CN115028989A - 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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- CN115028989A CN115028989A CN202210734888.6A CN202210734888A CN115028989A CN 115028989 A CN115028989 A CN 115028989A CN 202210734888 A CN202210734888 A CN 202210734888A CN 115028989 A CN115028989 A CN 115028989A
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- 239000000843 powder Substances 0.000 title claims abstract description 158
- 239000004677 Nylon Substances 0.000 title claims abstract description 145
- 229920001778 nylon Polymers 0.000 title claims abstract description 145
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000149 argon plasma sintering Methods 0.000 title claims 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
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 239000002019 doping agent Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction 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
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 26
- 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 12
- 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 4
- 239000002121 nanofiber Substances 0.000 claims 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 group 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 abstract description 4
- 239000000463 material Substances 0.000 description 32
- 238000003892 spreading Methods 0.000 description 28
- 230000007480 spreading Effects 0.000 description 28
- 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
- 239000008187 granular material Substances 0.000 description 14
- 238000000110 selective laser sintering Methods 0.000 description 14
- 239000011246 composite particle Substances 0.000 description 12
- 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
- 238000000465 moulding Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 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
- 239000002245 particle Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 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 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
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 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
- 239000007787 solid Substances 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
- 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
- 239000007788 liquid Substances 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
- 238000005245 sintering Methods 0.000 description 2
- 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
- 238000005238 degreasing Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001914 filtration Methods 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
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 239000000779 smoke 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
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- 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
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- 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
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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
- 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
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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
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C08K7/00—Use of ingredients characterised by shape
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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, dopant 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 post-treatment 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 piece formed by laser scanning has high mechanical property and dimensional accuracy, and also has high electric conduction, heat conduction and flame retardant 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 (AM), also called 3D printing, belongs to one of Rapid Prototyping (RP) technologies, and is a method for directly manufacturing a three-dimensional physical entity in a layer-by-layer stacking manner based on a three-dimensional CAD model of a computer. The additive manufacturing technology is not limited by the shape of a forming geometric solid, the three-dimensional solid model is directly processed into a plane, and parts with any complex shapes and structures can be rapidly and precisely manufactured on one device, so that 'free manufacturing' is realized. As a prospective and strategic technology, the method has strong engineering applicability and large field span, and is very important for the development of future manufacturing industry, especially high-end manufacturing. The method 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, appeared in the last 80 centuries and is a 3D printing technique based on additive manufacturing. The principle of the method is that a layer of powder material is paved on a workbench in advance, laser is used for sintering the powder of the solid part under the control of a computer according to the interface profile information, and then the powder is circulated continuously and piled layer by layer for forming. The technical requirements of the powder material include uniform particle size distribution and good fluidity, which is beneficial to powder bed powder laying. The forming method has the characteristics of simple manufacturing process, high flexibility, high material utilization rate, high forming speed and the like.
Nylon material is used as the first major 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, particularly, the wear resistance and self-lubricating property are excellent, the friction coefficient is small, so that the nylon is steadily and rapidly increased in the fierce competition with other engineering plastics, and the nylon material is widely applied to the manufacture of parts such as automobile household appliances, sports equipment and the like. However, the nylon material has low oxygen index and high combustion speed, generates a large amount of dense smoke and molten drops in the combustion process, and is very easy to spread flame, so that the application of the nylon material in special fields such as aerospace, automobile manufacturing, electronic appliances and the like is greatly limited. The functional parts with higher density and better mechanical property can be directly formed by an SLS process, and become one of SLS forming materials which are most widely applied at present.
Chinese patent No. CN106426916A discloses a 3D printing method including the following steps: mixing the powdery material to be processed and the powdery nylon material. And melting the nylon material by adopting a selective laser sintering technology to bond the materials to be processed to form a green body. Heating the green body for thermal degreasing 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 is reduced to room temperature to obtain a dense part. According to the 3D printing method, the high-strength laser beam is not needed, the temperature is low in the processing process, the thermal strain and the residual stress cannot be generated, the problems of warping, cracking and/or delaminating of the part are avoided, and the mechanical property and the dimensional accuracy of the part are ensured. However, the mechanical properties of the pure nylon sample formed by the SLS technique are generally lower than those of the conventional injection molded sample, and the pure nylon sample lacks the functions of electric conduction, heat conduction and flame retardance, and cannot meet the performance requirements of certain high-end application fields.
