CN106903305A - A kind of preparation method of 3D printing metallic particles/inorganic nanoparticles/polymer compound powder body - Google Patents

A kind of preparation method of 3D printing metallic particles/inorganic nanoparticles/polymer compound powder body Download PDF

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Publication number
CN106903305A
CN106903305A CN201710235140.0A CN201710235140A CN106903305A CN 106903305 A CN106903305 A CN 106903305A CN 201710235140 A CN201710235140 A CN 201710235140A CN 106903305 A CN106903305 A CN 106903305A
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preparation
powder
plating
solution
printing
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Inventor
黄俊俊
周芳
吴健
纪君宇
葛天宇
张雅君
朱正玉
袁园
高敏
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Hefei University
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Hefei University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C23C18/1641—Organic substrates, e.g. resin, plastic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/285—Sensitising or activating with tin based compound or composition
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys
    • C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel

Abstract

A kind of preparation method of 3D printing metallic particles/inorganic nanoparticles/polymer compound powder body, is related to chemical plating and the field of composite material preparation, preparation method to be：(a) polymer powder material surface modifying；(b) polymer-modified powder surface sensitization and activation；(c) polymer powder surface chemical plating.The composite granule of preparation is classified, the powder for selecting particle diameter to be 50~80 μm can carry out the printing of 3D products as raw material.Nano-metal particle and one-dimensional (or two dimension) nano material can modified synergic polymeric matrix, good dispersion plays toughness reinforcing and enhanced effect；Simultaneously, metal nanoparticle can be adsorbed in one-dimensional (or two dimension) material surface, interface is good, increase the contact area with matrix resin, it is improved the transmission effects of interfacial stress, and then lift the interface cohesion of composite by force, so as to improve the mechanical property of the 3D printing product of composite powder material preparation.

