CN105209660B - 涂覆碳纳米材料的方法 - Google Patents
涂覆碳纳米材料的方法 Download PDFInfo
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- CN105209660B CN105209660B CN201480021818.XA CN201480021818A CN105209660B CN 105209660 B CN105209660 B CN 105209660B CN 201480021818 A CN201480021818 A CN 201480021818A CN 105209660 B CN105209660 B CN 105209660B
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- solution
- nano material
- plating
- reducing agent
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 21
- 238000000576 coating method Methods 0.000 title description 23
- 239000011248 coating agent Substances 0.000 title description 22
- 239000000243 solution Substances 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 238000007747 plating Methods 0.000 claims abstract description 25
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 30
- 229910052709 silver Inorganic materials 0.000 claims description 20
- 239000004332 silver Substances 0.000 claims description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 229910052763 palladium Inorganic materials 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002134 carbon nanofiber Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229960001484 edetic acid Drugs 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 3
- 229940005991 chloric acid Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229940079877 pyrogallol Drugs 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- -1 oxy radical Chemical class 0.000 description 9
- 239000010410 layer Substances 0.000 description 7
- 235000013339 cereals Nutrition 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 239000002082 metal nanoparticle Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 230000013016 learning Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002061 nanopillar Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1664—Process features with additional means during the plating process
- C23C18/1666—Ultrasonics
-
- 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
-
- 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
- C23C18/1675—Process conditions
- C23C18/1676—Heating of the solution
-
- 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
- C23C18/1675—Process conditions
- C23C18/1682—Control of atmosphere
-
- 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
- C23C18/1689—After-treatment
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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)
- Carbon And Carbon Compounds (AREA)
- Chemically Coating (AREA)
- Catalysts (AREA)
Abstract
提供了在碳纳米材料上自催化镀纳米颗粒的方法，所述方法包括：提供在包含氧化剂的溶液中的纳米材料，该溶液被维持在第一温度范围内并且搅拌该溶液持续第一预定的时间段；加热该溶液以达到高于第一温度范围的第二温度范围，并且搅拌该溶液持续短于第一时间段的第二预定的时间段，同时使该溶液维持在第二温度范围内；过滤并且冲洗纳米材料；使纳米材料分散在包含敏化剂的水溶液中；使纳米材料沉浸在包含粘附至纳米材料的种子颗粒的混合物中；收集纳米材料；通过沉浸在包含水性金属源和第一水性还原剂的镀液中镀纳米材料，使得金属层在纳米材料上从种子颗粒生长；从镀液移除纳米材料；使纳米材料分散在包含第二还原剂的水溶液中；加热该溶液以达到第三温度范围并且进行加热的溶液的超声处理持续第三预定的时间段，同时使该溶液维持在第三温度范围内。
Description
发明领域
本发明涉及碳基纳米材料，并且特别地涉及这类材料的涂覆。
技术背景
碳基纳米材料(CNM)最近已经吸引了大量的注意，这是因为其突出的机械性质和电学性质。例如，碳纳米管(CNT)、碳纳米纤维(CNF)和石墨烯是用于多种应用的理想原材料，这是由于其优良的机械特性，包括高抗张强度和高弹性模量以及高热导率和高电导率。
因此，积极推行用于CNM的实际应用的研究。特别地，并入这些纳米材料的金属复合材料示出作为提供改进的且独特的功能的新的材料的希望。例如，金属-CNF复合材料被期望具有高强度和高热导率。然而，在复合材料内可以检测到某些缺陷和空隙，这是因为CNF的与诸如锡合金、铝和银的熔融金属的差的润湿性，这也是所有种类的CNM中存在的常见问题。因此，在与金属合金组合之前CNM的表面改性是必需的。
在表面上应用金属涂层是改进其与熔融金属的润湿性的最有效的方法之一。金属涂层或沉积物还可以赋予CNM多种有益的性质，诸如高平均密度、在多种溶剂中的良好溶解性以及合意的磁性性质和催化性质。金属涂覆的CNM的高平均密度可以阻止其免于在回流之后作为杂质被焊剂移除。均匀的金属涂层还可以充当屏障以阻止纳米材料团聚，从而使其更易获得良好分散的CNM悬浮物。用铁磁金属涂覆的CNM可以通过磁场可受控制地被移动，这可以导致具有高度受控的微织构的CNM复合材料。用催化金属颗粒沉积的CNM可以提供优越的催化剂，具有诸如改进的燃料电池电极的应用。
因此，CNM的表面上的均匀分散的金属涂层对于实现前述引人注目的性质变得重要。然而，CNM的惰性性质还导致与周围环境弱的相互作用，因此在表面功能化(包括金属纳米颗粒的均匀沉积)方面提供了挑战。关于CNM的金属涂层工艺是已知的，但正常敏化工艺，像简单使用锡(II)离子作为敏化剂来预处理CNM，没有很好地起作用，这是因为CNM的强的表面惰性，并且传统的硝酸处理不能形成足够的活化点，因为碳和硝酸之间的反应不能被精确地控制。所有这些因素将对沉积的金属纳米颗粒的粒度分布和均匀性具有负面影响。
发明概述
鉴于涂覆的纳米材料的以上提及的期望的性质，以及现有技术的以上提及的和其他缺陷，本发明的目的是提供用于碳纳米材料的自催化镀的改进的方法。
根据本发明的第一方面，因此提供用于碳纳米材料的自催化镀的方法，所述方法包括以下的步骤：提供在包含至少两种氧化剂的氧化溶液中的碳纳米材料，溶液被维持在第一温度范围内并且搅拌溶液持续第一预定的时间段；加热溶液以达到高于第一温度范围的第二温度范围，并且搅拌该溶液持续短于第一时间段的第二预定的时间段，同时使溶液维持在第二温度范围内；从氧化溶液移除纳米材料；使纳米材料分散在包含敏化剂的水性敏化溶液中；从敏化溶液移除纳米材料；使纳米材料沉浸在包含粘附至纳米材料的种子颗粒的种子混合物中；从种子混合物移除纳米材料；通过使纳米材料沉浸在包含水性金属源和第一水性还原剂的镀液中镀纳米材料，使得金属层在纳米材料上从种子颗粒生长；从镀液移除纳米材料；使纳米材料分散在包含第二还原剂的水溶液中；以及加热溶液以达到第三温度范围并且进行加热的溶液的超声处理持续第三预定的时间段，同时使溶液维持在第三温度范围内。
在本上下文中，碳纳米材料(CNM)应该被理解为具有至少某些在纳米大小范围内的特征的碳基材料或结构。
自催化镀，也被称为无电镀或化学镀，涉及在不使用外部电功率的情况下在水溶液中发生反应的过程。
从相应的溶液和/或混合物移除碳纳米材料的步骤可以通过技术人员已知的诸如过滤和/或干燥的任何常规方法来进行。
本发明基于以下认识：在预处理步骤期间，通过使用至少两种不同氧化剂(多氧化剂)，CNM的表面被在某个温度范围下对碳具有强烈作用的多氧化剂氧化。从而，氧化的程度可以通过修改反应温度和反应时间来精确地控制。控制CNM的氧化的程度是重要的，因为过高的氧化程度可以破坏碳材料的结构。
这里，氧化被分成两个步骤，其中在工艺开始时，维持低温持续长时间，以使得氧化剂渗入碳分子间隔。接下来，温度被提高并且被维持较短的时间以引发反应。在此步骤，最初稳定的sp2碳碳键被突然破坏，且代替地在CNM的表面上形成充足的可逆的含氧基团，而不破坏材料的整体结构。可以快速提高温度。
在表面氧化之后，通过无电沉积过程合成金属层，在无电沉积过程中CNM的表面上的金属纳米颗粒的分散、大小和几何结构可以很好地被控制，这是因为络合剂的存在和还原剂使精制的和均匀的金属纳米颗粒沉积在基底表面上的特定性质。随后的金属涂覆的CNM的还原可以从碳表面移除大部分含氧基团并且使碳碳键重新形成。
在本发明的一个实施方案中，第一温度范围可以有利地是-10℃至10℃并且第一时间段可以是1h-8h。
在本发明的一个实施方案中，第二温度范围可以有利地是30-50℃并且第二时间段可以是10-60min。已经发现，以上提及的温度范围和时间段允许CNM的有效氧化，而不破坏CNM的原始结构。
根据本发明的一个实施方案，氧化剂可以有利地包括硫酸、硝酸、高锰酸钾、重铬酸钾和氮化钠中的至少两种。通过利用例如硫酸分子来渗透穿过CNT的不同层并且将高锰酸钾分子带入内部并且实现氧化，可以形成足够量的氧化斑点以促进随后的金属涂覆过程。
此外，敏化剂可以优选地包括甲醛、聚乙烯吡咯烷酮或氯化锡(II)。
在本发明的一个实施方案中，从氧化溶液移除纳米材料的步骤可以有利地包括过滤纳米材料且以去离子水冲洗直到冲洗液的pH值是约7。从而，通过监测pH值，可以确定所有氧化剂被移除以及可以确定仅碳纳米材料保留。
根据本发明的一个实施方案，种子颗粒可以有利地包含钯。例如，可以从氯化钯提供钯。然而，其他金属还可以被用作种子颗粒，诸如金、银和铜。
根据本发明的一个实施方案，第一还原剂可以包括硫酸钴、氯化亚铁、甲醛、聚乙烯吡咯烷酮、氨水、乙二胺、乙二胺四乙酸或苯并三唑。
根据本发明的一个实施方案，镀的步骤可以有利地包括通过超声波移除所述溶液中的溶解氧以避免所述还原剂的氧化。
根据本发明的一个实施方案，镀的步骤可以在密闭的容器中使氮气穿过所述溶液来进行。
根据本发明的一个实施方案，水性金属源可以包括钯、银、金或镍。
在本发明的一个实施方案中，水性金属源可以是选自包括以下的组的金属离子源：氮化银、氯酸钯、氯化金、氯化镍、氨水、硫酸铵、乙二胺和乙二胺四乙酸。
在本发明的一个实施方案中，第三温度范围可以是60-100℃并且第三时间段可以是至少一个小时。
在本发明的一个实施方案中，碳纳米材料可以是碳纳米管、碳纳米纤维或石墨烯。当然，还可以使用其他类似的碳基纳米材料。此外，类似的碳纳米材料可以通过不同的名称被提到，诸如纳米棒、纳米柱、纳米线及类似物。
在本发明的一个实施方案中，镀的步骤可以被进行持续0.5h至24h。镀的时间确定CNM上获得的金属涂层的厚度。因此，可能通过控制镀的时间来实现期望的涂层厚度。
根据本发明的一个实施方案，第二还原剂可以有利地选自包括以下的组：氢氧化钾、硼氢化钠、焦棓酸、L-抗坏血酸和一水合肼。第二还原剂优选地是强还原剂。
当学习所附权利要求和以下描述时，本发明的另外的特征和优点将变得明显。技术人员认识到，在不背离本发明的范围的情况下，本发明的不同特征可以被组合以产生除了以下描述的那些以外的实施方案。
附图简述
现在将参考示出本发明的示例性实施方案的附图更详细地描述本发明的此方面和其他方面，在附图中：
图1是概述根据本发明的实施方案的方法的一般步骤的流程图；
图2a-b是示出根据本发明的实施方案制造的材料的TEM图像；
图3a-b是示出根据本发明的实施方案制造的材料的TEM图像；以及
图4是根据本发明的实施方案涂覆的材料的XRD图。
本发明的优选的实施方案的详细描述
在本详细描述中，参考诸如碳纳米管、碳纳米纤维或石墨烯(此后称为CNM)的碳纳米材料(CNM)主要讨论根据本发明的涂覆纳米材料的方法的各个实施方案。
将参考概述该工艺的一般步骤的图1的流程图描述制造涂覆的纳米材料的方法。
首先102，在丙酮和去离子水中冲洗选择的CNM以从CNM的表面移除任何杂质和保护层。
在冲洗之后，使CNM与多氧化剂在约-10℃至10℃的范围内的温度下混合104，随后在该温度下搅拌持续1-4h以确保氧化剂的分子侵入CNM的表面内而不发生强氧化。氧化剂包括硫酸、硝酸、高锰酸钾、重铬酸钾和氮化钠中的至少两种。硫酸和氮化钠充当插层剂以促使氧化剂进入CNT的内层，并且可以是高锰酸钾的氧化剂在CNT上引起表面氧化。氧化剂应该被非常慢地添加到硫酸中以避免爆炸反应。
然后，温度被升高并且控制以被维持在30-50℃的范围内，同时搅拌持续约0.5h至3h。
在那之后，通过使用真空过滤使氧化的CNM从溶液分离，并且随后用去离子水洗涤CNM若干次直到滤液的pH是约7以确保氧化剂完全被移除。
洗涤之后使氧化的CNM分散在敏化剂水溶液中，使得CNM被敏化106。敏化剂可以例如被选择为甲醛、聚乙烯吡咯烷酮或氯化锡(II)。
在敏化之后，通过浸入含有氯化钯的溶液中(在该溶液中钯颗粒粘附至CNM)、随后离心并且用蒸馏水冲洗直到过滤的溶液的pH是7，使CNM活化108。然后，收集涂覆有钯种子的CNM并且在真空烘箱中干燥。钯种子颗粒作为随后银生长的成核点是特别有利的，因为钯是引发银自镀过程的良好催化剂。
接着，使活化的CNM浸入自催化镀液中。自催化镀液被制备成两种分开的溶液，水性金属离子源溶液和水性还原剂溶液，以在镀之前等量地被混合。在室温下实施镀110并且沉积时间取决于需要的涂层厚度。例如，CNM上的金属纳米颗粒的生长速率可以是约0.5nm/h。为避免还原剂氧化，通过超声波移除在去离子水中的溶解氧，并且在密闭的容器中使氮气穿过溶液进行沉积。从而，在不破坏碳纳米材料的结构下，提供具有良好定义的和均匀的金属涂层的碳基纳米材料。
水性钴还原剂溶液可以是以下化学品中的一种或若干种：硫酸钴、氯化亚铁、甲醛、聚乙烯吡咯烷酮、氨水、乙二胺、乙二胺四乙酸和苯并三唑。
水性金属离子源溶液可以是氮化银、氯酸钯、氯化金、氯化镍、氨水、硫酸铵、乙二胺和乙二胺四乙酸中的一种或若干种。从而，可以涂覆诸如，钯、银、金和镍的金属。通常，可以期望提供具有5nm至100nm的范围内的厚度的金属涂层。
在反应完成之后，即在已经达到期望的厚度之后，金属涂覆的CNM被过滤并且被洗涤直到滤液的颜色变成大体上透明的。洗涤之后使用超声使CNM再分散在具有强还原剂的去离子水中，112。第二还原溶液被用于移除CNM上的含氧基团并且可以是以下化学品中的一种或若干种：氢氧化钾、硼氢化钠、焦棓酸、L-抗坏血酸和一水合肼。还原过程在60-100℃下被实施持续若干小时，比如1h至12h之间。最后，将金属涂覆的CNM滤出并且在真空烘箱中干燥直到观察不到质量损失。
使用透射电子显微镜(TEM)检查涂覆有银层的CNM的形态学。使用X射线衍射(XRD)分析样品的元素组成和结构分析。
图2a示出原始碳纳米纤维(CNF)的TEM图像，并且图2b是涂覆有银纳米颗粒的碳纳米纤维的图像。选择具有50nm的直径的CNF来阐明涂覆过程。在涂覆之后，具有3～5nm的直径的银纳米颗粒的层被均匀分散在CNF的表面上，而不破坏其原始结构。
图3a-b是以不同放大率示出银涂覆的石墨烯的TEM图像。在涂覆之后，具有2～3nm的受控大小的银纳米颗粒的层被均匀分散在石墨烯片的两侧上以形成银/石墨烯/银混合材料。银涂层是足够薄的，以致不影响石墨烯的性质。
图4示出银涂覆的碳纳米纤维样品的X射线衍射(XRD)图。通过对应于金属银的面心立方(FCC)结构的峰的出现，最显著地(111)反射，在衍射图中确证银的存在。
尽管已经参考本发明的特定的示例性实施方案描述本发明，但许多不同改变、修改及类似物将对本领域技术人员变得明显。
此外，公开的实施方案的变型可由本领域技术人员通过对附图、公开内容和所附权利要求的学习而被理解并在实践所要求保护的发明中实现。在权利要求中，词“包括”不排除其他要素或步骤，且不定冠词“一(a)”或“一(an)”不排除复数。
Claims (14)
1.一种用于碳纳米材料的自催化镀的方法，所述方法包括以下的步骤：
提供在包含至少两种氧化剂的氧化溶液中的碳纳米材料，所述溶液被维持在-10℃至10℃的第一温度范围内，并且搅拌所述溶液持续1h-8h的第一预定的时间段；
加热所述溶液以达到30-50℃的第二温度范围，并且搅拌所述溶液持续10-60min的第二预定的时间段，同时使所述溶液维持在所述第二温度范围内；
从所述氧化溶液移除所述纳米材料；
使所述纳米材料分散在包含敏化剂的水性敏化溶液中；
从所述敏化溶液移除所述纳米材料；
使所述纳米材料沉浸在包含粘附至所述纳米材料的种子颗粒的种子混合物中；
从所述种子混合物移除所述纳米材料；
通过使所述纳米材料沉浸在包含水性金属源和第一水性还原剂的镀液中镀所述纳米材料，使得金属层在所述纳米材料上从所述种子颗粒生长；
从所述镀液移除所述纳米材料；
使所述纳米材料分散在包含第二还原剂的水溶液中；以及
加热所述溶液以达到第三温度范围并且进行所述加热的溶液的超声处理持续第三预定的时间段，同时使所述溶液维持在所述第三温度范围内。
2.根据权利要求1所述的方法，其中所述氧化剂包括硫酸、高锰酸钾、重铬酸钾和氮化钠中的至少两种。
3.根据权利要求1或2所述的方法，其中所述敏化剂包括甲醛、聚乙烯吡咯烷酮或氯化锡(II)。
4.根据权利要求1或2所述的方法，其中从所述氧化溶液移除所述纳米材料的所述步骤包括过滤所述纳米材料且以去离子水冲洗直到冲洗液的pH值是约7。
5.根据权利要求1或2所述的方法，其中所述种子颗粒包含钯。
6.根据权利要求1或2所述的方法，其中所述第一还原剂包括硫酸钴、氯化亚铁、甲醛、聚乙烯吡咯烷酮、氨水、乙二胺、乙二胺四乙酸或苯并三唑。
7.根据权利要求1或2所述的方法，其中所述镀的步骤包括通过超声波移除所述溶液中的溶解氧，使得避免所述还原剂的氧化。
8.根据权利要求1或2所述的方法，其中所述镀的步骤在密闭的容器中使氮气穿过所述溶液来进行。
9.根据权利要求1或2所述的方法，其中所述水性金属源包括钯、银、金或镍。
10.根据权利要求1或2所述的方法，其中所述水性金属源是选自包括以下的组的金属离子源：氮化银、氯酸钯、氯化金或氯化镍。
11.根据权利要求1或2所述的方法，其中所述第三温度范围是60-100℃并且所述第三时间段是至少一小时。
12.根据权利要求1或2所述的方法，其中所述碳纳米材料是碳纳米管、碳纳米纤维或石墨烯。
13.根据权利要求1或2所述的方法，其中所述镀的步骤被进行持续0.5h至24h的时间段。
14.根据权利要求1或2所述的方法，其中所述第二还原剂选自包括以下的组：氢氧化钾、硼氢化钠、焦棓酸、L-抗坏血酸和一水合肼。
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| PCT/EP2014/057859 WO2014173793A1 (en) | 2013-04-21 | 2014-04-17 | Method for coating of carbon nanomaterials |
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| CN101952906A (zh) * | 2008-03-25 | 2011-01-19 | 东丽株式会社 | 导电性复合体及其制造方法 |
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| JP2016526092A (ja) | 2016-09-01 |
| KR20160002912A (ko) | 2016-01-08 |
| WO2014173793A1 (en) | 2014-10-30 |
| US20160068965A1 (en) | 2016-03-10 |
| CN105209660A8 (zh) | 2017-04-12 |
| JP6415540B2 (ja) | 2018-10-31 |
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