CN106903305A - 一种3d打印用金属颗粒/无机纳米颗粒/聚合物复合粉体的制备方法 - Google Patents
一种3d打印用金属颗粒/无机纳米颗粒/聚合物复合粉体的制备方法 Download PDFInfo
- 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
- Authority
- CN
- China
- Prior art keywords
- preparation
- powder
- plating
- solution
- printing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
一种3D打印用金属颗粒/无机纳米颗粒/聚合物复合粉体的制备方法,涉及化学镀及复合材料制备领域,制备方法为:(a)聚合物粉体材料表面改性;(b)改性聚合物粉体表面敏化和活化;(c)聚合物粉体表面化学镀。将制备的复合粉体进行分级,选择粒径为50~80μm的粉体作为原料可进行3D产品的打印。纳米金属颗粒和一维(或二维)纳米材料可协同改性聚合物基体,分散性好,起到增韧和增强的效果;同时,金属纳米粒子能吸附在一维(或二维)材料表面,界面好,增加与基体树脂的接触面积,使界面应力的传递效应得到提高,进而提升复合材料的界面结合强,从而提高复合粉体材料制备的3D打印制件的力学性能。
Description
技术领域
本发明涉及化学镀及复合材料制备领域,特别涉及到一种3D打印用金属颗粒/无机纳米颗粒/聚合物复合粉体的制备方法。
背景技术
化学镀作为制备金属包覆型粉体,其制备的复合粉体中金属颗粒有效润湿了基体粉体,实现了粉体颗粒均匀分散,同时实现原子层面上晶须与基体相匹配的界面结构,从而有利于增强体优良性能的发挥,提高复合材料的综合性能。金属包覆无机粉体是指以无机粉体为核心,以金属为外壳的复合粉体。这种复合粉体由于具有优异的电磁学、光学、化学催化以及可以改善金属和陶瓷之间的润湿性等优异的性质,近年来广泛应用于3D打印领域。
金属包覆无机粉体复合粉体的制备方法有溶胶凝胶法、机械混合法、化学镀法、非均相沉淀法等,其中化学镀法由于可以在任何基体表面都能制备出均匀、孔隙率低、厚度可控的金属镀层,且工艺易于控制、设备简单受到广泛的关注。
目前粉体表面化学镀工艺为:(1)粉体表面引入活性基团;(2)活性基团吸附催化剂;(3)吸附催化剂的粉体表面通过化学镀沉积金属粒子。例如,专利:02131262.1公开了无机粉体表面金属化的方法。此方法首先无机粉体经过铬酐的溶液粗化;然后经氯化亚锡盐酸溶液敏化,氯化钯盐酸溶液活化;最后进行表面化学镀覆金属层。其中粗化、敏化和活化过程均在酸性条件下,这种工艺不能实现如碳酸钙、粉煤灰、碳酸镁等粉体的表面化学镀。再如专利200780011903.8公开了导电性非电解电镀粉体及其制造方法。此方法是将芯材粉体与三聚氰胺树脂的初期缩合物接触,进行该初期缩合物的聚合反应,利用三聚氰胺树脂中的氨基吸附催化剂,从而实现化学镀。该方法是采用聚合物单体通过聚合反应在粉体表面引入活性基团,工艺复杂,另外聚合物同粉体表面缩合反应很难实现粉体表面完全包裹。因此,现有无机粉体化学镀的方法有待改善。
发明内容
本发明的目的在于克服现有粉体表面化学镀方法的不足,提供一种适用于各种无机粉体、工艺简单和环保的3D打印用金属颗粒/无机纳米颗粒/聚合物复合粉体的制备方法。
为了实现上述目的,本发明的技术方案如下:
一种3D打印用金属颗粒/无机纳米颗粒/聚合物复合粉体的制备方法,包含以下步骤:
(1)将聚合物粉体浸泡在表面改性溶液中1~30min,清洗、离心;
(2)将步骤(1)所得聚合物粉体浸入pH为1~3的敏化液中进行敏化,敏化温度为30~60℃,敏化时间为10~50min,水洗至中性;
(3)将步骤(2)所得敏化聚合物粉体浸入pH为1~4的活化液中进行活化,活化温度为30~60℃,活化时间为10~50min,水洗至中性;
(4)将步骤(3)所得活化后聚合物粉体化学施镀,在镀液中加入无机纳米颗粒分散液,采用机械搅拌以均匀分散粉体,化学镀时间为20~60min,化学镀镀液的温度为30~60℃,水洗,60℃干燥40min,得到3D打印用金属颗粒/无机纳米颗粒/聚合物复合粉体。
优选地,制备方法中,所述步骤(1)中聚合物粉体为尼龙、聚丙烯、聚乙烯、塑料聚苯硫醚、丙烯腈/苯乙烯/丁二烯共聚物中的至少一种。
优选地,制备方法中,所述步骤(1)中表面改性溶液为硅烷偶联剂KH550、硅烷偶联剂KH560、硅烷偶联剂KH792中的至少一种。硅烷偶联剂分子中含有两种不同的活性基因--氨基和氧基,用来偶联有机高分子和无机填料,增强其粘结性。
优选地,制备方法中,所述步骤(2)中的敏化液为氯化亚锡溶液。
