EP2358489A1 - Verfahren zur herstellung von metallnanopartikeln und auf diese weise erhaltene metallnanopartikel und ihre verwendung - Google Patents
Verfahren zur herstellung von metallnanopartikeln und auf diese weise erhaltene metallnanopartikel und ihre verwendungInfo
- Publication number
- EP2358489A1 EP2358489A1 EP09760108A EP09760108A EP2358489A1 EP 2358489 A1 EP2358489 A1 EP 2358489A1 EP 09760108 A EP09760108 A EP 09760108A EP 09760108 A EP09760108 A EP 09760108A EP 2358489 A1 EP2358489 A1 EP 2358489A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal nanoparticles
- functionalized
- metal
- particularly preferably
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 109
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 title description 26
- 239000003381 stabilizer Substances 0.000 claims abstract description 42
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 29
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 117
- 230000008569 process Effects 0.000 claims description 52
- 229910052751 metal Inorganic materials 0.000 claims description 44
- 239000002184 metal Substances 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 28
- 239000006185 dispersion Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000080 wetting agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 20
- 239000002270 dispersing agent Substances 0.000 claims description 20
- 229910052737 gold Inorganic materials 0.000 claims description 19
- 229910052709 silver Inorganic materials 0.000 claims description 18
- 230000009467 reduction Effects 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 239000000976 ink Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 11
- 239000003973 paint Substances 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 10
- 239000004033 plastic Substances 0.000 claims description 10
- 229920003023 plastic Polymers 0.000 claims description 10
- 238000009736 wetting Methods 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 239000012736 aqueous medium Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052741 iridium Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 229910000510 noble metal Inorganic materials 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000002537 cosmetic Substances 0.000 claims description 6
- 239000006184 cosolvent Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 229910052762 osmium Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 239000000565 sealant Substances 0.000 claims description 6
- 229910052711 selenium Inorganic materials 0.000 claims description 6
- 150000003573 thiols Chemical class 0.000 claims description 6
- 229920001400 block copolymer Polymers 0.000 claims description 5
- 239000013530 defoamer Substances 0.000 claims description 5
- 239000002609 medium Substances 0.000 claims description 5
- 229920000768 polyamine Polymers 0.000 claims description 5
- 238000007639 printing Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000002966 varnish Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 230000002902 bimodal effect Effects 0.000 claims description 4
- 239000012459 cleaning agent Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 238000009987 spinning Methods 0.000 claims description 4
- 229910052714 tellurium Inorganic materials 0.000 claims description 4
- 229910002695 AgAu Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229910016317 BiTe Inorganic materials 0.000 claims description 3
- 229910004613 CdTe Inorganic materials 0.000 claims description 3
- 229910018979 CoPt Inorganic materials 0.000 claims description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 3
- 229910000673 Indium arsenide Inorganic materials 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910010276 inorganic hydride Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- 229920000193 polymethacrylate Polymers 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229920006163 vinyl copolymer Polymers 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 238000001069 Raman spectroscopy Methods 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 230000003321 amplification Effects 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 2
- 210000003298 dental enamel Anatomy 0.000 claims description 2
- 238000004870 electrical engineering Methods 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- 150000002429 hydrazines Chemical class 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 150000002443 hydroxylamines Chemical class 0.000 claims description 2
- 229910001867 inorganic solvent Inorganic materials 0.000 claims description 2
- 239000003049 inorganic solvent Substances 0.000 claims description 2
- 229910052945 inorganic sulfide Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 2
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 230000006911 nucleation Effects 0.000 claims description 2
- 238000010899 nucleation Methods 0.000 claims description 2
- 238000003199 nucleic acid amplification method Methods 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000006174 pH buffer Substances 0.000 claims description 2
- 229920000151 polyglycol Polymers 0.000 claims description 2
- 239000010695 polyglycol Substances 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000006254 rheological additive Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000004611 spectroscopical analysis Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 150000003892 tartrate salts Chemical class 0.000 claims description 2
- 230000002123 temporal effect Effects 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 2
- 239000003086 colorant Substances 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 17
- 239000010931 gold Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000008901 benefit Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 7
- CCTFMNIEFHGTDU-UHFFFAOYSA-N 3-methoxypropyl acetate Chemical compound COCCCOC(C)=O CCTFMNIEFHGTDU-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 239000013049 sediment Substances 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 5
- 101710134784 Agnoprotein Proteins 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009739 binding Methods 0.000 description 2
- 230000027455 binding Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229940098773 bovine serum albumin Drugs 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004917 polyol method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 229940038773 trisodium citrate Drugs 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 229920000028 Gradient copolymer Polymers 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 102000007474 Multiprotein Complexes Human genes 0.000 description 1
- 108010085220 Multiprotein Complexes Proteins 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229920000469 amphiphilic block copolymer Polymers 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- 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
-
- 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
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0545—Dispersions or suspensions of nanosized particles
-
- 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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/62—Metallic pigments or fillers
-
- 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
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
- B22F2304/054—Particle size between 1 and 100 nm
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/84—Manufacture, treatment, or detection of nanostructure
- Y10S977/895—Manufacture, treatment, or detection of nanostructure having step or means utilizing chemical property
- Y10S977/896—Chemical synthesis, e.g. chemical bonding or breaking
Definitions
- the present invention relates to the technical field of nanotechnology.
