CN106119818B - 一种无机粉体表面化学镀的方法及其薄膜 - Google Patents
一种无机粉体表面化学镀的方法及其薄膜 Download PDFInfo
- Publication number
- CN106119818B CN106119818B CN201610784409.6A CN201610784409A CN106119818B CN 106119818 B CN106119818 B CN 106119818B CN 201610784409 A CN201610784409 A CN 201610784409A CN 106119818 B CN106119818 B CN 106119818B
- Authority
- CN
- China
- Prior art keywords
- minutes
- inorganic particle
- chemical plating
- inorganic
- dispersing agent
- 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.)
- Active
Links
- 239000000843 powder Substances 0.000 title claims abstract description 58
- 238000007747 plating Methods 0.000 title claims abstract description 57
- 239000000126 substance Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000010954 inorganic particle Substances 0.000 claims abstract description 42
- 230000004913 activation Effects 0.000 claims abstract description 27
- 239000012188 paraffin wax Substances 0.000 claims abstract description 14
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000002270 dispersing agent Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 206010070834 Sensitisation Diseases 0.000 claims description 10
- 230000008313 sensitization Effects 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 8
- 239000010881 fly ash Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 7
- 239000001119 stannous chloride Substances 0.000 claims description 7
- 235000011150 stannous chloride Nutrition 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 206010013786 Dry skin Diseases 0.000 claims description 5
- 239000004640 Melamine resin Substances 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- 150000008431 aliphatic amides Chemical class 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000005253 cladding Methods 0.000 abstract description 2
- 238000001994 activation Methods 0.000 description 25
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000002156 mixing Methods 0.000 description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 238000007772 electroless plating Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- JEZHBSJTXKKFMV-UHFFFAOYSA-N calcium nickel Chemical compound [Ca].[Ni] JEZHBSJTXKKFMV-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Classifications