优选地,制备方法中,所述步骤(3)中所述活化液为包含金属胶体催化剂的硼酸溶液,其中所述金属胶体催化剂为钯、铂、银和金中的至少一种。
优选地,制备方法中,所述步骤(4)中无机纳米颗粒分散液为多层石墨片分散液、石墨烯分散液、碳纳米管分散液、碳纤维分散液中的至少一种,尺寸为50~800nm,含量为1~100mg/L。
优选地,制备方法中,所述步骤(4)中化学镀包括化学镀铜、化学镀镍、化学镀钴和化学镀银中的至少一种。
同时,将上述方法制备的复合粉体进行分级,选择粒径为50~80μm的粉体作为原料可进行3D产品的打印。
纳米金属颗粒和一维(或二维)纳米材料可协同改性聚合物基体,分散性好,起到增韧和增强的效果;同时,金属纳米粒子能吸附在一维(或二维)材料表面,界面好,增加与基体树脂的接触面积,使界面应力的传递效应得到提高,进而提升复合材料的界面结合强,从而提高复合粉体材料制备的3D打印制件的力学性能。与现有技术相比,本发明的有益效果表现在:
1、本发明制备的复合粉体中,金属颗粒和无机纳米颗粒分散性能好且同基团表面粘接性能优异。
2、本发明制备工艺简单,可连续化生产。
3、本发明方案得到的复合粉体材料可提高3D打印制件的力学性能,流动性好、分散性好和界面粘接强度高,可广泛应用于3D打印领域。
具体实施方式
以下对本发明实施做进一步详述,以下实施例只是描述性的,不是限定性的,不能以此限定本发明的保护范围。该领域的技术人员根据上述本发明内容对本发明作出一些非本质的改进和调整,均视为本发明的保护范围之内。
实施例1
将干燥后的尼龙浸泡在硅烷偶联剂KH550(20%,其中水为40%,乙醇为40%)溶液中,时间30min,温度为60℃,取出后用净化水清洗一次,再离心。采用改性后的尼龙浸泡在5g/L的SnCl2(用盐酸调pH至1)溶液中敏化10min,温度30℃。取出后用去离子水清洗后浸入含有0.15g/L的PdCl2和20g/L的H3BO3(用盐酸调pH至2)溶液中10min进行活化,温度30℃,活化后的尼龙用去离子水冲洗。
配置化学镀镍镀液,镀液组分为:NiSO4·7H2O(15g/L)、NaH2PO2·H2O(15g/L)、Na3C6H5O7·2H2O(8g/L)、NH4Cl(18g/L)、多层石墨片分散液(600~800nm,含量为50mg/L)。将活化后的尼龙浸入30℃的化学镀镍镀液中施镀20min。化学镀镍后,用去离子水清洗,在烘箱中60℃干燥40min,即得表面包覆镍的尼龙粉体。
以粒径为50~80μm的镍颗粒/多层石墨片/尼龙复合粉体为原料,采用3D打印技术制备的成型件外观颗粒均匀、力学性能优良,拉伸强度为4.5MPa。
实施例2
将干燥后的聚丙烯浸泡在硅烷偶联剂KH792(20%,其中水为40%,乙醇为40%)溶液中,时间30min,温度为60℃,取出后用净化水清洗一次,再离心。采用改性后的聚丙烯浸泡在5g/L的SnCl2(用盐酸调pH至1)溶液中敏化20min,温度40℃。取出后用去离子水清洗后浸入含有0.15g/L的PdCl2和20g/L的H3BO3(用盐酸调pH至2)溶液中20min进行活化,温度40℃,活化后的聚丙烯用去离子水冲洗。
配制化学镀铜镀液,镀液组分为:NiSO4·7H2O(1g/L)、CuSO4·5H2O(24g/L)、NaH2PO2·H2O(55g/L)、Na3C6H5O7·2H2O(1.5g/L)、H3BO3(70g/L)、石墨烯分散液(100~300nm,含量为20mg/L)。将活化后的聚丙烯浸入40℃的化学镀铜镀液中施镀30min。化学镀铜后,用去离子水清洗,在烘箱中60℃干燥40min,即得表面包覆铜的聚丙烯粉体。
以粒径为50~80μm的铜颗粒/石墨烯/聚丙烯复合粉体为原料,采用3D打印技术制备的成型件外观颗粒均匀、力学性能优良,拉伸强度为4.5MPa。
实施例3
将干燥后的聚乙烯浸泡在硅烷偶联剂KH550(20%,其中水为40%,乙醇为40%)溶液中,时间30min,温度为60℃,取出后用净化水清洗一次,再离心。采用改性后的聚乙烯浸泡在5g/L的SnCl2(用盐酸调pH至1)溶液中敏化30min,温度50℃。取出后用去离子水清洗后浸入含有0.15g/L的PdCl2和20g/L的H3BO3(用盐酸调pH至2)溶液中30min进行活化,温度50℃,活化后的聚乙烯用去离子水冲洗。
配制化学镀银镀液,镀液组分为:AgNO3(29g/L)、NH3·H2O(4g/L)、和HCHO(55g/L)、碳纳米管分散液(300~600nm,含量为80mg/L)。将活化后的聚乙烯浸入50℃的化学镀银镀液中施镀40min。化学镀银后,用去离子水清洗,在烘箱中60℃干燥40min,即得表面包覆银的聚乙烯粉体。
以粒径为50~80μm的银颗粒/碳纳米管/聚乙烯复合粉体为原料,采用3D打印技术制备的成型件外观颗粒均匀、力学性能优良,拉伸强度为4.5MPa。