- the present invention relates to a process for the preparation of metal nanoparticles and the metal nanoparticles obtainable in this way and to their use. Furthermore, the present invention relates to the invention containing metal nanoparticles dispersions. Finally, the present invention relates to coating materials and coating systems, glasses and glassy coatings, inks and printing inks, plastics, foams, cosmetics, cleaning agents and impregnating agents, adhesives, sealants and catalyst systems which contain the metal nanoparticles according to the invention or the dispersions of the invention.
- the preparation of such metal nanoparticles can be carried out via the reduction of a metal salt (eg a silver salt) in a two-phase reaction with sodium borohydride as the reducing agent.
- a metal salt eg a silver salt
- the metal salt is first using z. B. of tetraoctylammonium bromide from the aqueous into the organic phase (eg., Toluene or chloroform) and then reduced by means of sodium borohydride.
- the organic phase eg., Toluene or chloroform
- a stabilizer such.
- dodecanethiol almost monodisperse metal nanoparticles can be synthesized and dispersed in various media due to the surface modification. For use in water, it requires in most cases a phase transfer catalyst such.
- Another alternative is the so-called polyol method (see, for example, US 2006/0090599 A1), according to which a reduction of a metal ion source in or by a polyol at elevated temperatures above 100 0 C, in general above 150 ° C, is performed.
- the polyol also serves as a stabilizer and solvent, ie no additional solvent is required.
- a disadvantage of this method is that the resulting metal nanoparticles as such are not or at most very expensive isolatable. In addition, the resulting metal nanoparticles are not or only with difficulty modifiable for non-polar systems.
- Another disadvantage is the use of relatively expensive starting chemicals and the relatively high process temperatures.
- metal nanoparticles in particular gold nanoparticles
- sonolysis is possible, but generally only on an experimental scale.
- This method is based on an energy input by means of ultrasound.
- An aqueous solution of, for example, HAuCl 4 is reacted with glucose, the actual reducing agent being hydroxyl radicals and sugar pyrolysis radicals which form at the interface region between the collapsing cavities of the glucose and the water.
- So-called nanoribbons with widths of 30 to 50 nm and lengths of a few micrometers are created, these bands are flexible and more than 90 ° flexible.
- JP 2003-147418 A relates to the preparation of metal nanoparticles (for example Au or Pd) by reduction in micelles in aqueous media, the micelles being produced from amphiphilic block copolymers.
- metal nanoparticles for example Au or Pd
- the necessary for Micellbil- formation block copolymers are relatively expensive to produce and also act as a reducing agent.
- US 2006/0266156 A1 relates to metal particles which comprise on their surface two mutually different wetting or dispersing agents with different evaporation temperatures, and a process for their preparation.
- US 2006/0266157 A1 describes the preparation of metal nanoparticles by reduction of aqueous metal salt solutions in the presence of a wetting agent, such. Cetyltrimethylammonium bromide (CTAB).
- CTCAB Cetyltrimethylammonium bromide
- the particles obtained in this way can be dispersed with the addition of wetting or dispersing agents and combined for bindings with binders.
- the preparation is not carried out in a purely aqueous medium.
- the reaction is a combination of citrate method on the one hand and two-phase reaction on the other hand.
- the coverage of the particle surfaces, for example with CTAB as wetting agent provides readily dispersible particles in nonpolar media, but CTAB is relatively expensive and must be used in significant excess.
- the addition of further dispersants is required in order to achieve a certain coating compatibility at all.
- WO 2006/053225 A2 relates to the preparation of metal nanoparticles / protein complexes.
- the preparation is carried out in an aqueous medium below
- WO 2006/072959 A1 relates to water-based dispersions of metal nanoparticles and to a process for their preparation in the presence of a reducing water-soluble polymer which allows metal formation to form metal cores.
- US 2007/0034052 A1 and US 2006/0159603 A1 describe the preparation of metal nanoparticles, in particular silver nanoparticles, by reduction of metal ions by means of polyols.
- No. 6,992,039 B2 relates to the preparation of supported monodisperse noble metal nanoparticles on oxidic substrates.
- the in situ preparation of noble metal nanoparticles on porous ceramics is described.
- the reduction of the noble metal salts occurs in the presence of metal alkoxides and wetting agents, followed by a subsequent step of calcining.