Description

A kind of system of 3D printing metallic particles/inorganic nanoparticles/polymer compound powder body Preparation Method
Technical field
The present invention relates to chemical plating and field of composite material preparation, a kind of 3D printing metallic particles/nothing is related specifically to The preparation method of machine nano particle/polymer compound powder body.
Background technology
Chemical plating as preparing metallic cover type powder, metallic particles effective wetting matrix in its composite granule for preparing Powder, realizes that powder granule is dispersed, while the interfacial structure that whisker matches with matrix on atomic scale is realized, so that Be conducive to the performance of reinforcement premium properties, improve the combination property of composite.Metallic cover inorganic particle refers to inorganic Powder is core, the composite granule with metal as shell.This composite granule is due to excellent electromagnetism, optics, chemistry It is catalyzed and the excellent properties such as the wetability between metal and ceramics can be improved, 3D printing neck is widely used in recent years Domain.
The preparation method of metallic cover inorganic particle composite granule has sol-gal process, mechanical mixing, electroless plating method, non- Homogeneous precipitation method etc., wherein electroless plating method due to can any matrix surface can prepare uniformly, porosity is low, thickness can The coat of metal of control, and technique is easily controllable, equipment is simply widely paid close attention to.
Electroless plating on powders technique is at present：(1) powder surface introduces active group；(2) active group adsoption catalysis Agent；(3) powder surface of adsorption catalyst passes through electroless-deposited metal particle.For example, patent：02131262.1 discloses nothing The method of machine powder surface metallizing.The method inorganic particle first is roughened by the solution of chromic anhydride；Then through protochloride pink salt Acid solution is sensitized, the activation of palladium bichloride hydrochloric acid solution；Finally carry out surface chemistry metal plating layer.Wherein it is roughened, be sensitized and activates In acid condition, this technique can not realize such as calcium carbonate, flyash, the surface chemical plating of magnesium carbonate powder to process. For another example patent 200780011903.8 discloses conductive powder plated by electroless plating and its manufacture method.The method is by core powder Body is contacted with the initial condensation thing of melmac, the polymerisation of the initial condensation thing is carried out, using melmac In amino adsorption catalyst, so as to realize chemical plating.The method is in powder table using polymer monomer by polymerisation Face introducing active group, complex process, polymer is fully wrapped around with powder surface condensation reaction powder surface difficult to realize in addition. Therefore, the method for existing inorganic particle chemical plating is to be improved.
The content of the invention
It is an object of the invention to overcome the shortcomings of existing electroless plating on powders method, there is provided one kind is applied to various nothings The preparation side of the 3D printing of machine powder, process is simple and environmental protection metallic particles/inorganic nanoparticles/polymer compound powder body Method.
To achieve these goals, technical scheme is as follows：
The preparation method of a kind of 3D printing metallic particles/inorganic nanoparticles/polymer compound powder body, comprising following step Suddenly：
(1) polymer powder is immersed in 1~30min in surface modification solution, cleaning, centrifugation；
(2) step (1) resulting polymers powder is immersed and is sensitized in the sensitizing solution that pH is 1~3, sensitizing temperature is 30 ~60 DEG C, sensitization time is 10~50min, is washed to neutrality；
(3) step (2) gained sensitization polymer powder is immersed and is activated in the activating solution that pH is 1~4, activation temperature It it is 30~60 DEG C, soak time is 10~50min, is washed to neutrality；
(4) by step (3) gained activation post-consumer polymer powder chemistry plating, inorganic nanoparticles dispersion is added in the plating solution Liquid, uses mechanical agitation with dispersed powder, and electroless plating time is 20~60min, and the temperature of chemical plating bath is 30~60 DEG C, washing, 60 DEG C dry 40min, obtain 3D printing metallic particles/inorganic nanoparticles/polymer compound powder body.
Preferably, in preparation method, in the step (1) polymer powder be nylon, polypropylene, polyethylene, plastics gather At least one in diphenyl sulfide, acrylonitrile/styrene/butadiene copolymers.
Preferably, in preparation method, surface modification solution is Silane coupling agent KH550, silane coupled in the step (1) At least one in agent KH560, silane coupler KH792.Contain two kinds of different active genes in silane coupled agent molecule -- Amino and epoxide, for being coupled organic polymer and inorganic filler, strengthen its caking property.