实施例4
将干燥后的塑料聚苯硫醚浸泡在硅烷偶联剂KH792(20%,其中水为40%,乙醇为40%)溶液中,时间30min,温度为60℃,取出后用净化水清洗一次,再离心。采用改性后的塑料聚苯硫醚浸泡在5g/L的SnCl2(用盐酸调pH至1)溶液中敏化40min,温度60℃。取出后用去离子水清洗后浸入含有0.15g/L的PdCl2和20g/L的H3BO3(用盐酸调pH至2)溶液中40min进行活化,温度60℃,活化后的塑料聚苯硫醚用去离子水冲洗。
配置化学镀镍镀液,镀液组分为:NiSO4·7H2O(15g/L)、NaH2PO2·H2O(15g/L)、Na3C6H5O7·2H2O(8g/L)、NH4Cl(18g/L)、碳纤维分散液(100~500nm,含量为40mg/L)。将活化后的塑料聚苯硫醚浸入60℃的化学镀镍镀液中施镀50min。化学镀镍后,用去离子水清洗,在烘箱中60℃干燥40min,即得表面包覆镍的塑料聚苯硫醚粉体。
以粒径为50~80μm的镍颗粒/碳纤维/塑料聚苯硫醚复合粉体为原料,采用3D打印技术制备的成型件外观颗粒均匀、力学性能优良,拉伸强度为4.5MPa。
实施例5
将干燥后的丙烯腈/苯乙烯/丁二烯共聚物浸泡在硅烷偶联剂KH560(20%,其中水为40%,乙醇为40%)溶液中,时间30min,温度为60℃,取出后用净化水清洗一次,再离心。采用改性后的丙烯腈/苯乙烯/丁二烯共聚物浸泡在5g/L的SnCl2(用盐酸调pH至1)溶液中敏化50min,温度60℃。取出后用去离子水清洗后浸入含有0.15g/L的PdCl2和20g/L的H3BO3(用盐酸调pH至2)溶液中50min进行活化,温度60℃,活化后的丙烯腈/苯乙烯/丁二烯共聚物用去离子水冲洗。
配置化学镀钴镀液,镀液组分为:CoCl2(25g/L)、NaH2PO2·H2O(25g/L)、Na3C6H5O7·2H2O(55g/L)、NH4Cl(45g/L)、H3BO3(25g/L)、石墨烯分散液(100~250nm,含量为25mg/L)。将活化后的丙烯腈/苯乙烯/丁二烯共聚物浸入60℃的化学镀钴镀液中施镀60min。化学镀钴后,用去离子水清洗,在烘箱中60℃干燥40min,即得表面包覆钴的丙烯腈/苯乙烯/丁二烯共聚物粉体。
以粒径为50~80μm的钴颗粒/石墨烯/丙烯腈/苯乙烯/丁二烯共聚物复合粉体为原料,采用3D打印技术制备的成型件外观颗粒均匀、力学性能优良,拉伸强度为4.5MPa。
Claims (8)
1.一种3D打印用金属颗粒/无机纳米颗粒/聚合物复合粉体的制备方法,其特征在于:包含以下步骤:
(1)将聚合物粉体浸泡在表面改性溶液中1~30min,清洗、离心;
(2)将步骤(1)所得聚合物粉体浸入pH为1~3的敏化液中进行敏化,敏化温度为30~60℃,敏化时间为10~50min,水洗至中性;
(3)将步骤(2)所得敏化聚合物粉体浸入pH为1~4的活化液中进行活化,活化温度为30~60℃,活化时间为10~50min,水洗至中性;
(4)将步骤(3)所得活化后聚合物粉体化学施镀,在镀液中加入无机纳米颗粒分散液,采用机械搅拌以均匀分散粉体,化学镀时间为20~60min,化学镀镀液的温度为30~60℃,水洗,60℃干燥40min,得到3D打印用金属颗粒/无机纳米颗粒/聚合物复合粉体。
2.如权利要求1所述的制备方法,其特征在于:所述步骤(1)中聚合物粉体为尼龙、聚丙烯、聚乙烯、塑料聚苯硫醚、丙烯腈/苯乙烯/丁二烯共聚物中的至少一种。
3.如权利要求1所述的制备方法,其特征在于:所述步骤(1)中表面改性溶液为硅烷偶联剂KH550、硅烷偶联剂KH560、硅烷偶联剂KH792中的至少一种。
4.如权利要求1所述的制备方法,其特征在于:所述步骤(2)中的敏化液为氯化亚锡溶液。
5.如权利要求1所述的制备方法,其特征在于:所述步骤(3)中所述活化液为包含金属胶体催化剂的硼酸溶液,其中所述金属胶体催化剂为钯、铂、银和金中的至少一种。
6.如权利要求1所述的制备方法,其特征在于:所述步骤(4)中无机纳米颗粒分散液为多层石墨片分散液、石墨烯分散液、碳纳米管分散液、碳纤维分散液中的至少一种,尺寸为50~800nm,含量为1~100mg/L。
7.如权利要求1所述的制备方法,其特征在于:所述步骤(4)中化学镀包括化学镀铜、化学镀镍、化学镀钴和化学镀银中的至少一种。
