CN106270500A - A kind of carbon nano tube surface is uniformly coated with the method and device of argent - Google Patents
A kind of carbon nano tube surface is uniformly coated with the method and device of argent Download PDFInfo
- Publication number
- CN106270500A CN106270500A CN201610868742.5A CN201610868742A CN106270500A CN 106270500 A CN106270500 A CN 106270500A CN 201610868742 A CN201610868742 A CN 201610868742A CN 106270500 A CN106270500 A CN 106270500A
- Authority
- CN
- China
- Prior art keywords
- cnt
- argent
- solution
- nano tube
- carbon nano
- Prior art date
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 59
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000007747 plating Methods 0.000 claims abstract description 38
- 239000000126 substance Substances 0.000 claims abstract description 37
- 239000010453 quartz Substances 0.000 claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003708 ampul Substances 0.000 claims abstract description 31
- 229910052709 silver Inorganic materials 0.000 claims abstract description 31
- 239000004332 silver Substances 0.000 claims abstract description 31
- 230000007935 neutral effect Effects 0.000 claims abstract description 24
- 239000012159 carrier gas Substances 0.000 claims abstract description 20
- 238000002604 ultrasonography Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000010304 firing Methods 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 8
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 4
- 239000000443 aerosol Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 56
- 239000000725 suspension Substances 0.000 claims description 52
- 239000008367 deionised water Substances 0.000 claims description 48
- 229910021641 deionized water Inorganic materials 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 238000000926 separation method Methods 0.000 claims description 20
- 238000006396 nitration reaction Methods 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 230000003213 activating effect Effects 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 230000001235 sensitizing effect Effects 0.000 claims description 13
- 230000020477 pH reduction Effects 0.000 claims description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 12
- 206010070834 Sensitisation Diseases 0.000 claims description 11
- 230000008313 sensitization Effects 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 230000033228 biological regulation Effects 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 238000005276 aerator Methods 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000001117 sulphuric acid Substances 0.000 claims description 7
- 235000011149 sulphuric acid Nutrition 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000004568 cement Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 230000009514 concussion Effects 0.000 claims description 4
- 239000011521 glass 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
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 3
- 239000001263 FEMA 3042 Substances 0.000 claims description 3
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims description 3
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims description 3
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 3
- 229940033123 tannic acid Drugs 0.000 claims description 3
- 235000015523 tannic acid Nutrition 0.000 claims description 3
- 229920002258 tannic acid Polymers 0.000 claims description 3
- -1 Aldolactol Chemical compound 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- ZGCHATBSUIJLRL-UHFFFAOYSA-N hydrazine sulfate Chemical compound NN.OS(O)(=O)=O ZGCHATBSUIJLRL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000377 hydrazine sulfate Inorganic materials 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 238000005352 clarification Methods 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 12
- 239000007921 spray Substances 0.000 abstract description 8
- 238000009713 electroplating Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000178 monomer Substances 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000007788 liquid Substances 0.000 description 8
- 238000002242 deionisation method Methods 0.000 description 6
- 101150003085 Pdcl gene Proteins 0.000 description 5
- 238000005253 cladding Methods 0.000 description 5
- 239000002071 nanotube Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000006199 nebulizer Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 210000000476 body water Anatomy 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000006250 one-dimensional material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006557 surface reaction 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
- C23C18/1619—Apparatus for electroless plating
- C23C18/1632—Features specific for the apparatus, e.g. layout of cells and of its equipment, multiple cells
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1619—Apparatus for electroless plating
- C23C18/1628—Specific elements or parts of the apparatus
-
- 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
-
- 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
- C23C18/18—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
- C23C18/42—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)
- Carbon And Carbon Compounds (AREA)
- Chemically Coating (AREA)
Abstract
The present invention discloses a kind of carbon nano tube surface and is uniformly coated with the method and device of argent, first carry out CNT pretreatment, and prepare silver ammino solution and chemical plating solution, the device using the present invention to use carries out chemical plating, this device includes vacuum pump, receiving flask, quartz ampoule, ultrasound atomizer, Microwave-assisted firing device, anti-microwave leakage device, carrier gas conveyer device, two kinds of solution are carried out ultrasonic atomizatio respectively, and make two kinds of aerosol contact with each other the raw reaction of hybrid concurrency, gained powder body cyclic washing is to neutral, obtain the CNT of coated with uniform argent after drying；CNT is scattered in spray droplet by the present invention, improve CNT and silver-plated dispersibility, avoiding generation and the generation of silver mirror reaction of the solution selfdecomposition phenomenon in conventional chemical electroplating method, bulky grain monomer silver, prepared coating is uniform, and Argent grain size is at nanoscale；Integrated artistic is simple, and device is easy, easy to operate, energy-conserving and environment-protective, it is possible to realize volume production.
Description
Technical field
The invention discloses a kind of carbon nano tube surface and be uniformly coated with the method and device of argent, belong to CNT
The technical field that method is silver-plated.
