CN101259531A - Surface finish nano copper/copper alloy particles and preparation thereof - Google Patents
Surface finish nano copper/copper alloy particles and preparation thereof Download PDFInfo
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- CN101259531A CN101259531A CNA2008100494468A CN200810049446A CN101259531A CN 101259531 A CN101259531 A CN 101259531A CN A2008100494468 A CNA2008100494468 A CN A2008100494468A CN 200810049446 A CN200810049446 A CN 200810049446A CN 101259531 A CN101259531 A CN 101259531A
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- salt
- copper alloy
- surface finish
- alloy particles
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- 239000010949 copper Substances 0.000 title claims abstract description 40
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 28
- 239000002245 particle Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 239000000956 alloy Substances 0.000 claims abstract description 16
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 208000035126 Facies Diseases 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkyl xanthogenic acid Chemical compound 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 claims description 3
- 239000002262 Schiff base Substances 0.000 claims description 3
- 150000004753 Schiff bases Chemical class 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000001186 cumulative effect Effects 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 3
- 229960001860 salicylate Drugs 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 239000002105 nanoparticle Substances 0.000 abstract description 20
- 239000006185 dispersion Substances 0.000 abstract description 6
- 239000003607 modifier Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract 4
- 238000012986 modification Methods 0.000 abstract 4
- 150000001879 copper Chemical class 0.000 abstract 2
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 238000009826 distribution Methods 0.000 abstract 1
- 239000012074 organic phase Substances 0.000 abstract 1
- 239000003495 polar organic solvent Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 20
- 239000003921 oil Substances 0.000 description 13
- 239000012071 phase Substances 0.000 description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000012266 salt solution Substances 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- JIXICPMXYVZHBP-UHFFFAOYSA-N OC(C)CCC(CCCC)C(=NO)C(CCC(C)O)CCCC Chemical compound OC(C)CCC(CCCC)C(=NO)C(CCC(C)O)CCCC JIXICPMXYVZHBP-UHFFFAOYSA-N 0.000 description 2
- 229910001080 W alloy Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910001309 Ferromolybdenum Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- PQJKKINZCUWVKL-UHFFFAOYSA-N [Ni].[Cu].[Ag] Chemical compound [Ni].[Cu].[Ag] PQJKKINZCUWVKL-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 239000003831 antifriction material Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- UTICYDQJEHVLJZ-UHFFFAOYSA-N copper manganese nickel Chemical compound [Mn].[Ni].[Cu] UTICYDQJEHVLJZ-UHFFFAOYSA-N 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- SBYXRAKIOMOBFF-UHFFFAOYSA-N copper tungsten Chemical compound [Cu].[W] SBYXRAKIOMOBFF-UHFFFAOYSA-N 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- MGJYZNJAQSLHOL-UHFFFAOYSA-N dioctylcarbamodithioic acid Chemical compound CCCCCCCCN(C(S)=S)CCCCCCCC MGJYZNJAQSLHOL-UHFFFAOYSA-N 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- RZFBEFUNINJXRQ-UHFFFAOYSA-M sodium ethyl xanthate Chemical compound [Na+].CCOC([S-])=S RZFBEFUNINJXRQ-UHFFFAOYSA-M 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Images
Abstract
The invention relates to a nano-copper/copper alloy particle for surface modification, which is prepared by the following method that: water solution of copper salt or copper salt and alloy component salt with the concentration of 0.001 to 1 mol/L is prepared, then the water solution is fully mixed with the mixed solution of a reductant, a surface modifier and a weak polar or non-polar organic solvent, the still placement is carried out for 30 to 180min after the reaction for 30 to 180min under the alkaline environment with pH of 8 to 13, the organic phase is obtained by separation, and the nano-copper/copper alloy particle for surface modification is obtained after the concentration. The copper/copper alloy nanoparticle for surface modification which is provided by the invention has controllable particle size and distribution, difficult clustering, good antioxidant property, monodisperse property and good dispersion stability in the organic solvent. The preparation process and a device of the nano-copper/copper alloy particle for surface modification are simple, the raw materials are cheap and easy to obtain, the cost is low, and the yield is high, thus being applicable to the large-scale industrial production.