Preferably, in preparation method, the sensitizing solution in the step (2) is stannous chloride solution.
Preferably, in preparation method, activating solution is that the boric acid comprising metallic colloid catalyst is molten described in the step (3) Liquid, wherein the metallic colloid catalyst is at least one in palladium, platinum, silver and gold.
Preferably, in preparation method, in the step (4) inorganic nanoparticles dispersion liquid be Multi-layer graphite piece dispersion liquid, At least one in graphene dispersing solution, carbon nano tube dispersion liquid, carbon fiber dispersion liquid, size is 50~800nm, and content is 1 ~100mg/L.
Preferably, in preparation method, in the step (4) chemical plating include electroless copper, chemical nickel plating, electroless cobalt plating and At least one in chemical silvering.
Meanwhile, composite granule prepared by the above method is classified, selection particle diameter is 50~80 μm of powder as original Material can carry out the printing of 3D products.
Nano-metal particle and one-dimensional (or two dimension) nano material can modified synergic polymeric matrix, good dispersion plays Toughness reinforcing and enhanced effect；Meanwhile, metal nanoparticle can be adsorbed in one-dimensional (or two dimension) material surface, and interface is good, increase with The contact area of matrix resin, is improved the transmission effects of interfacial stress, and then lifts the interface cohesion of composite by force, So as to improve the mechanical property of the 3D printing product of composite powder material preparation.Compared with prior art, beneficial effect of the invention Fruit shows：
1st, in composite granule prepared by the present invention, metallic particles and inorganic nanoparticles dispersive property is good and same substrate surface Adhesive property is excellent.
2nd, preparation process is simple of the present invention, can be continuously produced.
3rd, the composite powder material that the present invention program is obtained can improve the mechanical property of 3D printing product, good fluidity, point Scattered property is good and interfacial adhesion strength is high, can be widely applied to 3D printing field.
Specific embodiment
Present invention implementation is further described below, following examples are descriptive, are not limited, it is impossible to Protection scope of the present invention is limited with this.It is non-that person skilled in art makes some according to the invention described above content to the present invention The modifications and adaptations of essence, are accordingly to be regarded as within protection scope of the present invention.
Embodiment 1
Dried nylon is immersed in into Silane coupling agent KH550, and (20%, its reclaimed water is 40%, and ethanol is 40%) solution In, time 30min, temperature is 60 DEG C, is cleaned once with purified water after taking-up, then be centrifuged.It is immersed in using modified nylon The SnCl of 5g/L210min, 30 DEG C of temperature are sensitized in (adjusting pH to 1 with hydrochloric acid) solution.Immersed after being cleaned with deionized water after taking-up PdCl containing 0.15g/L2With the H of 20g/L3BO310min is activated in (adjusting pH to 2 with hydrochloric acid) solution, and 30 DEG C of temperature is living Nylon deionized water rinsing after change.
Chemical nickel-plating plating solution is configured, bath composition is：NiSO4·7H2O(15g/L)、NaH2PO2·H2O(15g/L)、 Na3C6H5O7·2H2O(8g/L)、NH4Cl (18g/L), Multi-layer graphite piece dispersion liquid (600~800nm, content is 50mg/L).Will Plating 20min in the chemical nickel-plating plating solution of 30 DEG C of nylon immersion after activation.After chemical nickel plating, cleaned with deionized water, dried 60 DEG C dry 40min in case, obtain final product the nylon powder of surface cladded with nickel.
With nickel particle/Multi-layer graphite piece/nylon composite granule that particle diameter is 50~80 μm as raw material, using 3D printing technique The profiled member outward appearance particle of preparation is uniform, good mechanical performance, and tensile strength is 4.5MPa.
Embodiment 2
Dried polypropylene is immersed in into silane coupler KH792, and (20%, its reclaimed water is 40%, and ethanol is 40%) molten In liquid, time 30min, temperature is 60 DEG C, is cleaned once with purified water after taking-up, then be centrifuged.Soaked using modified polypropylene Steep the SnCl in 5g/L220min, 40 DEG C of temperature are sensitized in (adjusting pH to 1 with hydrochloric acid) solution.After being cleaned with deionized water after taking-up PdCl of the immersion containing 0.15g/L2With the H of 20g/L3BO320min is activated in (adjusting pH to 2 with hydrochloric acid) solution, temperature 40 DEG C, the polypropylene deionized water rinsing after activation.
Electroless copper plating solution is prepared, bath composition is：NiSO4·7H2O(1g/L)、CuSO4·5H2O(24g/L)、 NaH2PO2·H2O(55g/L)、Na3C6H5O7·2H2O(1.5g/L)、H3BO3(70g/L), graphene dispersing solution (100~ 300nm, content is 20mg/L).Polypropylene after activation is immersed plating 30min in 40 DEG C of electroless copper plating solution.Chemical plating After copper, cleaned with deionized water, 60 DEG C dry 40min in an oven, obtain final product the polypropylene powder of Surface coating copper.