8.如权利要求1~7任一项所述方法制备的金属颗粒/无机纳米颗粒/聚合物复合粉体在3D产品打印中的应用,其特征在于:将制备的复合粉体进行分级,选择粒径为50~80μm的粉体作为原料进行3D产品的打印。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710235140.0A CN106903305A (zh) | 2017-04-12 | 2017-04-12 | 一种3d打印用金属颗粒/无机纳米颗粒/聚合物复合粉体的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710235140.0A CN106903305A (zh) | 2017-04-12 | 2017-04-12 | 一种3d打印用金属颗粒/无机纳米颗粒/聚合物复合粉体的制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN106903305A true CN106903305A (zh) | 2017-06-30 |
Family
ID=59195054
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710235140.0A Pending CN106903305A (zh) | 2017-04-12 | 2017-04-12 | 一种3d打印用金属颗粒/无机纳米颗粒/聚合物复合粉体的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106903305A (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108161017A (zh) * | 2018-01-04 | 2018-06-15 | 广东银纳科技有限公司 | 一种用于3d打印的金属粉及其制备方法 |
CN108914096A (zh) * | 2018-07-25 | 2018-11-30 | 芜湖昌菱金刚石工具有限公司 | 一种金刚石表面包覆Ni-W-P金属化镀层的制备方法 |
CN113621203A (zh) * | 2021-09-15 | 2021-11-09 | 南通理工学院 | 一种导电3d打印材料及其制备方法 |
CN114276675A (zh) * | 2022-01-26 | 2022-04-05 | 福州大学 | 一种用于mjr3d打印尼龙12复合材料及其制备方法 |
US11299642B2 (en) * | 2017-09-18 | 2022-04-12 | Morningbird Media Corporation | Systems and methods of additive printing of functional electronic circuits |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2939804A (en) * | 1958-01-23 | 1960-06-07 | Uarco Inc | Resin particle coated with metal |
US3647514A (en) * | 1968-08-28 | 1972-03-07 | Knapsack Ag | Surface-pretreatment of articles made from polyethylene or polypropylene or corresponding copolymers for chemical nickel-plating |
CN1401819A (zh) * | 2002-09-23 | 2003-03-12 | 北京工业大学 | 无机粉体表面金属化的方法 |
CN1740390A (zh) * | 2005-09-09 | 2006-03-01 | 清华大学 | 化学镀活化工艺和使用该工艺进行金属沉积的化学镀方法 |
CN1820876A (zh) * | 2006-03-23 | 2006-08-23 | 北京科技大学 | 一种制备镍、钴包覆无机粉体颗粒热涂层材料的方法 |
CN101415863A (zh) * | 2006-03-28 | 2009-04-22 | 日本化学工业株式会社 | 导电性非电解电镀粉体及其制造方法 |
CN105296973A (zh) * | 2015-12-01 | 2016-02-03 | 中北大学 | 一种超高分子量聚乙烯粉末表面化学镀镍方法 |
CN105821396A (zh) * | 2016-03-27 | 2016-08-03 | 华南理工大学 | 一种无钯化学镀铜的方法 |
CN106119818A (zh) * | 2016-08-30 | 2016-11-16 | 合肥乐凯科技产业有限公司 | 一种无机粉体表面化学镀的方法及其薄膜 |
CN106435537A (zh) * | 2016-12-06 | 2017-02-22 | 合肥乐凯科技产业有限公司 | 一种聚合物基材表面选择性化学镀的方法 |
-
2017