Description
(1) technical field
The present invention relates to a kind of surface finish nano copper/copper alloy particles and preparation method.
(2) background technology
Nano material shows special advantages because of its special nano effect and high surface in tribological field.Particularly can repair automatically the abrading section of plant equipment friction pair, and have significant wear-resistant and energy saving effect as the selfreparing nano lubricating anti-friction material of novel high-performance lubricating oil and grease additive.Wherein copper and alloy nano particles thereof be as the selfreparing nano-lubricating material, its antifriction, wear-resistant and self-repair function is particularly outstanding.But the nano copper/copper alloy material exist oxidation stability poor, in the medium problem of dispersiveness and monodispersity difference in the oil medium particularly, therefore limited their extensive use, preparation has good chemical stability and has the nano-powder of good dispersion to become the main trend of nano materials research and suitability for industrialized production in medium.
At present, the preparation method of nano metal and alloy thereof is in the majority with physical method and chemical method, physical method mainly contains melt-blending process, co-reducing process, gas phase co-electrodeposition method, the nano copper/copper alloy particles component of these method preparations is pure, but its easily oxidation of surface, and can't in solvent, disperse,, sedimentation take place easily still even utilize a large amount of surfactants to disperse.Chemical method mainly contains co-reducing process, metal ion displacement method etc., but also can't solve aerial stability of the nanoparticle of preparing and the dispersion problem in organic media.
(3) summary of the invention
The object of the present invention is to provide a kind of surface finish nano copper/copper alloy particles, non-oxidizability is strong, the dispersiveness in organic solvent and monodispersity are good.
The technical solution used in the present invention is as follows:
A kind of surface finish nano copper/copper alloy particles, got by following method preparation: compound concentration is the mantoquita of 0.001～1mol/L or the aqueous solution of mantoquita and alloy compositions salt, mixed liquor with reducing agent, coating material, low pole or nonpolar organic solvent fully mixes then, be to leave standstill 30-180min again behind the reaction 30-180min under the alkaline environment of 8-13 at pH, separate organic facies, promptly get described surface finish nano copper/copper alloy particles after concentrating, wherein copper is 1 with the amount of substance ratio of alloy compositions: 0-0.4; Metallic element: reducing agent: the amount of substance ratio of coating material is 1: 2.5-20: 0.2-2; Reducing agent is one of following or several mixture arbitrarily: hydrazine hydrate, formaldehyde, sodium borohydride, hypophosphite, ascorbic acid; Coating material is dialkyl group phosphoric acid or its salt, alkyl xanthogenic acid or its salt, (O, O ')-and in dialkyl dithiophosphoric acid or its salt, dialkyl amido two bamic acids or its salt, 2-hydroxyl-5-alkylbenzene aldoxime, 2-hydroxyl-5-alkylbenzene ketoxime, alkyl salicylate, the schiff bases one or more, it is C1-C22 that described alkyl contains carbon number.
Further, the mixture of one or more in the alkane of described organic solvent selection chloroform, benzene,toluene,xylene, benzinum, C6～C12, consumption accounts for the 10%-90% of reaction system cumulative volume.
Concrete, described alloy compositions can be selected from one or more in zinc, tin, nickel, manganese, iron, silver, molybdenum, the tungsten.Alloy compositions salt and mantoquita must be water soluble salts, preferably sulfuric acid salt, hydrochloride, nitrate, acetate etc., and molybdenum, tungsten alloy component salt can be used molybdate, tungstates.
Separate the organic facies that obtains in the method and distill when concentrating, the thick liquid that obtains rufous is finished product.