Background technology
CNT has caused people's extensive concern since 1991 are found, and CNT has higher major diameter
Ratio (within a diameter of tens nanometers, a length of several microns are arrived hundreds of micron), is the thinnest fibrous material, and it shows
Go out the mechanical property of excellence and unique electric property.With different materials, CNT is coated with, available another kind of
One-dimensional material, experiment shows, single multilayer carbon nanotube young modulus average out to 1.8 TPa, demonstrates superpower mechanical property,
Bending strength reaches 14.2Gpa, demonstrates superpower toughness, and therefore CNT will have huge prospect in field of compound material.
At carbon nano tube surface plating, can be conducive to improving the wettability with matrix and interface cohesion further
Improve the performances such as electric conductivity, corrosion stability, hardness, lubricity, can be used as the conductive material of a kind of improvement, it is also possible to as resistance to
Erosion, wear-resistant coating, thermal boundary and seal coating, microwave absorbing material etc..
It is coated with metallics at CNT outer surface, will make between CNT and Metal Substrate, to form continuous high intensity knot
Closing, overcome the shortcoming that CNT is very poor with metallic matrix associativity, this is to utilize CNT to prepare superpower composite not
The key link that can lack, because many metals can be transferred through chemical plating method and are deposited on nearly all substrate after treatment
On, therefore can utilize chemical plating method enveloped carbon nanometer tube, up to now, people are to micron-sized granule or the chemistry of fiber
Plating has carried out more research, and some technology is the most ripe, but, the chemical plating research for nano-scale particle is but carried out
Obtaining seldom, for CNT, surface curvature is big, difficulties in dispersion, and technology requires higher, graphitization knot of its height
Structure so that surface reaction activity is the lowest, is difficult to obtain the preferable coating of seriality compactness, in the process of traditional chemical plating
In, CNT itself is difficult to dispersed, and metal also is difficult to be plated on its surface uniformly, and anti-due to occur in solution
Existential Space inhomogeneities, part metals granule is answered the most too to grow up, it is impossible to according to the coating carbon nanotubes of anticipation.
Understand the main solution for these problems from document and have following several: 1) chemical plating fluid, add dispersion
Agent, so can relatively reduce the generation of agglomeration traits, but can affect the silver of chemical plating and the adhesion of CNT.2)
Use stirring and ultrasonic vibration combine way, but be typically now ultrasonic vibration device is placed in container outside, its concussion
Effect greatly weaken.3) use and slow down the instillation speed of solution and solve to react too fast plating problem of non-uniform, but due to
There is excessive Concentraton gradient at reactant liquor, therefore instilling speed by control merely is to be difficult to solve problem above.
Summary of the invention
For the problem overcoming prior art to exist, it is an object of the invention to provide a kind of carbon nano tube surface and uniformly wrap
The method covering argent, specifically includes following steps:
(1) pretreatment of CNT
Carry out CNT successively being acidified, sensitization and the pretreatment of activation, by pretreated CNT according to mass body
Long-pending ratio is in 1:200g/mL addition dispersant, and supersound process obtains carbon nano tube suspension；
(2) preparation of silver ammino solution
Add, at the suspension that concentration is 15g/L-20g/L silver nitrate, the ammonia that mass fraction is 25% to clarify to suspension, then use
Concentration is that the NaOH solution regulation pH value of 5mol/L obtains main saline solution A to 10-11；
(3) preparation of chemical plating solution
Reducing agent and deionized water 1:3-1:5 by volume are mixed to get mixed solution B, by the main saline solution A of step (2) and
After the carbon nano tube suspension 3:1-5:1 by volume mixing of step (1), ultrasonic vibration mix homogeneously obtains suspension C；Will be mixed
After closing the carbon nano tube suspension 3:1-5:1 by volume mixing of solution B and step (1), in ultrasonic instrument, concussion mixing is all
Even acquisition suspension D；
(4) chemical silvering of CNT
Choose main saline solution A and suspension D combination, mixed solution B and suspension C in combination, suspension C and suspension D combination, this
One in three kinds of combinations carries out subsequent chemistry plating reaction, and two kinds of solution in the combination that will choose carry out ultrasonic atomizatio respectively,
And making two kinds of aerosol contact with each other the raw reaction of hybrid concurrency, course of reaction uses microwave heating to 60-80 DEG C, and gained powder body exists
In deionized water, cyclic washing is to neutral, obtains the CNT of coated with uniform argent after drying.
Step (1) described acidifying is the ratio according to 1.5:100g/mL-3:100g/mL, is added in nitration mixture by CNT
The mixture obtained, is again heated to 70 DEG C of backflow 3h, then dilutes with deionized water and washs to neutral, the carbon nanometer that will obtain
Pipe separates, and the CNT after being acidified after drying, wherein nitration mixture is the concentrated sulphuric acid by mass fraction 98% and mass fraction
The concentrated nitric acid of 65% 3:1 by volume mixes.
Step (1) described sensitization is according to 1:100g/mL-2:100g/mL, adds quick by the CNT after acidification
In change liquid after supersound process, dilute with deionized water and wash to neutral, the carbon nanotube separation that will obtain, 60 DEG C of dry 24h
After obtain the CNT after sensitization, wherein sensitizing solution by the deionized water of 100mL, the concentrated hydrochloric acid 3.5mL of mass fraction 37%,
1.9g SnCl2It is configured to.