-
- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- 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
-
- 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
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
-
- 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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
-
- 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
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
本发明涉及一种无机粉体表面化学镀的方法。其制备方法为：(a)无机粉体材料表面包覆石蜡；(b)无机粉体材料表面亲水改性；(c)无机粉体材料表面敏化和活化改性；(d)无机粉体表面化学镀。本发明提供的无机粉体化学镀的方法工艺流程简单，成本低廉，不受无机粉体表面形态限制，同时表面金属包覆完整，可广泛应用于导电涂料、电磁屏蔽等领域。
Description
技术领域：
本发明涉及化学镀技术领域，尤其涉及一种无机粉体表面化学镀的方法。
背景技术：
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，近年来广泛应用于电磁学材料、催化材料、导电等方面领域。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，中国专利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。再如中国专利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，提供一种无机粉体表面化学镀的方法，它适用于各种无机粉体、工艺简单、安全环保。
为了实现上述目的，本发明采取的技术方案如下：
(1)无机粉体在干燥设备中100℃-180℃温度下干燥至含水量<0.1％；
(2)将步骤(1)所得无机粉体与设定比例的分散剂在高混机内搅拌，100℃-160℃温度下活化混合10分钟-20分钟，继续加入设定比例的石蜡在高混机内搅拌，70℃-120℃下混合1分钟-30分钟；
(3)将步骤(2)所得无机粉体与设定比例的活性树脂在高混机内搅拌，60℃-120℃下混合1分钟-40分钟；
(4)将步骤(3)所得无机粉体浸入pH为1-3的敏化液中进行敏化，敏化温度为30℃-90℃，敏化时间为5分钟-50分钟，水洗至中性；
(5)将步骤(4)所得无机粉体浸入pH为1-4的活化液中进行活化，活化温度为40℃-80℃，活化时间为10分钟-50分钟，水洗至中性；
(6)将步骤(5)所得活化后无机粉体化学施镀，同时采用机械搅拌以均匀分散粉体，化学镀10分钟-30分钟后水洗，40℃-60℃干燥5分钟-20分钟，得到表面化学镀的无机粉体。
分散剂用于填料表面改性，防止无机粉体间团聚和提高无机粉体和石蜡间相容性；石蜡用于均匀包覆无机粉体，防止无机粉体在敏化和活化过程中同酸反应和接枝活性树脂；活性树脂用于吸附催化剂，有利于化学施镀。
上述无机粉体表面化学镀的方法，所述无机粉体为碳酸钙、硅藻土、硫酸钙、沸石、粉煤灰、滑石粉、云母粉、高岭土、硅灰石、碳酸镁中的一种或几种的混合物。
上述无机粉体表面化学镀的方法，所述分散剂为脂肪酸类分散剂、脂肪族酰胺类分散剂、石蜡类分散剂、金属皂类分散剂和低分子蜡类分散剂中的一种或几种的混合物，分散剂加入量为无机粉体重量0.5％-2％。
上述无机粉体表面化学镀的方法，所述活性树脂为硅烷偶联剂、三聚氰胺树脂、尿素、硫脲、苯胍胺中的一种或几种的混合物，活性树脂加入量为无机粉体重量1％-6％。
上述无机粉体表面化学镀的方法，所述石蜡加入量为无机粉体重量1％-5％。
上述无机粉体表面化学镀的方法，所述敏化液为氯化亚锡溶液，其中所述活化液包含金属胶体催化剂的溶液，其中金属胶体催化剂为钯、铂、银和金中的至少一种。
上述无机粉体表面化学镀的方法，所述无机粉体粒径为10微米-500微米。
本发明的另一个目的是这样实现的：
一种薄膜，其表面含有涂层，所述涂层中上述表面化学镀的无机粉体。
与现有技术相比，本发明存在以下有益效果：
1.本发明无机粉体采用石蜡包裹，能够避免无机粉体在敏化和活化过程中同酸反应，可以实现碳酸钙、粉煤灰、碳酸镁等无机粉体表面化学镀。
2.本发明采用的制备工艺简单，可以实现连续化生产。
3.本发明制备的产品中金属层均匀包覆在无机粉体表面，且包覆不受粉体形貌限制。
4.本发明方案得到的改性无机粉体，可用于导电涂料、电磁防护涂料中的导电填料。
附图说明：