Surface coated organic modifier when the copper/copper alloy nanoparticle just generates, stoped the generation of further growing up and reuniting of nano particle, thereby particle size and the particle diameter of having controlled the copper/copper alloy nano particle distribute, the prepared finishing copper/copper alloy nanoparticle particle diameter that goes out is evenly distributed, and monodispersity is good.Simultaneously, the coating of coating material has also stoped the aerial oxidation of metallic nano-particle, thereby has obtained good oxidation stability, can steady in a long-termly exist.And the existence of different organic modifiers also give metallic nano-particle in a lot of organic medias as good dispersion and dispersion stabilization in organic solvent such as toluene, benzinum and the multiple lube base oil.The industrial use of the finishing copper/copper alloy nanoparticle that obtains has obtained expansion.Employed preparation method is based on in-situ surface finishing technology and phase transfer method, when being reduced to nano copper/copper alloy, copper ion and other alloy compositions ions finish the in-situ surface finishing of nanoparticle and from the transfer of water to organic facies, method is simple, and controllability is strong.
The present invention has following advantage with respect to prior art:
Finishing copper/copper alloy nanoparticle provided by the invention, particle size and distribute controlled, be difficult for to reunite, antioxygenic property is good, monodispersity and the dispersion stabilization in organic solvent are good, product for example of the present invention quality addition in HVI S200 base oil is 2.0% o'clock of solvent quality, it still is transparent observing oil product, and its stable resting period can reach more than 3 years.Preparation technology of the present invention, equipment are simple, and raw material is cheap and easy to get, and cost is low, and the productive rate height is fit to large-scale industrial production.
(4) description of drawings
Fig. 1 is the TEM photo that makes the oil-soluble copper nanoparticle of example 1 preparation.
Fig. 2 is the TEM photo of the signal bronze nano particle of embodiment 2 preparations.
Fig. 3 is the TEM photo of the corronil nano particle of embodiment 3 preparations.
(5) specific embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1
The 0.03mol cupric sulfate pentahydrate is dissolved in the 100mL distilled water, with 15mL concentration 25% ammoniacal liquor, 0.075mol formaldehyde, 0.03mol (O, O ')-two two of normal octane base phosphordithiic acid, 0.005mol (2-ethyl-hexyl) phosphoric acid, 100mL dimethylbenzene mixes, slowly be added dropwise to the copper-bath that has prepared, there is bubble to emit, stirring reaction 30 minutes.After leaving standstill 60 minutes, separatory, the upper strata is an oil phase liquid, lower floor is the water white transparency water, discards lower floor's water, upper oil phase through distill thick liquid, be oil soluble, surface modified nanometer copper particulate, its transmission electron micrograph is seen Fig. 1.
Embodiment 2
With 0.03mol copper chloride (CuCl
22H
2O) and the 0.0016mol stannous chloride be dissolved in the 100mL distilled water; With 18mL concentration is two (2-ethyl-hexyl) phosphoric acid of 25% ammoniacal liquor, 0.09mol sodium borohydride, 0.03mol octyl group sodium xanthogenate, 0.03mol, the mixed solution of 100mL benzene and toluene mixes, slowly be added dropwise to the metal salt solution that has prepared, there is bubble to emit, stirring reaction 60 minutes.Left standstill 120 minutes, separatory, the upper strata is an oil phase liquid, lower floor is the water white transparency water, discards lower floor's water, upper oil phase through distill thick liquid, be oil-soluble copper ashbury metal nanoparticle.Its transmission electron micrograph is seen Fig. 2.