- 2017-04-12 CN CN201710235140.0A patent/CN106903305A/zh active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2939804A (en) * | 1958-01-23 | 1960-06-07 | Uarco Inc | Resin particle coated with metal |
US3647514A (en) * | 1968-08-28 | 1972-03-07 | Knapsack Ag | Surface-pretreatment of articles made from polyethylene or polypropylene or corresponding copolymers for chemical nickel-plating |
CN1401819A (zh) * | 2002-09-23 | 2003-03-12 | 北京工业大学 | 无机粉体表面金属化的方法 |
CN1740390A (zh) * | 2005-09-09 | 2006-03-01 | 清华大学 | 化学镀活化工艺和使用该工艺进行金属沉积的化学镀方法 |
CN1820876A (zh) * | 2006-03-23 | 2006-08-23 | 北京科技大学 | 一种制备镍、钴包覆无机粉体颗粒热涂层材料的方法 |
CN101415863A (zh) * | 2006-03-28 | 2009-04-22 | 日本化学工业株式会社 | 导电性非电解电镀粉体及其制造方法 |
CN105296973A (zh) * | 2015-12-01 | 2016-02-03 | 中北大学 | 一种超高分子量聚乙烯粉末表面化学镀镍方法 |
CN105821396A (zh) * | 2016-03-27 | 2016-08-03 | 华南理工大学 | 一种无钯化学镀铜的方法 |
CN106119818A (zh) * | 2016-08-30 | 2016-11-16 | 合肥乐凯科技产业有限公司 | 一种无机粉体表面化学镀的方法及其薄膜 |
CN106435537A (zh) * | 2016-12-06 | 2017-02-22 | 合肥乐凯科技产业有限公司 | 一种聚合物基材表面选择性化学镀的方法 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11299642B2 (en) * | 2017-09-18 | 2022-04-12 | Morningbird Media Corporation | Systems and methods of additive printing of functional electronic circuits |
CN108161017A (zh) * | 2018-01-04 | 2018-06-15 | 广东银纳科技有限公司 | 一种用于3d打印的金属粉及其制备方法 |
CN108914096A (zh) * | 2018-07-25 | 2018-11-30 | 芜湖昌菱金刚石工具有限公司 | 一种金刚石表面包覆Ni-W-P金属化镀层的制备方法 |
CN113621203A (zh) * | 2021-09-15 | 2021-11-09 | 南通理工学院 | 一种导电3d打印材料及其制备方法 |
CN114276675A (zh) * | 2022-01-26 | 2022-04-05 | 福州大学 | 一种用于mjr3d打印尼龙12复合材料及其制备方法 |
CN114276675B (zh) * | 2022-01-26 | 2022-12-23 | 福州大学 | 一种用于mjr3d打印尼龙12复合材料及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106903305A (zh) | 一种3d打印用金属颗粒/无机纳米颗粒/聚合物复合粉体的制备方法 | |
Olivera et al. | Plating on acrylonitrile–butadiene–styrene (ABS) plastic: a review | |
Zhu et al. | A Nature‐Inspired, Flexible Substrate Strategy for Future Wearable Electronics | |
Montazer et al. | Electroless plating of silver nanoparticles/nanolayer on polyester fabric using AgNO3/NaOH and ammonia | |