图1：a：碳酸钙颗粒的扫描电镜图，b：碳酸钙颗粒的扫描电镜局部放大图，c：碳酸钙表面包覆镍颗粒的扫描电镜图，d:碳酸钙表面包覆镍颗粒的扫描电镜局部放大图；
图2：碳酸钙表面包覆镍颗粒的X射线衍射。
具体实施方式
下面通过实施例对本发明作进一步具体描述，所述实施例只用于理解本发明，并不能理解为对本发明保护范围的限制，本领域技术人员根据本发明核心技术对其作出一些等同改进和调整，均应视为在本发明的保护范围之内。
实施例1：
将50微米沸石在干燥设备中100℃温度下干燥10分钟，至含水量<0.1％；再将干燥后的沸石与占其重量2％的金属皂类分散剂在高混机内搅拌，100℃温度下活化混合20分钟，然后加入占沸石重量1％的石蜡在高混机内搅拌，90℃下混合30分钟，继续加入占沸石重量6％的尿素在高混机内搅拌，90℃下混合30分钟；将所得表面改性的无机粉体浸入pH为1的氯化亚锡溶液中进行敏化，敏化温度为90℃，敏化时间为5分钟，水洗至中性；接下来将所得粉体浸入pH为4的氯化钯溶液中进行活化，活化温度为40℃，活化时间为50分钟，取出，用去离子水清洗，40℃干燥20分钟。
配制化学镀铜镀液，镀液组分为：NiSO4·7H2O(1克/升)、CuSO4·5H2O(24克/升)、NaH2PO2·H2O(55克/升)、Na3C6H5O7·2H2O(1.5克/升)、H3BO3(70克/升)。将活化后的基材浸入40℃的化学镀铜镀液中施镀30分钟。化学镀铜后，用去离子水清洗，在烘箱中40℃干燥20分钟，即得表面包覆铜的沸石粉体，粉末体积电阻率小于8×10-3Ωcm。
实施例2：
将10微米硅藻土在干燥设备中180℃温度下干燥20分钟，至含水量<0.1％；再将干燥后的硅藻土与占硅藻土重量0.5％的脂肪族酰胺类分散剂在高混机内搅拌，160℃温度下活化混合10分钟，然后加入占硅藻土重量5％的石蜡在高混机内搅拌，90℃下混合30分钟，继续加入占硅藻土重量1％的三聚氰胺树脂在高混机内搅拌，90℃下混合30分钟；将所得表面改性的无机粉体浸入pH为3的氯化亚锡溶液中进行敏化，敏化温度为30℃，敏化时间为50分钟，水洗至中性；接下来将所得粉体浸入pH为1的氯化钯溶液中进行活化，活化温度为80℃，活化时间为10分钟，取出用去离子水清洗，60℃干燥5分钟。
配制化学镀银镀液，镀液组分为：AgNO3(29克/升)、NH3·H2O(4克/升)、和HCHO(55克/升)。将活化后的基材浸入45℃的化学镀银镀液中施镀25分钟。化学镀银后，用去离子水清洗，在烘箱中50℃干燥15分钟，即得表面包覆银的硅藻土粉体，粉末体积电阻率小于3×10-2Ωcm。
实施例3：
将85微米碳酸钙在干燥设备中145℃温度下干燥14分钟，至含水量<0.1％；再将干燥后的碳酸钙与占碳酸钙重量1％的脂肪酸类分散剂在高混机内搅拌，120℃温度下活化混合15分钟，然后加入占碳酸钙重量2％的石蜡在高混机内搅拌，90℃下混合30分钟，继续加入占碳酸钙重量2.8％的硅烷偶联剂(KH550)在高混机内搅拌，90℃下混合30分钟；将所得表面改性的无机粉体浸入pH为2的氯化亚锡溶液中进行敏化，敏化温度为80℃，敏化时间为30分钟，水洗至中性；接下来将所得粉体浸入pH为2.8的氯化钯溶液中进行活化，活化温度为60℃，活化时间为30分钟，取出用去离子水清，58℃干燥18分钟。
配制化学镀镍镀液，镀液组分为：NiSO4·7H2O(50克/升)、NaH2PO2·H2O(25克/升)、(NH4)2·SO4(11克/升)、C6H8O7(7克/升)。将活化后的基材浸入55℃的化学镀镍镀液中施镀20分钟。化学镀镍后，用去离子水清洗，在烘箱中45℃干燥18分钟，即得表面包覆镍的碳酸钙粉体，粉末体积电阻率小于2×10-2Ωcm。
实施例4：
将500微米粉煤灰在干燥设备中125℃温度下干燥16分钟，至含水量<0.1％；再将干燥后的碳酸钙与占粉煤灰重量1％的脂肪酸类分散剂在高混机内搅拌，110℃温度下活化混合12分钟，然后加入占粉煤灰重量2.5％的石蜡在高混机内搅拌，120℃下混合1分钟，继续加入占粉煤灰重量2.8％的硫脲在高混机内搅拌，120℃下混合1分钟；将所得表面改性的无机粉体浸入pH为2的氯化亚锡溶液中进行敏化，敏化温度为80℃，敏化时间为30分钟，水洗至中性；接下来将所得粉体浸入pH为2.8的氯化钯溶液中进行活化，活化温度为60℃，活化时间为30分钟，取出用去离子水清洗，55℃干燥15分钟。
配制化学镀镍镀液，镀液组分为：NiSO4·7H2O(50克/升)、NaH2PO2·H2O(25克/升)、(NH4)2·SO4(11克/升)、C6H8O7(7克/升)。将活化后的基材浸入55℃的化学镀镍镀液中施镀15分钟。化学镀镍后，用去离子水清洗，在烘箱中55℃干燥13分钟，即得表面包覆镍的粉煤灰粉体，粉末体积电阻率小于8×10-3Ωcm。
实施例5：
将200微米滑石粉在干燥设备中110℃温度下干燥18分钟，至含水量<0.1％；再将干燥后的滑石粉与占滑石粉重量0.5％的脂肪族酰胺类分散剂在高混机内搅拌，140℃温度下活化混合18分钟，然后加入占滑石粉重量4％的石蜡在高混机内搅拌，70℃下混合30分钟，继续加入占滑石粉重量1％的苯胍胺在高混机内搅拌，60℃下混合40分钟；将所得表面改性的无机粉体浸入pH为3的氯化亚锡溶液中进行敏化，敏化温度为30℃，敏化时间为50分钟，水洗至中性；接下来将所得粉体浸入pH为1的氯化钯溶液中进行活化，活化温度为80℃，活化时间为10分钟，取出用去离子水清洗，45干燥18分钟。