Step (1) described activation is according to 1:100g/mL-2:100g/mL, is added by the CNT after sensitized treatment and lives
Change supersound process 30min-60min in liquid, dilute with deionized water and wash to neutral, the carbon nanotube separation that will obtain, dry
CNT after being activated after dry, wherein activating solution is by the deionized water of 100mL, the concentrated hydrochloric acid of mass fraction 37%
1.7mL、0.09g PdCl2It is configured to.
The mixture that dispersant described in step (1) is dehydrated alcohol and water mixes according to volume ratio 1:1.
Reducing agent described in step (3) be hydrazine hydrate, formaldehyde, D-glucose, sodium potassium tartrate tetrahydrate, Hydrazinium sulfate, ethylenediamine,
Biformyl, sodium borohydride, aldolactol, triethanolamine, glycerol, tannic acid or Mitouer.
Described being dried of step (4) is at 50-60 DEG C of dry 24h.
Another object of the present invention is to the side providing described step (4) described carbon nano tube surface to be uniformly coated with argent
Device used in method, the device that i.e. step (4) chemical plating is used, including vacuum pump 1, receiving flask 2, quartz ampoule 4, ultrasonic atomizatio
Device, Microwave-assisted firing device 7, anti-microwave leakage device 5, carrier gas conveyer device 6, Microwave-assisted firing device 7 is wrapped in quartz ampoule 4
Outside, anti-microwave leakage device 5 is wrapped in Microwave-assisted firing device 7 outside and quartz ampoule 4 two ends, and quartz ampoule 4 is through anti-microwave
Leakage device 5, its one end is connected with plural ultrasound atomizer and carrier gas conveyer device 8 respectively, the other end and receiving flask 2
Connecting, receiving flask 2 is also connected with vacuum pump 1, and the powder body reacted in quartz ampoule 4 is extracted in receiving flask 2 by vacuum pump 1.
Described carrier gas conveyer device 6 is aerator, and anti-microwave leakage device 5 is metal-back, such as steel plate shell.
Described quartz ampoule 4 two ends are provided with end cap 3, and end cap 3 is provided with connecting hole, or quartz ampoule 4 is blocked by glass cement,
Leave connecting hole during closure, realized the connection of two end devices by connecting hole.
The purity of CNT of the present invention is 95-99.9%.
Present invention have the advantage that compared with prior art and positive effect:
(1) experiment flow of the present invention is simple, and safe and reliable, equipment is simple, it is easy to accomplish prepared by serialization.
(2) present invention's is that ultrasonic atomization technique can make the drop of reaction control in 1-10 micron level, carbon nanometer
Pipe sprays with atomized drop, greatly improves the dispersibility of CNT.
(3) the inventive method is by the contact between drop, the raw reaction of hybrid concurrency, and volume and the concentration of the drop of formation have
Limit, thus incident solution selfdecomposition in conventional chemical plating method, silver mirror reaction and the formation of bulky grain silver simple substance can be avoided
Generation etc. situation.
(4) in the present invention two kinds of mist bodies be relatively atomized and to spray into speed adjustable, course of reaction is optional applies microwave field
To promote the carrying out of reaction, it is achieved the regulation and control of electroless plating reaction speed, it is easy to control the grain size of silver coating.
Accompanying drawing explanation
Fig. 1 is the ullrasonic spraying chemical plating appts schematic diagram that the present invention uses；
Fig. 2 is schematic diagram at the ullrasonic spraying chemical plating appts quartz ampoule end cap that the present invention uses
Fig. 3 is the TEM figure of the CNT of the uniformly cladding argent that the embodiment of the present invention 1 obtains；
Fig. 4 is the XRD figure of the CNT of the uniformly cladding argent that the embodiment of the present invention 1 obtains；
Fig. 5 is the TEM figure of the CNT of the uniformly cladding argent that the embodiment of the present invention 2 obtains；
Fig. 6 is the TEM figure of the CNT of the uniformly cladding argent that the embodiment of the present invention 3 obtains；
Fig. 7 is the TEM figure of the CNT of the uniformly cladding argent that the embodiment of the present invention 5 obtains；
In figure, 1-vacuum pump, 2-receiving flask, 3-end cap, 4-quartz ampoule, 5-microwave leakage prevention device, 6-carrier gas conveyer device, 7-
Microwave-assisted firing device, 8-ultrasound atomizer I, 9-ultrasound atomizer II.
Detailed description of the invention
Below in conjunction with the accompanying drawings the present invention is described in further details, but protection scope of the present invention is not limited in
This.