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 high mechanical property and high electric conduction, heat conduction and flame retardant functions.
A method for preparing nylon composite powder comprises the following steps:
mixing attapulgite, aniline monomer, oxidant, dopant and deionized water, and reacting for 5-8h 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 post-treatment to obtain the nylon composite powder.
The attapulgite is monodisperse nano-fiber with the length of 0.5-2um and the 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 form through in-situ polymerization to realize effective and complete 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 powder, so that the mechanical property, the electric conduction function, the heat conduction function and the flame retardant function 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 dopant 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 doping agent is 1:1.1-1.5, and the mass ratio of the attapulgite to the doping agent is 1: 1.3.
The mass ratio of the attapulgite to the deionized water is 1:20-30, and further 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 130-200 ℃, the heating time is 0.5-2h, and further preferably, the heating temperature is 150-180 ℃.
The cooling rate is 2-5 ℃/min, and in order to make the particle size distribution more uniform, the cooling rate is preferably 4 ℃/min.
The post-treatment is filtration, drying and sieving. Agglomerated large particles were 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 paving the nylon composite powder on a processing platform, heating the processing platform to a processing temperature, and performing laser scanning based on a set two-dimensional sheet layer;
(2) moving down a powder layer thickness after the laser scanning is finished, and repeating the step (1);
(3) repeating the steps (1) and (2) until a laser sintering piece 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 from inside to outside.
Further, the thickness of each powder layer is 0.10-0.11 mm.
Further, the processing temperature is 180 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, polyaniline is uniformly coated on the surface of attapulgite through the in-situ polymerization of 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 the interaction of a large number of aniline groups and amide groups on the surface of the fibrous conductive powder, so that the 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 and forming has good mechanical properties and good functions of electric conduction, heat conduction and flame retardance.
(2) The fibrous attapulgite material is introduced into the nylon composite powder provided by the invention, the attapulgite is an inorganic rigid nano material, has a lower thermal expansion coefficient, and the uniform distribution of the attapulgite material in a 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 the 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 electron microscope SEM photograph of the pure attapulgite/nylon composite powder material prepared in comparative example 2.
Detailed Description
To further clarify the objects, technical solutions and advantages of the present invention, the following detailed description of the present invention is provided with reference to the examples, which should not be construed as limiting the scope of the present invention.
Example 1
(1) Weighing 1000g of nylon granules, 200g of attapulgite powder, 60g of aniline monomer, 80g of oxidant ammonium persulfate and 75g of dopant benzenesulfonic acid;
(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-bis-lauramide 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%;
(4) placing the fibrous powder prepared in the step (2) and the nylon mixed solution prepared in the step (3) in a high-pressure reaction kettle, introducing nitrogen, pressurizing to 1MPa, and stirring at high speed (630 rpm); raising the temperature to 175 ℃, and keeping the temperature 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 to obtain nylon composite particle suspension;
(5) carrying out vacuum drying treatment on the nylon composite particles prepared in the step (4), and sieving 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 figure 1, and the SEM photograph shows that the conductive fibers in the nylon composite powder material are uniformly dispersed in a nylon matrix and play a good role in enhancing and modifying.
(6) Adding the prepared nylon composite powder into a powder supply bin of selective laser sintering molding equipment, uniformly spreading the nylon composite powder on a processing platform by a powder spreading scraper, emitting laser by a laser, spreading the powder for 6mm, setting the processing temperature to be 185 ℃, setting the processing platform temperature to be 130 ℃, and pre-baking the powder for 2 hours; starting processing after powder baking is finished, controlling the switch of a laser and the angle of a scanner by a computer to enable a laser beam to scan on a processing plane according to the shape of a corresponding two-dimensional slice layer, moving a workbench downwards by one layer thickness after the laser beam is swept, spreading powder, scanning the laser beam, and repeating the steps to obtain a laser sintering piece; the scanning mode of the laser beam on the processing platform is from inside to outside, the laser power is 60W, the scanning speed is 5m/s, and the thickness of the powder layer is 0.95 mm.