配制化学镀银镀液，镀液组分为：AgNO3(29克/升)、NH3·H2O(4克/升)、和HCHO(55克/升)。将活化后的基材浸入45℃的化学镀银镀液中施镀10分钟。化学镀银后，用去离子水清洗，在烘箱中60℃干燥10分钟，即得表面包覆银的滑石粉粉体，粉末体积电阻率小于9×10-3Ωcm。
Claims (6)
1.一种无机粉体表面化学镀的方法，其特征在于，包含以下步骤：
(1)无机粉体在干燥设备中100℃-180℃温度下干燥至含水量<0.1％；
(2)将步骤(1)所得无机粉体与设定比例的分散剂在高混机内搅拌，100℃-160℃温度下活化混合10分钟-20分钟，继续加入设定比例的石蜡在高混机内搅拌，70℃-120℃下混合1分钟-30分钟；
(3)将步骤(2)所得无机粉体与设定比例的树脂在高混机内搅拌，60℃-120℃下混合1分钟-40分钟；所述树脂为硅烷偶联剂、三聚氰胺树脂、尿素、硫脲或苯胍胺中的一种或几种的混合物；所述树脂的加入量为步骤(1)中的无机粉体重量1％-6％；
(4)将步骤(3)所得无机粉体浸入pH为1-3的敏化液中进行敏化，敏化温度为30℃-90℃，敏化时间为5分钟-50分钟，水洗至中性；
(5)将步骤(4)所得无机粉体浸入pH为1-4的活化液中进行活化，活化温度为40℃-80℃，活化时间为10分钟-50分钟，水洗至中性；
(6)将步骤(5)所得活化后无机粉体化学施镀，采用机械搅拌以均匀分散粉体，化学镀10分钟-30分钟后水洗，40℃-60℃干燥5分钟-20分钟，得到表面化学镀的无机粉体；
所述步骤(2)中的分散剂为脂肪酸类分散剂、脂肪族酰胺类分散剂、石蜡类分散剂、金属皂类分散剂和低分子蜡类分散剂中的一种或几种的混合物，分散剂加入量为步骤(1)中的无机粉体重量0.5％-2％。
2.根据权利要求1所述的一种无机粉体表面化学镀的方法，其特征在于：所述步骤(1)中的无机粉体为碳酸钙、硅藻土、硫酸钙、沸石、粉煤灰、滑石粉、云母粉、高岭土、硅灰石、碳酸镁中的一种或几种的混合物，无机粉体粒径为10微米-500微米。
3.根据权利要求2所述的一种无机粉体表面化学镀的方法，其特征在于：所述步骤(2)中石蜡加入量为步骤(1)中的无机粉体重量1％-5％。
4.根据权利要求3所述的一种无机粉体表面化学镀的方法，其特征在于：所述步骤(4)中敏化液为氯化亚锡溶液，所述活化液包含金属胶体催化剂的溶液，其中所述金属胶体催化剂为钯、铂、银和金中的至少一种。
5.根据权利要求4所述的一种无机粉体表面化学镀的方法，其特征在于：所述步骤(5)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。
6.一种薄膜，其特征在于，所述薄膜表面含有涂层，所述涂层中含有如权利要求1-5中任一项权利所得到的表面化学镀的无机粉体。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610784409.6A CN106119818B (zh) | 2016-08-30 | 2016-08-30 | 一种无机粉体表面化学镀的方法及其薄膜 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610784409.6A CN106119818B (zh) | 2016-08-30 | 2016-08-30 | 一种无机粉体表面化学镀的方法及其薄膜 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106119818A CN106119818A (zh) | 2016-11-16 |
| CN106119818B true CN106119818B (zh) | 2019-05-07 |
Family
ID=57273377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610784409.6A Active CN106119818B (zh) | 2016-08-30 | 2016-08-30 | 一种无机粉体表面化学镀的方法及其薄膜 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106119818B (zh) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106903305A (zh) * | 2017-04-12 | 2017-06-30 | 合肥学院 | 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 |
| CN106947960A (zh) * | 2017-04-12 | 2017-07-14 | 合肥学院 | 一种3d打印用聚合物/金属复合粉体材料的制备方法 |