Embodiment 1
Carbon nano tube surface of the present invention is uniformly coated with the method for argent, specifically includes following steps:
The pretreatment of step 1) CNT
(1) acidification of CNT: added by CNT in nitration mixture, nitration mixture is by the concentrated sulphuric acid of mass fraction 98% and matter
Amount mark 65% concentrated nitric acid 3:1 by volume mixing be made into, the addition of CNT be every 100mL nitration mixture in add
1.5g CNT, is then heated to reflux 3h in the water-bath of 70 DEG C, then dilutes with deionized water and washs to neutral, will
The carbon nanotube separation obtained, the CNT after being acidified after drying；
(2) sensitized treatment: the CNT after acidification is added ultrasonic 30min process in sensitizing solution according to 1:100g/mL
After, dilute with deionized water and wash to neutral, the carbon nanotube separation that will obtain, after obtaining sensitization after 60 DEG C of dry 24h
CNT, wherein sensitizing solution is concentrated hydrochloric acid 3.5mL, 1.9g SnCl of the deionized water of 100mL, mass fraction 37%2Mixing
Obtain；
(3) activation processing: the CNT after sensitized treatment is added ultrasonic 30min process in activating solution according to 1:100g/mL
After, dilute with deionized water and wash to neutral, the carbon nanotube separation that will obtain, obtaining the carbon after pretreatment completes after drying
Nanotube, wherein activating solution is concentrated hydrochloric acid 1.7mL, 0.09g PdCl of the deionization of 100mL, mass fraction 37%2Mix
Arrive；
CNT 1g after activation processing is added in the dispersant of 200mL, supersound process 60min, obtain CNT and hang
Supernatant liquid, the mixture that wherein dispersant is dehydrated alcohol and deionized water mixes according to volume ratio 1:1；
Step 2) preparation of silver ammino solution
Adding mass fraction in the silver nitrate suspension that 100mL concentration is 15g/L is that the ammonia of 25% is clear to silver nitrate suspension
Clearly, then with the NaOH solution regulation pH value that concentration is 5mol/L after 10, main saline solution A is obtained；
The preparation of step 3) chemical plating solution
Reducing agent formaldehyde and deionized water 1:3 by volume are mixed to get mixed solution B, by mixed solution B and step (1)
After carbon nano tube suspension 4:1 by volume mixing, ultrasonic instrument shakes mix homogeneously and obtains suspension D；
The chemical plating of step 4) CNT
The device that the chemical plating that this step is used is used, as shown in Figure 1, 2, including vacuum pump 1, receiving flask 2, end cap 3, quartz
Pipe 4, microwave leakage prevention device 5, carrier gas conveyer device 6, Microwave-assisted firing device 7, ultrasound atomizer I 8, ultrasound atomizer II 9,
It is outside that Microwave-assisted firing device 7 is wrapped in quartz ampoule 4, and anti-microwave leakage device 5 is wrapped in Microwave-assisted firing device 7 outside and stone
English pipe 4 two ends, quartz ampoule 4 two ends pass anti-microwave leakage device 5, and quartz ampoule 4 two ends are provided with end cap 3, and end cap 3 is provided with connection
Hole, the end cap 3 of quartz ampoule 4 one end is connected with ultrasound atomizer I 8, ultrasound atomizer II 9 and carrier gas conveyer device 6 respectively, another
The end cap 3 of end is connected with receiving flask 2, and receiving flask 2 is also connected with vacuum pump 1, the powder that vacuum pump 1 will react in quartz ampoule 4
Body is extracted in receiving flask 2, and anti-microwave leakage device 7 is metal foil shell；
Being added in ultrasound atomizer I 8 and ultrasound atomizer II 9 by main saline solution A and suspension D respectively, energising carries out ultrasonic mist
Change, use carrier gas conveyer device aerator 6 to be sent in quartz ampoule 4 by atomized drop as carrier gas by air, spray into maximum atomization
Rate is more than 3 ml/min, and using Microwave-assisted firing device 7 to control the temperature in quartz ampoule 4 is 60 DEG C, will be anti-by vacuum pump 1
Powder body after should is extracted out and is collected in receiving flask 2, by the powder body of collection with after deionized water cyclic washing to neutrality, in temperature is
60 DEG C of baking ovens are dried 24h, obtain the CNT of coated with uniform argent.
Fig. 3 is the TEM figure of the CNT of the coated with uniform argent that the present embodiment obtains, and as seen from the figure, carbon is received
The silver coating of mitron is mainly wrapped in the surface of CNT with silver bunch and graininess, and the silver reunited occurs in few places
Grain；Fig. 4 is the XRD diffracting spectrum of the CNT of the coated with uniform argent obtained of the present embodiment, it is seen that carbon nanometer
After pipe chemical silvering the base peak collection of illustrative plates of silver of the strong peak of master and FCC of XRD diffracting spectrum corresponding, CNT is described
Learn the silver-colored crystal that silver-plated silver coating is FCC.