Embodiment 3
With 0.021mol copper nitrate (Cu (NO
3)
26H
2O) and the 0.0002mol nickel acetate be dissolved in the 100mL distilled water; With 18mL concentration is 25% ammoniacal liquor, the hydrazine hydrate of 0.1mol, 2-hydroxyl-5-nonyl-ketoxime of 0.01mol, two (2-ethyl-hexyl) phosphoric acid of 0.01mol, the 100mL benzinum mixes, slowly be added dropwise to the metal salt solution that has prepared, there is bubble to emit, stir and leave standstill after 15 minutes, separatory, the upper strata is an oil phase liquid, lower floor is the water white transparency aqueous phase liquid, discard lower floor's water, upper oil phase through distill thick liquid, be oil-soluble copper nickel alloy nanoparticle, grain diameter is about 5nm, and its transmission electron micrograph is seen Fig. 3.
Embodiment 4
With 0.02mol Schweinfurt green (Cu (CH3COO)
2H
2O), 0.0001mol manganese nitrate (Mn (NO
3)
26H
2O) and 0.0001mol nickel nitrate (Ni (NO
3)
26H
2O) be dissolved in the 100mL distilled water; With 4.60mL concentration is that 25% ammoniacal liquor, 0.04mol hydrazine hydrate and 0.04mol inferior sodium phosphate, dioctyl aminodithioformic acid and the 150mL chloroform of 0.03mol mix, the metal salt solution that slow dropping has prepared, there is bubble to emit, stirring reaction 120 minutes.After leaving standstill 120 minutes, separatory, the upper strata is the water white transparency aqueous phase liquid, lower floor is an oil phase brownish red transparency liquid.Collect lower floor's organic facies, through distill thick liquid, be oil-soluble copper manganese-nickel nanoparticle.
Embodiment 5
With 0.004mol copper nitrate (Cu (NO
3)
26H
2O), 0.0005mol silver nitrate and 0.00002mol nickel nitrate (Ni (NO
3)
26H
2O) be dissolved in the 100mL distilled water; With 4.60mL concentration is that 25% ammoniacal liquor, 0.03mol hydrazine hydrate and 0.03mol ortho phosphorous acid potassium, 2-hydroxyl-5-nonyl-ketoxime and the 150mL chloroform of 0.008mol mix, slowly be added dropwise to the metal salt solution for preparing, there is bubble to emit, stirring reaction left standstill after 120 minutes, separatory after 60 minutes, the upper strata is the water white transparency aqueous phase liquid, and lower floor is an oil phase brownish red transparency liquid.Collect lower floor's organic facies, through distill thick liquid, be oil-soluble copper silver-nickel nanoparticle.
Embodiment 6
0.006mol cupric sulfate pentahydrate, 0.0001mol ferric sulfate, 0.0002mol ammonium molybdate are dissolved in the 100mL distilled water; With 4.60mL concentration is 25% ammoniacal liquor, 0.024mol hydrazine hydrate and 0.022mol inferior sodium phosphate, the N of 0.006mol, N '-two (the special octyl group benzene of 2-hydroxyl-5-methylene base)-1,2-ethylenediamine and 150mL heptane mix, slowly be added dropwise to the metal salt solution that has prepared, have bubble to emit, stirring reaction left standstill after 180 minutes, separatory after 120 minutes, the upper strata is the water white transparency aqueous phase liquid, and lower floor is an oil phase brownish red transparency liquid.Collect lower floor's organic facies, through distill thick liquid, be oil-soluble copper ferromolybdenum nanoparticle.
Embodiment 7
With 0.075mol Schweinfurt green (Cu (CH
3COO)
2H
2O), 0.0002mol sodium tungstate (Na
2WO
42H
2O) be dissolved in the 100mL distilled water; With 4.60mL concentration is that 4-heptane base salicylic acid and the 150mL benzinum of 25% ammoniacal liquor, 0.75mol ascorbic acid, 0.075mol mixes, and slowly is added dropwise to the metal salt solution for preparing, and has bubble to emit, and stirs and leaves standstill after 30 minutes.Separatory after 120 minutes, upper strata are the water white transparency aqueous phase liquid, and lower floor is an oil phase brownish red transparency liquid.Collect lower floor's organic facies, through distill thick liquid, be oil-soluble copper tungsten alloy nanoparticle.
Claims (8)
1. surface finish nano copper/copper alloy particles, it is characterized in that being prepared by following method: compound concentration is the mantoquita of 0.001～1mol/L or the aqueous solution of mantoquita and alloy compositions salt, mixed liquor with reducing agent, coating material, low pole or nonpolar organic solvent fully mixes then, be to leave standstill 30-180min again behind the reaction 30-180min under the alkaline environment of 8-13 at pH, separate organic facies, promptly get described surface finish nano copper/copper alloy particles after concentrating, wherein copper is 1 with the amount of substance ratio of alloy compositions: 0-0.4; Metallic element: reducing agent: the amount of substance ratio of coating material is 1: 2.5-20: 0.2-2; Reducing agent is one of following or several mixture arbitrarily: hydrazine hydrate, formaldehyde, sodium borohydride, hypophosphite, ascorbic acid; Coating material is dialkyl group phosphoric acid or its salt, alkyl xanthogenic acid or its salt, O, in O '-dialkyl dithiophosphoric acid or its salt, dialkyl amido two bamic acids or its salt, 2-hydroxyl-5-alkylbenzene aldoxime, 2-hydroxyl-5-alkylbenzene ketoxime, alkyl salicylate, the schiff bases one or more, wherein said alkyl is the alkyl of C1-C22.
2. surface finish nano copper/copper alloy particles according to claim 1 is characterized in that described organic solvent is one or more the mixture in the alkane of chloroform, benzene,toluene,xylene, benzinum, C6～C12.
3. as surface finish nano copper/copper alloy particles as described in the claim 2, it is characterized in that the consumption of described organic solvent accounts for the 10%-90% of reaction system cumulative volume.
4. surface finish nano copper/copper alloy particles according to claim 1 is characterized in that described alloy compositions is one or more in zinc, tin, nickel, manganese, iron, silver, molybdenum, the tungsten.
5. the preparation method of surface finish nano copper/copper alloy particles according to claim 1, it is characterized in that compound concentration is the mantoquita of 0.001～1mol/L or the aqueous solution of mantoquita and alloy compositions salt, mixed liquor with reducing agent, coating material, low pole or nonpolar organic solvent fully mixes then, be to leave standstill 30-180min again behind the reaction 30-180min under the alkaline environment of 8-13 at pH, separate organic facies, promptly get described surface finish nano copper/copper alloy particles after concentrating, wherein copper is 1 with the amount of substance ratio of alloy compositions: 0-0.4; Metallic element: reducing agent: the amount of substance ratio of coating material is 1: 2.5-20: 0.2-2; Reducing agent is one of following or several mixture arbitrarily: hydrazine hydrate, formaldehyde, sodium borohydride, hypophosphite, ascorbic acid; Coating material is dialkyl group phosphoric acid or its salt, alkyl xanthogenic acid or its salt, O, in O '-dialkyl dithiophosphoric acid or its salt, dialkyl amido two bamic acids or its salt, 2-hydroxyl-5-alkylbenzene aldoxime, 2-hydroxyl-5-alkylbenzene ketoxime, alkyl salicylate, the schiff bases one or more, wherein said alkyl is the alkyl of C1-C22.
6. the preparation method of nano copper/copper alloy particles as claimed in claim 5 is characterized in that described organic solvent is one or more the mixture in the alkane of chloroform, benzene,toluene,xylene, benzinum, C6～C12.
7. the preparation method of surface finish nano copper/copper alloy particles as claimed in claim 6, the consumption that it is characterized in that described organic solvent is the 10%-90% of reaction system cumulative volume.
8. the preparation method of surface finish nano copper/copper alloy particles as claimed in claim 6 is characterized in that described alloy compositions is one or more in zinc, tin, nickel, manganese, iron, silver, molybdenum, the tungsten.
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