| CN108384233A (zh) * | 2018-03-08 | 2018-08-10 | 东华理工大学 | 一种镍包覆粉煤灰/聚吡咯复合吸波材料的制备方法 |
| CN108866520B (zh) * | 2018-09-25 | 2020-01-03 | 合肥工业大学 | 钛合金表面化学镀耐磨涂层的制备方法 |
| CN110964355B (zh) * | 2018-09-29 | 2021-09-07 | 中国科学院过程工程研究所 | 一种包覆镍的粉煤灰及其制备方法和用途 |
| CN110845923A (zh) * | 2019-12-04 | 2020-02-28 | 厦门珉瑶贸易有限公司 | 一种镀钴煤灰的有机-无机复合富锌涂料 |
| CN113501976B (zh) * | 2021-08-11 | 2022-06-03 | 电子科技大学 | 一种电磁屏蔽自修复亲肤水凝胶的制备方法 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5445631A (en) * | 1977-09-17 | 1979-04-11 | Fujitsu Ltd | Partial plating for plastic members |
| JPS6041718B2 (ja) * | 1978-10-27 | 1985-09-18 | 日立電線株式会社 | 打抜条材の部分メツキ法 |
-
2016
- 2016-08-30 CN CN201610784409.6A patent/CN106119818B/zh active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 关于石膏电镀;刘仁志;《电镀与精饰》;19830531;54 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106119818A (zh) | 2016-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106119818B (zh) | 一种无机粉体表面化学镀的方法及其薄膜 | |
| CN103433485B (zh) | 一种镍包铝粉及制备方法 | |
| CN106011809B (zh) | 一种通过邻苯二酚-多胺制备表面包覆银的复合材料的方法 | |
| CN102176337B (zh) | 各向异性导电胶膜用复合导电粒子及制备方法 | |
| CN1299863C (zh) | 空心或包覆型镍合金球形粉末的制备方法 | |
| CN1936078A (zh) | 一种新型复合导电微球及其制备方法 | |
| CN100355939C (zh) | 镍或镍合金粉末表面包覆蜂窝状金属钴或钴合金的方法 | |
| Zhang et al. | Roughening of hollow glass microspheres by NaF for Ni electroless plating | |
| CN109112508B (zh) | 一种钴包覆氧化铝复合粉体的制备方法 | |
| JPH0344149B2 (zh) | ||
| JPS63103900A (ja) | 金属被覆無水硫酸カルシウム・ウイスカ− | |
| CN107034453B (zh) | 一种钯胶体活化液的制备方法 | |
| JPS6059070A (ja) | 粉粒体メツキ品の製造法 | |
| CN104195532A (zh) | 一种石墨片表面化学镀铁镍合金层的制备方法 | |
| Zheng et al. | Fabrication of Ag–C composite materials with core–shell structure | |
| CN1333387A (zh) | 轻型复合空心金属微球的制备方法 | |
| CN103071788A (zh) | 一种制备镍银核壳结构纳米粒子的方法 | |
| JP2001247714A (ja) | 導電性充填剤 | |
| JP3858971B2 (ja) | 微粒子の無電解めっき方法 | |
| JPH0224358A (ja) | 無電解めっき粉末含有ポリマー組成物 | |
| JPH0215176A (ja) | 磁性無電解めっき粉体の製造方法 | |
| CN100372966C (zh) | 一种非晶态镍磷核-壳、空壳结构材料的制备方法 | |
| CN101250695A (zh) | 一种铁硼合金化学镀液及其铁硼合金镀层材料和制备方法 | |
| CN115007855B (zh) | 一种银包镍铝粉复合物及其制备方法和应用 | |
| Jia et al. | Preparation of microwave absorbing nickel-based activated carbon by electroless plating with palladium-free activation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |