starting processing after baking powder, controlling the switch of the laser and the angle of the scanner by the computer, so that the laser beam scans on a processing plane according to the shape of the corresponding two-dimensional slice, moving the workbench downwards for one layer thickness after the laser beam scans, paving powder again, scanning the laser beam, and repeating the steps to obtain a laser sintering piece; wherein the laser beam scans on the processing platform from inside to outside, the laser power is 60W, the scanning speed is 5m/s, and the thickness of the powder layer is 0.95mm.
Example 2
(1) 1000g of nylon granules, 100g of attapulgite powder, 20g of aniline monomer, 26g of oxidant iron chloride and 22g of doping agent hydrochloric acid are weighed;
(2) Adding the attapulgite, aniline monomer, ferric chloride and hydrochloric acid into 2000g of deionized water, stirring and carrying out ultrasonic oscillation for 5 hours to obtain fibrous powder;
(3) Adding the nylon granules and the ethanol bis-stearamide anti-sticking agent into n-butanol according to the mass ratio of 1:0.001 to prepare a mixed solution with the mass concentration of nylon of 5 percent;
(4) Placing the fibrous powder prepared in the step (2) and the nylon mixed solution prepared in the step (3) into a high-pressure reaction kettle, introducing nitrogen to pressurize to 1MPa, and stirring at a high speed (630 rpm); raising the temperature to 130 ℃, and preserving heat for 0.5 to completely dissolve nylon; after complete dissolution, the high pressure is released, and the temperature is reduced to room temperature at the speed of 4 ℃/min, so as to obtain nylon composite particle suspension;
(5) And (3) carrying out vacuum drying treatment on the nylon composite particles prepared in the step (4), and sieving the nylon composite particles with a 200-mesh sieve to obtain the nylon composite powder material.
(6) Adding the prepared nylon composite powder into a powder supply bin of selective laser sintering forming equipment, uniformly paving the nylon composite powder on a processing platform by a powder paving scraper, emitting laser by a laser, paving the powder for 6mm, setting the processing temperature to 175 ℃, setting the processing platform temperature to 130 ℃, and pre-baking the powder for 2 hours; starting processing after baking powder, controlling the switch of the laser and the angle of the scanner by the computer, so that the laser beam scans on a processing plane according to the shape of the corresponding two-dimensional slice, moving the workbench downwards for one layer thickness after the laser beam scans, paving powder again, scanning the laser beam, and repeating the steps to obtain a laser sintering piece; wherein the laser beam scans on the processing platform from inside to outside, the laser power is 30W, the scanning speed is 4m/s, and the thickness of the powder layer is 0.08mm.
Example 3
(1) 1000g of nylon granules, 350g of attapulgite powder, 140g of aniline monomer, 224g of oxidant ammonium persulfate and 210g of dopant phosphoric acid are weighed;
(2) Adding the attapulgite, aniline monomer, ammonium persulfate and phosphoric acid into 10500g of deionized water, stirring and ultrasonically oscillating for 8 hours to obtain fibrous powder;
(3) Adding the nylon granules and the erucamide anti-sticking agent into isopropanol according to the mass ratio of 1:0.01 to prepare a mixed solution with the mass concentration of nylon of 25 percent;
(4) Placing the fibrous powder prepared in the step (2) and the nylon mixed solution prepared in the step (3) into a high-pressure reaction kettle, introducing nitrogen to pressurize to 1MPa, and stirring at a high speed (630 rpm); raising the temperature to 200 ℃, and preserving the heat for 2 hours until the nylon is completely dissolved; after complete dissolution, the high pressure is released, and the temperature is reduced to room temperature at the speed of 4 ℃/min, so as to obtain nylon composite particle suspension;
(5) And (3) carrying out vacuum drying treatment on the nylon composite particles prepared in the step (4), and sieving the nylon composite particles with a 200-mesh sieve to obtain the nylon composite powder material.
(6) Adding the prepared nylon composite powder into a powder supply bin of selective laser sintering forming equipment, uniformly paving the nylon composite powder on a processing platform by a powder paving scraper, emitting laser by a laser, paving the powder for 6mm, setting the processing temperature to be 200 ℃, setting the processing platform temperature to be 130 ℃, and pre-baking the powder for 2 hours; starting processing after baking powder, controlling the switch of the laser and the angle of the scanner by the computer, so that the laser beam scans on a processing plane according to the shape of the corresponding two-dimensional slice, moving the workbench downwards for one layer thickness after the laser beam scans, paving powder again, scanning the laser beam, and repeating the steps to obtain a laser sintering piece; wherein the laser beam scans on the processing platform from inside to outside, the laser power is 80W, the scanning speed is 6m/s, and the thickness of the powder layer is 0.15mm.