Kim et al. | EMI shielding behaviors of Ni-coated MWCNTs-filled epoxy matrix nanocomposites | |
Equbal et al. | Investigations on metallization in FDM build ABS part using electroless deposition method | |
Wang et al. | Adhesion improvement of electroless copper plating on phenolic resin matrix composite through a tin-free sensitization process | |
CN106119818B (zh) | 一种无机粉体表面化学镀的方法及其薄膜 | |
Lien et al. | Electroless silver plating on tetraethoxy silane-bridged fiber glass | |
US20070148457A1 (en) | Radiation absorptive composites and methods for production | |
CN102557487A (zh) | 一种镀银玻璃纤维及其制备方法 | |
Zhai et al. | Ni–P electroless deposition directly induced by sodium borohydride at interconnected pores of poly (ether ether ketone)/multiwalled carbon nanotubes composites surface | |
Lu et al. | Electroless nickel deposition on silane modified bamboo fabric through silver, copper or nickel activation | |
CN109957144A (zh) | 一种表面镀银导电填料的制备方法 | |
You et al. | Utilizing a pH-responsive palladium nanocomposite to fabricate adhesion-enhanced and highly reliable copper coating on nylon 6 fabrics | |
CN114260450B (zh) | 镀银微米级颗粒及其制备方法和用途 | |
Muraliraja et al. | A review of electroless coatings on non-metals: Bath conditions, properties and applications | |
JPH01230784A (ja) | 表面金属化重合体成形物の製造方法 | |
Chen et al. | PET Surface Modification with Inkjet-Printing Pd2+/Epoxy Resin Solution for Selective Electroless Copper Plating | |
JPH0254772A (ja) | 導電性プラスチック製品の製造方法 | |
Li et al. | Silane modification of semi-curing epoxy surface: High interfacial adhesion for conductive coatings | |
Geng et al. | Conductive aramid fibers from electroless Silver plating of crosslinked HPAMAM-modified PPTA: preparation and properties | |
Zhang et al. | Roughening of hollow glass microspheres by NaF for Ni electroless plating | |
KR101811994B1 (ko) | 전자파 차폐용 금속도금 유리섬유 강화 열가소성 수지 펠릿 및 그 제조방법 | |
KR101811995B1 (ko) | 금속도금 유리섬유를 포함하는 전기전도성 직물, 이의 제조방법 및 이를 이용하여 제조된 섬유강화복합재용 프리프레그 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170630 |