With copper particle/Graphene/polypropylene composite materials powder that particle diameter is 50~80 μm as raw material, using 3D printing technique system Standby profiled member outward appearance particle is uniform, good mechanical performance, and tensile strength is 4.5MPa.
Embodiment 3
Dried polyethylene is immersed in into Silane coupling agent KH550, and (20%, its reclaimed water is 40%, and ethanol is 40%) molten In liquid, time 30min, temperature is 60 DEG C, is cleaned once with purified water after taking-up, then be centrifuged.Soaked using modified polyethylene Steep the SnCl in 5g/L230min, temperature 50 C are sensitized in (adjusting pH to 1 with hydrochloric acid) solution.After being cleaned with deionized water after taking-up PdCl of the immersion containing 0.15g/L2With the H of 20g/L3BO330min is activated in (adjusting pH to 2 with hydrochloric acid) solution, temperature 50 DEG C, the polyethylene deionized water rinsing after activation.
Chemical silvering plating solution is prepared, bath composition is：AgNO3(29g/L)、NH3·H2O (4g/L) and HCHO (55g/L), Carbon nano tube dispersion liquid (300~600nm, content is 80mg/L).Polyethylene after activation is immersed 50 DEG C of chemical silvering plating Plating 40min in liquid.After chemical silvering, cleaned with deionized water, 60 DEG C dry 40min in an oven, obtain final product coated with silver on surface Polyethylene powder.
With Argent grain/carbon nano-tube/poly ethene composite granule that particle diameter is 50~80 μm as raw material, using 3D printing technique The profiled member outward appearance particle of preparation is uniform, good mechanical performance, and tensile strength is 4.5MPa.
Embodiment 4
Dried plastics polyphenylene sulfide is immersed in into silane coupler KH792, and (20%, its reclaimed water is 40%, and ethanol is 40%) in solution, time 30min, temperature is 60 DEG C, is cleaned once with purified water after taking-up, then be centrifuged.Using modified modeling Material polyphenylene sulfide is immersed in the SnCl of 5g/L240min, temperature 60 C are sensitized in (adjusting pH to 1 with hydrochloric acid) solution.Spent after taking-up The PdCl containing 0.15g/L is immersed after ionized water cleaning2With the H of 20g/L3BO340min is carried out in (adjusting pH to 2 with hydrochloric acid) solution Activation, temperature 60 C, the plastics polyphenylene sulfide deionized water rinsing after activation.
Chemical nickel-plating plating solution is configured, bath composition is：NiSO4·7H2O(15g/L)、NaH2PO2·H2O(15g/L)、 Na3C6H5O7·2H2O(8g/L)、NH4Cl (18g/L), carbon fiber dispersion liquid (100~500nm, content is 40mg/L).Will activation Plating 50min in the chemical nickel-plating plating solution of 60 DEG C of plastics polyphenylene sulfide immersion afterwards.After chemical nickel plating, cleaned with deionized water, 60 DEG C dry 40min in an oven, obtain final product the plastics polyphenylene sulfide powder of surface cladded with nickel.
With nickel particle/carbon fiber/plastics polyphenylene sulfide composite granule that particle diameter is 50~80 μm as raw material, using 3D printing Profiled member outward appearance particle prepared by technology is uniform, good mechanical performance, and tensile strength is 4.5MPa.
Embodiment 5
Dried acrylonitrile/styrene/butadiene copolymers are immersed in silane coupler KH560 (20%, its reclaimed water It is 40%, ethanol is that 40%) in solution, time 30min, temperature is 60 DEG C, is cleaned once with purified water after taking-up, then be centrifuged. The SnCl of 5g/L is immersed in using modified acrylonitrile/styrene/butadiene copolymers2In (adjusting pH to 1 with hydrochloric acid) solution Sensitization 50min, temperature 60 C.The PdCl containing 0.15g/L is immersed after being cleaned with deionized water after taking-up2With the H of 20g/L3BO3 50min is activated in (adjusting pH to 2 with hydrochloric acid) solution, temperature 60 C, the acrylonitrile/phenylethylene/butadiene copolymerization after activation Thing deionized water rinsing.
Electroless cobalt plating plating solution is configured, bath composition is：CoCl2(25g/L)、NaH2PO2·H2O(25g/L)、Na3C6H5O7· 2H2O(55g/L)、NH4Cl(45g/L)、H3BO3(25g/L), graphene dispersing solution (100~250nm, content is 25mg/L).Will Plating 60min in the electroless cobalt plating plating solution of acrylonitrile/60 DEG C of the styrene/butadiene copolymers immersion after activation.Electroless cobalt plating Afterwards, cleaned with deionized water, 60 DEG C dry 40min in an oven, obtain final product the acrylonitrile/phenylethylene/butadiene of Surface coating cobalt Copolymerization powder.
It is with cobalt granule/Graphene/acrylonitrile/styrene/butadiene copolymers composite granule that particle diameter is 50~80 μm Raw material, the profiled member outward appearance particle that is prepared using 3D printing technique is uniform, good mechanical performance, and tensile strength is 4.5MPa.

Claims (8)

1. the preparation method of a kind of 3D printing metallic particles/inorganic nanoparticles/polymer compound powder body, it is characterised in that： Comprise the steps of：
(1) polymer powder is immersed in 1~30min in surface modification solution, cleaning, centrifugation；
(2) step (1) resulting polymers powder is immersed and is sensitized in the sensitizing solution that pH is 1~3, sensitizing temperature is 30~60 DEG C, sensitization time is 10~50min, is washed to neutrality；
(3) step (2) gained sensitization polymer powder is immersed and is activated in the activating solution that pH is 1~4, activation temperature is 30 ~60 DEG C, soak time is 10~50min, is washed to neutrality；
(4) by step (3) gained activation post-consumer polymer powder chemistry plating, inorganic nanoparticles dispersion liquid is added in the plating solution, Mechanical agitation is used with dispersed powder, electroless plating time is 20~60min, and the temperature of chemical plating bath is 30~60 DEG C, Washing, 60 DEG C dry 40min, obtain 3D printing metallic particles/inorganic nanoparticles/polymer compound powder body.
2. preparation method as claimed in claim 1, it is characterised in that：Polymer powder is nylon, poly- third in the step (1) At least one in alkene, polyethylene, plastics polyphenylene sulfide, acrylonitrile/styrene/butadiene copolymers.
3. preparation method as claimed in claim 1, it is characterised in that：Surface modification solution is silane idol in the step (1) At least one in connection agent KH550, silane coupler KH560, silane coupler KH792.
4. preparation method as claimed in claim 1, it is characterised in that：Sensitizing solution in the step (2) is that stannous chloride is molten Liquid.
5. preparation method as claimed in claim 1, it is characterised in that：Activating solution is comprising metal described in the step (3) The BAS of colloid catalyst, wherein the metallic colloid catalyst is at least one in palladium, platinum, silver and gold.
6. preparation method as claimed in claim 1, it is characterised in that：Inorganic nanoparticles dispersion liquid is in the step (4) At least one in Multi-layer graphite piece dispersion liquid, graphene dispersing solution, carbon nano tube dispersion liquid, carbon fiber dispersion liquid, size is 50~800nm, content is 1~100mg/L.
7. preparation method as claimed in claim 1, it is characterised in that：Chemical plating includes electroless copper, changes in the step (4) Learn at least one in nickel plating, electroless cobalt plating and chemical silvering.
8. such as the metallic particles/inorganic nanoparticles/polymer compound powder body of any one of claim 1~7 methods described preparation Application in the printing of 3D products, it is characterised in that：The composite granule of preparation is classified, selection particle diameter is 50~80 μm Powder carries out the printing of 3D products as raw material.
CN201710235140.0A 2017-04-12 2017-04-12 A kind of preparation method of 3D printing metallic particles/inorganic nanoparticles/polymer compound powder body Pending CN106903305A (en)

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CN108161017A (en) * 2018-01-04 2018-06-15 广东银纳科技有限公司 It is a kind of for metal powder of 3D printing and preparation method thereof
CN108914096A (en) * 2018-07-25 2018-11-30 芜湖昌菱金刚石工具有限公司 A kind of preparation method of diamond surface cladding Ni-W-P metallization coating
CN113621203A (en) * 2021-09-15 2021-11-09 南通理工学院 Conductive 3D printing material and preparation method thereof
CN114276675A (en) * 2022-01-26 2022-04-05 福州大学 Nylon 12 composite material for MJR3D printing and preparation method thereof
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CN114276675B (en) * 2022-01-26 2022-12-23 福州大学 Nylon 12 composite material for MQR 3D printing and preparation method thereof

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Application publication date: 20170630