Example 4
(1) 1000g of nylon granules, 200g of attapulgite powder, 60g of aniline monomer, 80g of oxidant ammonium persulfate and 75g of dopant benzenesulfonic acid are weighed;
(2) Adding the attapulgite, aniline monomer, ammonium persulfate and benzenesulfonic acid into 5000g of deionized water, stirring and ultrasonically oscillating for 6 hours to obtain fibrous powder;
(3) Adding the nylon granules and the oleamide anti-sticking agent into ethylene glycol according to the mass ratio of 1:0.005 to prepare a mixed solution with the mass concentration of nylon of 15 percent;
(4) Placing the fibrous powder prepared in the step (2) and the nylon mixed solution prepared in the step (3) into a high-pressure reaction kettle, introducing nitrogen to pressurize to 1MPa, and stirring at a high speed (630 rpm); raising the temperature to 175 ℃, and preserving the heat for 1.5 hours until the nylon is completely dissolved; after complete dissolution, the high pressure is released, and the temperature is reduced to room temperature at the speed of 4 ℃/min, so as to obtain nylon composite particle suspension;
(5) And (3) carrying out vacuum drying treatment on the nylon composite particles prepared in the step (4), and sieving the nylon composite particles with a 200-mesh sieve to obtain the nylon composite powder material.
(6) Adding the prepared nylon composite powder into a powder supply bin of selective laser sintering forming equipment, uniformly paving the nylon composite powder on a processing platform by a powder paving scraper, emitting laser by a laser, paving the powder for 6mm, setting the processing temperature to 185 ℃, setting the processing platform temperature to 130 ℃, and pre-baking the powder for 2 hours; starting processing after baking powder, controlling the switch of the laser and the angle of the scanner by the computer, so that the laser beam scans on a processing plane according to the shape of the corresponding two-dimensional slice, moving the workbench downwards for one layer thickness after the laser beam scans, paving powder again, scanning the laser beam, and repeating the steps to obtain a laser sintering piece; wherein the laser beam scans on the processing platform from inside to outside, the laser power is 60W, the scanning speed is 5m/s, and the thickness of the powder layer is 0.95mm.
Comparative example 1
Pure nylon powder was prepared according to the method described in example 1
(1) Weighing 1000g of nylon granules, and adding the nylon granules and the ethanol dilauryl amide anti-sticking agent into N, N-dimethylformamide according to the mass ratio of 1:0.005 to prepare a mixed solution with the mass concentration of nylon of 15 percent;
(2) Placing the nylon mixed solution prepared in the step (1) into a high-pressure reaction kettle, introducing nitrogen to pressurize to 1MPa, and stirring at a high speed (630 rpm); raising the temperature to 175 ℃, and preserving the heat for 1.5 hours until the nylon is completely dissolved; after complete dissolution, the high pressure is released, and the temperature is reduced to room temperature at the speed of 4 ℃/min, so as to obtain nylon particle suspension;
(3) And (3) carrying out vacuum drying treatment on the nylon particles prepared in the step (2), and sieving the nylon particles with a 200-mesh sieve to obtain the nylon powder material. An electron microscope SEM photograph of the nylon powder material is shown in fig. 2.
(4) Adding the prepared nylon powder into a powder supply bin of selective laser sintering forming equipment, uniformly paving the nylon composite powder on a processing platform by a powder paving scraper, emitting laser by a laser, paving the powder for 6mm, setting the processing temperature to 185 ℃ and the processing platform temperature to 130 ℃, and pre-baking the powder for 2 hours; starting processing after baking powder, controlling the switch of the laser and the angle of the scanner by the computer, so that the laser beam scans on a processing plane according to the shape of the corresponding two-dimensional slice, moving the workbench downwards for one layer thickness after the laser beam scans, paving powder again, scanning the laser beam, and repeating the steps to obtain a laser sintering piece; wherein the laser beam scans on the processing platform from inside to outside, the laser power is 60W, the scanning speed is 5m/s, and the thickness of the powder layer is 0.95mm.
Comparative example 2
Pure attapulgite/nylon powder was prepared as described in example 1 without the addition of aniline monomer, oxidant and dopant
(1) 1000g of nylon pellets and 200g of attapulgite powder were weighed.
(2) Adding the nylon granules and the ethanol dilauryl amide anti-sticking agent into N, N-dimethylformamide according to the mass ratio of 1:0.005 to prepare a mixed solution with the mass concentration of nylon of 15 percent;
(3) Placing pure attapulgite powder and the nylon mixed solution prepared in the step (2) into a high-pressure reaction kettle, introducing nitrogen to pressurize to 1MPa, and stirring at a high speed (630 rpm); raising the temperature to 175 ℃, and preserving the heat for 1.5 hours until the nylon is completely dissolved; after complete dissolution, the high pressure is released, and the temperature is reduced to room temperature at the speed of 4 ℃/min, so as to obtain nylon composite particle suspension;
(4) Carrying out vacuum drying treatment on the nylon composite particles prepared in the step (3), and sieving the nylon composite particles with a 200-mesh sieve to obtain a nylon composite powder material; an electron microscope SEM photograph of the nylon composite powder material is shown in fig. 3, and the fibers in the pure attapulgite/nylon composite powder material are obviously agglomerated.
(5) Adding the prepared nylon composite powder into a powder supply bin of selective laser sintering forming equipment, uniformly paving the nylon composite powder on a processing platform by a powder paving scraper, emitting laser by a laser, paving the powder for 6mm, setting the processing temperature to 185 ℃, setting the processing platform temperature to 130 ℃, and pre-baking the powder for 2 hours; starting processing after baking powder, controlling the switch of the laser and the angle of the scanner by the computer, so that the laser beam scans on a processing plane according to the shape of the corresponding two-dimensional slice, moving the workbench downwards for one layer thickness after the laser beam scans, paving powder again, scanning the laser beam, and repeating the steps to obtain a laser sintering piece; wherein the laser beam scans on the processing platform from inside to outside, the laser power is 60W, the scanning speed is 5m/s, and the thickness of the powder layer is 0.95mm.
Comparative example 3
Nylon composite powder obtained when the mass ratio of aniline monomer to attapulgite was greater than 0.4 was prepared according to the method described in example 1.
(1) 1000g of nylon granules, 200g of attapulgite powder, 100g of aniline monomer, 80g of oxidant ammonium persulfate and 75g of dopant benzenesulfonic acid are weighed;
(2) Adding the attapulgite, aniline monomer, ammonium persulfate and benzenesulfonic acid into 5000g of deionized water, stirring and ultrasonically oscillating for 6 hours to obtain fibrous powder;
(3) Adding the nylon granules and the ethanol dilauryl amide anti-sticking agent into N, N-dimethylformamide according to the mass ratio of 1:0.005 to prepare a mixed solution with the mass concentration of nylon of 15 percent;
(4) Placing the fibrous powder prepared in the step (2) and the nylon mixed solution prepared in the step (3) into a high-pressure reaction kettle, introducing nitrogen to pressurize to 1MPa, and stirring at a high speed (630 rpm); raising the temperature to 175 ℃, and preserving the heat for 1.5 hours until the nylon is completely dissolved; after complete dissolution, the high pressure is released, and the temperature is reduced to room temperature at the speed of 4 ℃/min, so as to obtain nylon composite particle suspension;
(5) And (3) carrying out vacuum drying treatment on the nylon composite particles prepared in the step (4), and sieving the nylon composite particles with a 200-mesh sieve to obtain the nylon composite powder material.
(6) Adding the prepared nylon composite powder into a powder supply bin of selective laser sintering forming equipment, uniformly paving the nylon composite powder on a processing platform by a powder paving scraper, emitting laser by a laser, paving the powder for 6mm, setting the processing temperature to 185 ℃, setting the processing platform temperature to 130 ℃, and pre-baking the powder for 2 hours; starting processing after baking powder, controlling the switch of the laser and the angle of the scanner by the computer, so that the laser beam scans on a processing plane according to the shape of the corresponding two-dimensional slice, moving the workbench downwards for one layer thickness after the laser beam scans, paving powder again, scanning the laser beam, and repeating the steps to obtain a laser sintering piece; wherein the laser beam scans on the processing platform from inside to outside, the laser power is 60W, the scanning speed is 5m/s, and the thickness of the powder layer is 0.95mm.
Characterization of the properties:
table 1 tensile strength, dimensional accuracy, electrical conductivity, thermal conductivity and flame retardant property test data of the formed articles obtained in examples 1 to 4 and comparative examples 1 to 3.
Table 1 shows the test data of mechanical properties, dimensional accuracy, electric conductivity, heat conductivity and flame retardance of the molded articles obtained in examples 1 to 4 and comparative examples 1 to 3, wherein the tensile strength was measured according to the GB/T1447-related method, the heat conductivity was measured according to the GB/T22588-related method, the electric conductivity was measured according to the GB/T15738 or GB/T1410-related method, the dimensional accuracy was measured according to the GB/T14486-related method, and the flame retardance was measured according to the GB/T2408-related method.
As can be seen from the data in Table 1, compared with the laser sintering formed piece of the nylon composite powder obtained by excessively adding pure nylon powder, pure attapulgite/nylon powder and aniline monomers, the mechanical property, the dimensional accuracy, the electric conduction, the heat conduction and the flame retardance of the nylon composite powder laser sintering formed piece prepared by the invention are greatly improved.
The foregoing is merely illustrative of the present invention and is not to be construed as limiting the scope of the present invention, and any person skilled in the art can easily conceive of changes or substitutions within the technical scope of the present invention.
Claims (7)
1. The preparation method of the nylon composite powder is characterized by comprising the following steps:
mixing attapulgite, aniline monomer, oxidant and doping agent with deionized water for reaction for 5-8 hours to obtain fibrous conductive powder;
mixing nylon, an anti-sticking agent and an organic solvent to obtain a nylon mixed solution;
heating the fibrous conductive powder and the nylon mixed solution for reaction, decompressing, cooling to room temperature, and performing aftertreatment to obtain nylon composite powder;
the mass ratio of the attapulgite to the aniline monomer is 1:0.1-0.4;
the mass ratio of the fibrous conductive powder to the nylon mixed solution is 1:10-40;
the heating temperature is 130-200 ℃ and the heating time is 0.5-2h.
2. The method for preparing nylon composite powder according to claim 1, wherein the attapulgite is a monodisperse nanofiber with a length of 0.5-2um and a diameter of 20-50 nm.
3. The method for preparing nylon composite powder according to claim 1, wherein the oxidizing agent is ammonium persulfate or ferric trichloride.
4. The method for preparing nylon composite powder according to claim 1, wherein the mass ratio of the aniline to the oxidant is 1:1.3-1.8.
5. The method for preparing nylon composite powder according to claim 1, wherein the dopant is benzenesulfonic acid, hydrochloric acid or phosphoric acid.
6. A nylon composite powder produced by the method for producing a nylon composite powder according to any one of claims 1 to 5.
7. Use of the nylon composite powder of claim 6 in laser sinter molding comprising:
(1) Uniformly spreading the nylon composite powder on a processing platform, heating the processing platform to a processing temperature, and carrying out laser scanning based on a set two-dimensional sheet layer;
(2) After the laser scanning is finished, shifting down one powder layer thickness, and repeating the step (1);
(3) Repeating the steps (1) and (2) until a laser sintered part is obtained; the laser power is 30-80w, the laser scanning speed is 4-6m/s, the thickness of each powder layer is 0.08-0.95mm, and the processing temperature is 170-185 ℃.
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| CN101215418A (en) * | 2007-12-27 | 2008-07-09 | 江苏工业学院 | Method for preparing polyaniline/attapulgite clay nano conductive composite material |
| CN102757642A (en) * | 2011-04-28 | 2012-10-31 | 中国科学院合肥物质科学研究院 | Preparation method of conductive nylon 66 composite material |
| CN109233272A (en) * | 2018-09-27 | 2019-01-18 | 盱眙欧佰特粘土材料有限公司 | Nylon/attapulgite/carbon fiber composite granule and preparation method thereof and the application in Selective Laser Sintering |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215418A (en) * | 2007-12-27 | 2008-07-09 | 江苏工业学院 | Method for preparing polyaniline/attapulgite clay nano conductive composite material |
| CN102757642A (en) * | 2011-04-28 | 2012-10-31 | 中国科学院合肥物质科学研究院 | Preparation method of conductive nylon 66 composite material |
| CN109233272A (en) * | 2018-09-27 | 2019-01-18 | 盱眙欧佰特粘土材料有限公司 | Nylon/attapulgite/carbon fiber composite granule and preparation method thereof and the application in Selective Laser Sintering |
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