Embodiment 2
Carbon nano tube surface of the present invention is uniformly coated with the method for argent, specifically includes following steps:
The pretreatment of step 1) CNT
(1) acidification of CNT: added by CNT in nitration mixture, nitration mixture is by the concentrated sulphuric acid of mass fraction 98% and matter
Amount mark 65% concentrated nitric acid 3:1 by volume mixing be made into, the addition of CNT be every 100mL nitration mixture in add 2g
CNT, is then heated to reflux 3h in the water-bath of 70 DEG C, then dilutes with deionized water and washs to neutral, will obtain
Carbon nanotube separation, the CNT after being acidified after drying；
(2) sensitized treatment: the CNT after acidification is added ultrasonic 30min process in sensitizing solution according to 2:100g/mL
After, dilute with deionized water and wash to neutral, the carbon nanotube separation that will obtain, after obtaining sensitization after 60 DEG C of dry 24h
CNT, wherein sensitizing solution is concentrated hydrochloric acid 3.5mL, 1.9g SnCl of the deionized water of 100mL, mass fraction 37%2Mixing
Obtain；
(3) activation processing: the CNT after sensitized treatment is added ultrasonic 30min process in activating solution according to 2:100g/mL
After, dilute with deionized water and wash to neutral, the carbon nanotube separation that will obtain, obtaining the carbon after pretreatment completes after drying
Nanotube, wherein activating solution is concentrated hydrochloric acid 1.7mL, 0.09g PdCl of the deionization of 100mL, mass fraction 37%2Mix
Arrive；
CNT 1g after activation processing is added in the dispersant of 200mL, supersound process 60min, obtain CNT and hang
Supernatant liquid, the mixture that wherein dispersant is dehydrated alcohol and deionized water mixes according to volume ratio 1:1；
Step 2) preparation of silver ammino solution
Adding mass fraction in the silver nitrate suspension that 100mL concentration is 20g/L is that the ammonia of 25% is clear to silver nitrate suspension
Clearly, then with the NaOH solution regulation pH value that concentration is 5mol/L after 11, main saline solution A is obtained；
The preparation of step 3) chemical plating solution
Reducing agent hydrazine hydrate and deionized water 1:4 by volume are mixed to get mixed solution B, by the main saline solution A of step (2)
After mixing with the carbon nano tube suspension 3:1 by volume of step (1), ultrasonic vibration mix homogeneously obtains suspension C；
The chemical plating of step 4) CNT
The device that the chemical plating that this step is used is used is same as in Example 1, and simply quartz ampoule 4 is ground, and two ends use
Glass cement blocks, and glass cement leaves connecting hole, and mixed solution B and suspension C is added to ultrasound atomizer I 8 and ultrasonic respectively
In nebulizer II 9, energising carries out ultrasonic atomizatio, use carrier gas conveyer device aerator 6 using air as carrier gas by atomized drop
Send in quartz ampoule 4, spray into maximum condensation rate and control in quartz ampoule 4 more than 3 ml/min, employing Microwave-assisted firing device 7
Temperature is 70 DEG C, collects in receiving flask 2, by the powder body deionization of collection by vacuum pump 1 by the extraction of reacted powder body
Water cyclic washing, to after neutrality, is dried 24h in temperature is 60 DEG C of baking ovens, obtains the carbon nanometer of coated with uniform argent
Pipe.
Fig. 5 is the CNT TEM figure that the embodiment of the present invention 2 obtains coated with uniform argent, and as seen from the figure, carbon is received
The silver coating of mitron is mainly the surface being wrapped in CNT with the silver-colored shape of granule；XRD analysis understands carbon nanotube chemical plating
After silver the base peak collection of illustrative plates of silver of the strong peak of master and FCC of XRD diffracting spectrum corresponding, illustrate that carbon nanotube chemical is silver-plated
Silver coating is the silver-colored crystal of FCC.
Embodiment 3
Carbon nano tube surface of the present invention is uniformly coated with the method for argent, specifically includes following steps:
The pretreatment of step 1) CNT
(1) acidification of CNT: added by CNT in nitration mixture, nitration mixture is by the concentrated sulphuric acid of mass fraction 98% and matter
Amount mark 65% concentrated nitric acid 3:1 by volume mixing be made into, the addition of CNT be every 100mL nitration mixture in add 3g
CNT, is then heated to reflux 3h in the water-bath of 70 DEG C, then dilutes with deionized water and washs to neutral, will obtain
Carbon nanotube separation, the CNT after being acidified after drying；
(2) sensitized treatment: the CNT after acidification is added in sensitizing solution at ultrasonic 30min according to 1.5:100g/mL
After reason, diluting with deionized water and wash to neutral, the carbon nanotube separation that will obtain, after obtaining sensitization after 60 DEG C of dry 24h
CNT, wherein sensitizing solution is concentrated hydrochloric acid 3.5mL, 1.9g SnCl of the deionized water of 100mL, mass fraction 37%2Mixed
Conjunction obtains；
(3) activation processing: the CNT after sensitized treatment is added ultrasonic 60min process in activating solution according to 2:100g/mL
After, dilute with deionized water and wash to neutral, the carbon nanotube separation that will obtain, obtaining the carbon after pretreatment completes after drying
Nanotube, wherein activating solution is concentrated hydrochloric acid 1.7mL, 0.09g PdCl of the deionization of 100mL, mass fraction 37%2Mix
Arrive；
CNT 1g after activation processing is added in the dispersant of 200mL, supersound process 60min, obtain CNT and hang
Supernatant liquid, the mixture that wherein dispersant is dehydrated alcohol and deionized water mixes according to volume ratio 1:1；
Step 2) preparation of silver ammino solution
Adding mass fraction in the silver nitrate suspension that 100mL concentration is 18g/L is that the ammonia of 25% is clear to silver nitrate suspension
Clearly, then with the NaOH solution regulation pH value that concentration is 5mol/L after 10, main saline solution A is obtained；
The preparation of step 3) chemical plating solution
Borane reducing agent sodium hydride and deionized water 1:5 by volume are mixed to get mixed solution B, by molten for the main salt of step (2)
After the carbon nano tube suspension 4:1 by volume mixing of liquid A and step (1), ultrasonic vibration mix homogeneously obtains suspension C；Will
After the carbon nano tube suspension 5:1 by volume mixing of mixed solution B and step (1), ultrasonic instrument shakes mix homogeneously
Obtain suspension D；
The chemical plating of step 4) CNT
The device that the chemical plating that this step is used is used is same as in Example 1, is added to surpass by suspension C and suspension D respectively
In sound nebulizer I 8 and ultrasound atomizer II 9, energising carries out ultrasonic atomizatio, uses carrier gas conveyer device aerator 6 to be made by air
For carrier gas, atomized drop is sent in quartz ampoule 4, spray into maximum condensation rate more than 3 ml/min, employing Microwave-assisted firing device
7 temperature controlled in quartz ampoule 4 are 80 DEG C, collect in receiving flask 2 by vacuum pump 1 by the extraction of reacted powder body, will receive
The powder body of collection, with after deionized water cyclic washing to neutrality, is dried 24h in temperature is 55 DEG C of baking ovens, obtains coated with uniform
The CNT of argent.
Fig. 6 is the CNT TEM figure of the coated with uniform argent that the embodiment of the present invention 3 obtains, as seen from the figure, carbon
The silver coating of nanotube is mainly granular silver and is wrapped in the surface of CNT, and the big silver reunited occur in some places
Grain.XRD analysis result is identical with embodiment 1.
Embodiment 4
Carbon nano tube surface of the present invention is uniformly coated with the method for argent, specifically includes following steps:
The pretreatment of step 1) CNT
(1) acidification of CNT: added by CNT in nitration mixture, nitration mixture is by the concentrated sulphuric acid of mass fraction 98% and matter
Amount mark 65% concentrated nitric acid 3:1 by volume mixing be made into, the addition of CNT be every 100mL nitration mixture in add 3g
CNT, is then heated to reflux 3h in the water-bath of 70 DEG C, then dilutes with deionized water and washs to neutral, will obtain
Carbon nanotube separation, the CNT after being acidified after drying；
(2) sensitized treatment: the CNT after acidification is added in sensitizing solution at ultrasonic 30min according to 1.5:100g/mL
After reason, diluting with deionized water and wash to neutral, the carbon nanotube separation that will obtain, after obtaining sensitization after 60 DEG C of dry 24h
CNT, wherein sensitizing solution is concentrated hydrochloric acid 3.5mL, 1.9g SnCl of the deionized water of 100mL, mass fraction 37%2Mixed
Conjunction obtains；
(3) activation processing: the CNT after sensitized treatment is added ultrasonic 50min process in activating solution according to 2:100g/mL
After, dilute with deionized water and wash to neutral, the carbon nanotube separation that will obtain, obtaining the carbon after pretreatment completes after drying
Nanotube, wherein activating solution is concentrated hydrochloric acid 1.7mL, 0.09g PdCl of the deionization of 100mL, mass fraction 37%2Mix
Arrive；
CNT 1g after activation processing is added in the dispersant of 200mL, supersound process 60min, obtain CNT and hang
Supernatant liquid, the mixture that wherein dispersant is dehydrated alcohol and deionized water mixes according to volume ratio 1:1；
Step 2) preparation of silver ammino solution
Adding mass fraction in the silver nitrate suspension that 100mL concentration is 20g/L is that the ammonia of 25% is clear to silver nitrate suspension
Clearly, then with the NaOH solution regulation pH value that concentration is 5mol/L after 10, main saline solution A is obtained；
The preparation of step 3) chemical plating solution
Reducing agent tannic acid and deionized water 1:4 by volume are mixed to get mixed solution B, by the main saline solution A of step (2) and
After the carbon nano tube suspension 5:1 by volume mixing of step (1), ultrasonic vibration mix homogeneously obtains suspension C；
The chemical plating of step 4) CNT
The device that the chemical plating that this step is used is used is same as in Example 1, is added to by mixed solution B and suspension C respectively
In ultrasound atomizer I 8 and ultrasound atomizer II 9, energising carries out ultrasonic atomizatio, uses carrier gas conveyer device aerator 6 by air
As carrier gas, atomized drop is sent in quartz ampoule 4, spray into maximum condensation rate more than 3 ml/min, employing Microwave-assisted firing
It is 70 DEG C that device 7 controls the temperature in quartz ampoule 4, collects in receiving flask 2 by vacuum pump 1 by the extraction of reacted powder body, will
The powder body collected, with after deionized water cyclic washing to neutrality, is dried 24h in temperature is 50 DEG C of baking ovens, obtains surface and uniformly wrap
Cover the CNT of argent.
Fig. 7 is the TEM figure of the CNT of the coated with uniform argent that the embodiment of the present invention 4 obtains, as seen from the figure,
The silver coating of CNT is mainly granular silver and is wrapped in the surface of CNT, the Argent grain that minority is reunited occurs；XRD
Analysis result is identical with embodiment 1.
Embodiment 5
Carbon nano tube surface of the present invention is uniformly coated with the method for argent, specifically includes following steps:
The pretreatment of step 1) CNT
(1) acidification of CNT: added by CNT in nitration mixture, nitration mixture is by the concentrated sulphuric acid of mass fraction 98% and matter
Amount mark 65% concentrated nitric acid 3:1 by volume mixing be made into, the addition of CNT be every 100mL nitration mixture in add
2.5g CNT, is then heated to reflux 3h in the water-bath of 70 DEG C, then dilutes with deionized water and washs to neutral, will
The carbon nanotube separation obtained, the CNT after being acidified after drying；
(2) sensitized treatment: the CNT after acidification is added ultrasonic 30min process in sensitizing solution according to 2:100g/mL
After, dilute with deionized water and wash to neutral, the carbon nanotube separation that will obtain, after obtaining sensitization after 60 DEG C of dry 24h
CNT, wherein sensitizing solution is concentrated hydrochloric acid 3.5mL, 1.9g SnCl of the deionized water of 100mL, mass fraction 37%2Mixing
Obtain；
(3) activation processing: the CNT after sensitized treatment is added in activating solution at ultrasonic 30min according to 1.5:100g/mL
After reason, dilute with deionized water and wash to neutral, the carbon nanotube separation that will obtain, obtaining after pretreatment completes after drying
CNT, wherein activating solution is concentrated hydrochloric acid 1.7mL, 0.09g PdCl of the deionization of 100mL, mass fraction 37%2Mix
Arrive；
CNT 1g after activation processing is added in the dispersant of 200mL, supersound process 60min, obtain CNT and hang
Supernatant liquid, the mixture that wherein dispersant is dehydrated alcohol and deionized water mixes according to volume ratio 1:1；
Step 2) preparation of silver ammino solution
Adding mass fraction in the silver nitrate suspension that 100mL concentration is 20g/L is that the ammonia of 25% is clear to silver nitrate suspension
Clearly, then with the NaOH solution regulation pH value that concentration is 5mol/L after 10, main saline solution A is obtained；
The preparation of step 3) chemical plating solution
Reducing agent sodium potassium tartrate tetrahydrate and deionized water 1:5 by volume are mixed to get mixed solution B, by the main salt of step (2)
After the carbon nano tube suspension 3:1 by volume mixing of solution A and step (1), ultrasonic vibration mix homogeneously obtains suspension C；
After being mixed by the carbon nano tube suspension 3:1 by volume of mixed solution B and step (1), in ultrasonic instrument, concussion mixing is all
Even acquisition suspension D；
The chemical plating of step 4) CNT
The device that the chemical plating that this step is used is used is same as in Example 2, is added to surpass by suspension C and suspension D respectively
In sound nebulizer I 8 and ultrasound atomizer II 9, energising carries out ultrasonic atomizatio, uses carrier gas conveyer device aerator 6 to be made by air
For carrier gas, atomized drop is sent in quartz ampoule 4, spray into maximum condensation rate more than 3 ml/min, employing Microwave-assisted firing device
7 temperature controlled in quartz ampoule 4 are 60 DEG C, collect in receiving flask 2 by vacuum pump 1 by the extraction of reacted powder body, will receive
The powder body of collection, with after deionized water cyclic washing to neutrality, is dried 24h in temperature is 60 DEG C of baking ovens, obtains coated with uniform
The CNT of argent.
The TEM figure of the CNT of the coated with uniform argent that the present embodiment 5 obtains, as seen from the figure, the plating of CNT
Silver layer is mainly wrapped in the surface of CNT with silver bunch and granular silver, and the Argent grain reunited occurs in few places；XRD
Analysis result is identical with embodiment 1.
Embodiment described above is only the several embodiments of the present invention, and it describes more concrete and detailed, but can not
Therefore the restriction to the scope of the claims of the present invention it is interpreted as, it is noted that for the person of ordinary skill of the art,
Without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement, these broadly fall into the protection model of the present invention
Enclose.
Claims (10)
1. the method that a carbon nano tube surface is uniformly coated with argent, it is characterised in that specifically include following steps:
(1) pretreatment of CNT
Carry out CNT successively being acidified, sensitization and the pretreatment of activation, by pretreated CNT according to mass body
Long-pending ratio is in 1:200g/mL addition dispersant, and supersound process obtains carbon nano tube suspension；
(2) preparation of silver ammino solution
Add, at the suspension that concentration is 15g/L-20g/L silver nitrate, the ammonia extremely clarification that mass fraction is 25%, then by concentration be
The NaOH solution regulation pH value of 5mol/L obtains main saline solution A to 10-11；
(3) preparation of chemical plating solution
Reducing agent and deionized water 1:3-1:5 by volume are mixed to get mixed solution B, by the main saline solution A of step (2) and
After the carbon nano tube suspension 3:1-5:1 by volume mixing of step (1), ultrasonic vibration mix homogeneously obtains suspension C；Will be mixed
After closing the carbon nano tube suspension 3:1-5:1 by volume mixing of solution B and step (1), in ultrasonic instrument, concussion mixing is all
Even acquisition suspension D；
(4) chemical plating of CNT
Choose main saline solution A and suspension D combination, mixed solution B and suspension C in combination, suspension C and suspension D combination, this
One in three kinds of combinations carries out subsequent chemistry plating reaction, and two kinds of solution in the combination that will choose carry out ultrasonic atomizatio respectively,
And making two kinds of aerosol contact with each other the raw reaction of hybrid concurrency, course of reaction uses microwave heating to 60-80 DEG C, and gained powder body exists
In deionized water, cyclic washing is to neutral, obtains the CNT of coated with uniform argent after drying.
The method that the most according to claim 1, carbon nano tube surface is uniformly coated with argent, it is characterised in that step (1) institute
Stating acidifying is the ratio according to 1.5:100g/mL-3:100g/mL, CNT adds the mixture obtained in nitration mixture, then adds
Heat, to 70 DEG C of backflow 3h, then dilutes with deionized water and washs to neutral, the carbon nanotube separation that will obtain, obtaining after drying
CNT after acidifying, wherein nitration mixture be the concentrated nitric acid of the concentrated sulphuric acid by mass fraction 98% and mass fraction 65% by volume
3:1 mixes.
The method that the most according to claim 1, carbon nano tube surface is uniformly coated with argent, it is characterised in that step (1) institute
Stating sensitization is the ratio according to 1:100g/mL-2:100g/mL, adds in sensitizing solution ultrasonic by the CNT after acidification
After process, dilute with deionized water and wash to neutral, the carbon nanotube separation that will obtain, after 60 DEG C of dry 24h, obtaining sensitization
After CNT, wherein sensitizing solution is by the deionized water of 100mL, concentrated hydrochloric acid 3.5mL, 1.9g SnCl of mass fraction 37%2
It is configured to.
The method that the most according to claim 1, carbon nano tube surface is uniformly coated with argent, it is characterised in that step (1) institute
Stating activation is the ratio according to 1:100g/mL-2:100g/mL, adds in activating solution ultrasonic by the CNT after sensitized treatment
Process 30min-60min, dilute with deionized water and wash to neutral, the carbon nanotube separation that will obtain, being lived after drying
CNT after change, wherein activating solution is by the deionized water of 100mL, concentrated hydrochloric acid 1.7mL, 0.09g of mass fraction 37%
PdCl2It is configured to.
The method that the most according to claim 1, carbon nano tube surface is uniformly coated with argent, it is characterised in that described dispersion
The mixture that agent is dehydrated alcohol and water mixes according to volume ratio 1:1.
The method that the most according to claim 1, carbon nano tube surface is uniformly coated with argent, it is characterised in that step (3) institute
The reducing agent stated be hydrazine hydrate, formaldehyde, D-glucose, sodium potassium tartrate tetrahydrate, Hydrazinium sulfate, ethylenediamine, Biformyl, sodium borohydride,
Aldolactol, triethanolamine, glycerol, tannic acid or Mitouer.
The method that the most according to claim 1, carbon nano tube surface is uniformly coated with argent, it is characterised in that step (4) institute
Stating dry is at 50-60 DEG C of dry 24h.
8. carbon nano tube surface described in claim 1-7 any one is uniformly coated with the device used in method of argent, its
Being characterised by, the device that step (4) described chemical plating is used, including vacuum pump, receiving flask, quartz ampoule, ultrasound atomizer, microwave
Auxiliary heater, anti-microwave leakage device, carrier gas conveyer device, Microwave-assisted firing device is wrapped in outside quartz ampoule, anti-microwave
Leakage device is wrapped in Microwave-assisted firing device outside and quartz ampoule two ends, and quartz ampoule two ends pass anti-microwave leakage device, its
One end is connected with plural ultrasound atomizer and carrier gas conveyer device respectively, and the other end is connected with receiving flask, and receiving flask is also
It is connected with vacuum pump.
The method that the most according to claim 8, carbon nano tube surface is uniformly coated with argent, it is characterised in that described carrier gas is defeated
Sending device is aerator, and anti-microwave leakage device is metal shell.
The method that the most according to claim 8, carbon nano tube surface is uniformly coated with argent, it is characterised in that described quartz
Pipe two ends are provided with end cap, and end cap is provided with connecting hole, or quartz ampoule 4 is blocked by glass cement, leaves connecting hole during closure.
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