Example 2
(1) Weighing 1000g of nylon granules, 100g of attapulgite powder, 20g of aniline monomer, 26g of oxidant ferric chloride and 22g of dopant hydrochloric acid;
(2) adding the attapulgite, aniline monomer, ferric chloride and hydrochloric acid into 2000g of deionized water, stirring and ultrasonically oscillating 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 being 5%;
(4) placing the fibrous powder prepared in the step (2) and the nylon mixed solution prepared in the step (3) in a high-pressure reaction kettle, introducing nitrogen, pressurizing to 1MPa, and stirring at high speed (630 rpm); heating to 130 deg.C, and maintaining the temperature for 0.5 to dissolve nylon completely; after complete dissolution, the high pressure is released, and the temperature is reduced to room temperature at the speed of 4 ℃/min to obtain nylon composite particle suspension;
(5) and (4) carrying out vacuum drying treatment on the nylon composite particles prepared in the step (4), and sieving 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 molding equipment, uniformly spreading the nylon composite powder on a processing platform by a powder spreading scraper, emitting laser by a laser, spreading the powder for 6mm, setting the processing temperature to be 175 ℃, setting the processing platform temperature to be 130 ℃, and pre-baking the powder for 2 hours; starting processing after powder baking is finished, controlling the switch of a laser and the angle of a scanner by a computer to enable a laser beam to scan on a processing plane according to the shape of a corresponding two-dimensional slice layer, moving a workbench downwards by one layer thickness after the laser beam is swept, spreading powder, scanning the laser beam, and repeating the steps to obtain a laser sintering piece; the scanning mode of the laser beam on the processing platform is from inside to outside, the laser power is 30W, the scanning speed is 4m/s, and the thickness of the powder layer is 0.08 mm.
Example 3
(1) Weighing 1000g of nylon granules, 350g of attapulgite powder, 140g of aniline monomer, 224g of oxidant ammonium persulfate and 210g of dopant phosphoric acid;
(2) adding the attapulgite, aniline monomer, ammonium persulfate and phosphoric acid into 10500g of deionized water, stirring and ultrasonically oscillating for 8h 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 being 25%;
(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, pressurizing to 1MPa, and stirring at a high speed (630 rpm); raising the temperature to 200 ℃, and keeping the temperature 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 to obtain nylon composite particle suspension;
(5) and (4) carrying out vacuum drying treatment on the nylon composite particles prepared in the step (4), and sieving 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 molding equipment, uniformly spreading the nylon composite powder on a processing platform by a powder spreading scraper, emitting laser by a laser, spreading 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 powder baking is finished, controlling the switch of a laser and the angle of a scanner by a computer to enable a laser beam to scan on a processing plane according to the shape of a corresponding two-dimensional slice layer, moving a workbench downwards by one layer thickness after the laser beam is swept, spreading powder, scanning the laser beam, and repeating the steps to obtain a laser sintering piece; the scanning mode of the laser beam on the processing platform is from inside to outside, the laser power is 80W, the scanning speed is 6m/s, and the thickness of the powder layer is 0.15 mm.
Example 4
(1) Weighing 1000g of nylon granules, 200g of attapulgite powder, 60g of aniline monomer, 80g of oxidant ammonium persulfate and 75g of dopant benzenesulfonic acid;
(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 mixed liquid with the mass concentration of nylon being 15%;
(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, pressurizing to 1MPa, and stirring at a high speed (630 rpm); raising the temperature to 175 ℃, and keeping the temperature for 1.5h until the nylon is completely dissolved; after complete dissolution, releasing the high pressure, and cooling the temperature to room temperature at the speed of 4 ℃/min to obtain a nylon composite particle suspension;
(5) and (4) carrying out vacuum drying treatment on the nylon composite particles prepared in the step (4), and sieving 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 molding equipment, uniformly spreading the nylon composite powder on a processing platform by a powder spreading scraper, emitting laser by a laser, spreading the powder for 6mm, setting the processing temperature to be 185 ℃, setting the processing platform temperature to be 130 ℃, and pre-baking the powder for 2 hours; starting processing after powder baking is finished, controlling the switch of a laser and the angle of a scanner by a computer to enable a laser beam to scan on a processing plane according to the shape of a corresponding two-dimensional slice layer, moving a workbench downwards by one layer thickness after the laser beam is swept, spreading powder, scanning the laser beam, and repeating the steps to obtain a laser sintering piece; the scanning mode of the laser beam on the processing platform is from inside to outside, the laser power is 60W, the scanning speed is 5m/s, and the thickness of the powder layer is 0.95 mm.
Comparative example 1
Pure nylon powder was prepared as described in example 1
(1) Weighing 1000g of nylon granules, adding the nylon granules and the ethanol bis-lauramide anti-sticking agent into N, N-dimethylformamide according to the mass ratio of 1:0.005 to prepare mixed liquid with the mass concentration of nylon of 15%;
(2) putting the nylon mixed solution prepared in the step (1) into a high-pressure reaction kettle, introducing nitrogen, pressurizing to 1MPa, and stirring at a high speed (630 rpm); raising the temperature to 175 ℃, and keeping the temperature for 1.5h 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 to obtain nylon particle suspension;
(3) and (3) carrying out vacuum drying treatment on the nylon particles prepared in the step (2), and sieving 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 molding equipment, uniformly spreading the nylon composite powder on a processing platform by a powder spreading scraper, emitting laser by a laser, spreading the powder for 6mm, setting the processing temperature to be 185 ℃, the processing platform temperature to be 130 ℃, and pre-baking the powder for 2 hours; starting processing after powder baking is finished, controlling a switch of a laser and an angle of a scanner by a computer to enable a laser beam to scan on a processing plane according to the shape of a corresponding two-dimensional slice layer, moving a workbench downwards by one layer thickness after the laser beam scans, then spreading powder, scanning the laser beam, and repeating the steps to obtain a laser sintered part; the scanning mode of the laser beam on the processing platform is from inside to outside, the laser power is 60W, the scanning speed is 5m/s, and the thickness of the powder layer is 0.95 mm.
Comparative example 2
According to the method described in example 1, pure attapulgite/nylon powder was prepared without introducing aniline monomer, oxidant and dopant
(1) 1000g of nylon granules and 200g of attapulgite powder were weighed.
(2) Adding the nylon granules and the ethanol-bis-lauramide 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%;
(3) putting the pure attapulgite powder and the nylon mixed solution prepared in the step (2) into a high-pressure reaction kettle, introducing nitrogen, pressurizing to 1MPa, and stirring at high speed (630 rpm); raising the temperature to 175 ℃, and keeping the temperature 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 to obtain nylon composite particle suspension;
(4) carrying out vacuum drying treatment on the nylon composite particles prepared in the step (3), and sieving 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 figure 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 molding equipment, uniformly spreading the nylon composite powder on a processing platform by a powder spreading scraper, emitting laser by a laser, spreading the powder for 6mm, setting the processing temperature to be 185 ℃, setting the processing platform temperature to be 130 ℃, and pre-baking the powder for 2 hours; starting processing after powder baking is finished, controlling the switch of a laser and the angle of a scanner by a computer to enable a laser beam to scan on a processing plane according to the shape of a corresponding two-dimensional slice layer, moving a workbench downwards by one layer thickness after the laser beam is swept, spreading powder, scanning the laser beam, and repeating the steps to obtain a laser sintering piece; the scanning mode of the laser beam on the processing platform is from inside to outside, the laser power is 60W, the scanning speed is 5m/s, and the thickness of the powder layer is 0.95 mm.
Comparative example 3
According to the method described in the example 1, the nylon composite powder obtained when the mass ratio of the aniline monomer to the attapulgite is more than 0.4 is prepared.
(1) Weighing 1000g of nylon granules, 200g of attapulgite powder, 100g of aniline monomer, 80g of oxidant ammonium persulfate and 75g of dopant benzenesulfonic acid;
(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 bis-lauramide anti-sticking agent into N, N-dimethylformamide in a mass ratio of 1:0.005 to prepare a mixed solution with the mass concentration of nylon of 15%;
(4) placing the fibrous powder prepared in the step (2) and the nylon mixed solution prepared in the step (3) in a high-pressure reaction kettle, introducing nitrogen, pressurizing to 1MPa, and stirring at high speed (630 rpm); raising the temperature to 175 ℃, and keeping the temperature for 1.5h 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 to obtain nylon composite particle suspension;
(5) and (4) carrying out vacuum drying treatment on the nylon composite particles prepared in the step (4), and sieving 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 molding equipment, uniformly spreading the nylon composite powder on a processing platform by a powder spreading scraper, emitting laser by a laser, spreading the powder for 6mm, setting the processing temperature to be 185 ℃, setting the processing platform temperature to be 130 ℃, and pre-baking the powder for 2 hours; starting processing after powder baking is finished, controlling the switch of a laser and the angle of a scanner by a computer to enable a laser beam to scan on a processing plane according to the shape of a corresponding two-dimensional slice layer, moving a workbench downwards by one layer thickness after the laser beam is swept, spreading powder, scanning the laser beam, and repeating the steps to obtain a laser sintering piece; the scanning mode of the laser beam on the processing platform is from inside to outside, the laser power is 60W, the scanning speed is 5m/s, and the thickness of the powder layer is 0.95 mm.
And (3) performance characterization:
table 1 test data for tensile strength, dimensional accuracy, electrical conductivity, thermal conductivity and flame retardancy 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, electrical conductivity, thermal conductivity and flame retardancy of the formed parts obtained in examples 1 to 4 and comparative examples 1 to 3, wherein the tensile strength is measured according to the method related to GB/T1447, the thermal conductivity is measured according to the method related to GB/T22588, the electrical conductivity is measured according to GB/T15738 or GB/T1410, the dimensional accuracy is measured according to the method related to GB/T14486, and the flame retardancy is measured according to GB/T2408.
The data in table 1 show that compared with a laser sintered part of nylon composite powder obtained by adding pure nylon powder, pure attapulgite/nylon powder and aniline monomer in excess, the mechanical property, dimensional accuracy, and electric, heat and flame retardant functions of the laser sintered part of nylon composite powder prepared by the invention are greatly improved.
The above description is only an embodiment of the present invention and should not 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 (10)
1. A preparation method of nylon composite powder is characterized by comprising the following steps:
mixing attapulgite, aniline monomer, oxidant, dopant and deionized water, and reacting for 5-8h 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 post-treatment to obtain the nylon composite powder.
2. The method for preparing nylon composite powder according to claim 1, wherein the attapulgite has monodisperse nanofibers with a length of 0.5-2um and a diameter of 20-50 nm.
3. The preparation method of the nylon composite powder according to claim 1, wherein the mass ratio of the attapulgite to the aniline monomer is 1: 0.1-0.4.
4. The method for preparing nylon composite powder according to claim 1, wherein the oxidant is ammonium persulfate or ferric trichloride.
5. The method for preparing nylon composite powder according to claim 1, wherein the mass ratio of aniline to oxidant is 1: 1.3-1.8.
6. The method for preparing nylon composite powder according to claim 1, wherein the dopant is benzenesulfonic acid, hydrochloric acid or phosphoric acid.
7. The method for producing a nylon composite powder according to claim 1, wherein the mass ratio of the fibrous conductive powder to the nylon mixed solution is 1:10 to 40.
8. The method for preparing nylon composite powder according to claim 1, wherein the heating temperature is 130-200 ℃ and the heating time is 0.5-2 h.
9. A nylon composite powder prepared by the method for preparing a nylon composite powder according to any one of claims 1 to 8.
10. Use of the nylon composite powder of claim 9 in laser sintering forming comprising:
(1) uniformly paving the nylon composite powder on a processing platform, heating the processing platform to a processing temperature, and performing laser scanning based on a set two-dimensional sheet layer;
(2) moving down a powder layer thickness after the laser scanning is finished, and repeating the step (1);
(3) repeating the steps (1) and (2) until a laser sintering piece 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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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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