- US 2003/0199653 A1 relates to the preparation of metal nanoparticles in an aqueous medium in the presence of sulfur-containing copolymers by reduction with NaBH 4 . Due to the use of sulfur-containing stabilizers, the particles obtained in this way can not be used for catalysis. Furthermore, the synthesis is relatively expensive. Also, the redispersibility of the particles thus obtained is not very large.
- WO 02/087749 A1 CA 2 445 877 A1 and US 2004/0147618 A1 describe the preparation of silver nanoparticles in various media using gamma radiation or ultrasound in the presence of polymeric stabilizers.
- the problem underlying the present invention is thus to provide a process for the production of metal nanoparticles, which at least largely avoids or at least mitigates the previously described disadvantages of the prior art processes.
- the present invention proposes a method according to claim 1; Further, advantageous embodiments are the subject of the relevant sub-claims.
- the subject of the present invention are dispersions of the metal nanoparticles according to the invention in a carrier or dispersion medium according to claim 44.
- the invention further relates to coating materials and coating systems, in particular paints, paints and the like, glasses and glassy coatings, inks and printing inks, plastics, foams, cosmetics, in particular nail varnishes, cleaning agents and impregnating agents, adhesives, sealants and catalyst systems, which are known from US Pat Metal nanoparticles according to the invention or the dispersions according to the invention contain (claim 45).
- coating materials and coating systems in particular paints, paints and the like, glasses and glassy coatings, inks and printing inks, plastics, foams, cosmetics, in particular nail varnishes, cleaning agents and impregnating agents, adhesives, sealants and catalyst systems, which are known from US Pat Metal nanoparticles according to the invention or the dispersions according to the invention contain (claim 45).
- the subject matter of the present invention is a process for the preparation of metal nanoparticles in which metal ions are reduced by means of at least one reducing agent in the presence of at least one polymeric stabilizer and converted into metal nanoparticles. This results in dispersions of metal nanoparticles, which are modified or coated on their surface with the polymeric stabilizer.
- the reducing agent effects the reduction to elemental metal in the oxidation state 0, while the polymeric stabilizer ensures that the metal particles formed are produced as so-called nanoparticles, in particular agglomerate or not as an amorphous precipitate can separate or the like.
- the inventive method is carried out in a liquid, preferably an aqueous medium or medium.
- a liquid preferably an aqueous medium or medium.
- the metal ions are dissolved in the respective medium or finely distributed in the form of salts.
- the process according to the invention is carried out as a liquid-phase process, in particular as a single-phase reaction. This is a significant advantage over the initially described in the prior art reactions with two liquid phases to see.
- defoamers known per se to the person skilled in the art can be used for this purpose.
- the amount of defoamer can vary within wide ranges; Usually, the defoamer in amounts of 0.0001 to 5 wt .-%, preferably 0.001 to 2 wt .-%, particularly preferably 0.01 to 1 wt .-%, based on the total reaction mixture used.
- Additives suitable according to the invention are selected, for example, from the group of pH regulators, pH buffer substances, emulsifiers, rheology modifiers, preservatives, surfactants or the like.
- co-solvent may also be added to the reaction mixture.
- the amount of co-solvent (s) can likewise vary widely; Usually amounts of from 0.01 to 10% by weight, particularly preferably from 0.1 to 7% by weight, very particularly preferably from 0.5 to 5% by weight, of co-solvent (s) are used on the entire reaction.
- the co-solvent may in particular be selected from organic, preferably polar solvents, such as alcohols, glycols (eg butylglycol etc.) or the like, or else from inorganic solvents, such as acids and bases.
- inorganic acids or bases for metal salts can be used as co-solvents for starting materials.
- NH 3 to achieve the solubility of AgCl in water, which leads to the formation of [Ag (NH 3 ) 2 ] Cl, or HCl for AuCl 3 as the starting material, which in turn leads to the formation of HAuCl 4 .
- the process according to the invention can be carried out over a wide temperature range. Since the process is carried out as a liquid phase process, the temperature range is limited downwards by the melting point of the reaction milieu and upwards by its boiling point. In general, especially when using an aqueous medium, the process in the temperature range of> 0 0 C and ⁇ 100 0 C, in particular 5 to 90 0 C, preferably 10 to 80 0 C, particularly preferably 10 to 40 0 C, very particularly preferably 10 to 30 0 C, performed. Lower temperatures have the advantage that generally more stable dispersions are obtained and, in addition, the resulting nanoparticles generally show better redispersibility.
- a further advantage of the method according to the invention can be seen in the relatively short process times, which is of great advantage, especially in the case of large-scale implementation or implementation on an industrial scale.
- the process according to the invention is usually carried out with a reaction time of ⁇ 10 minutes, in particular ⁇ 5 minutes, preferably ⁇ 1 minute, more preferably ⁇ 0.5 minutes.
- the process according to the present invention is carried out with a reaction time in the range of 0.0001 to 10 minutes, in particular 0.0001 to 5 minutes, preferably 0.0001 to 1 minute, particularly preferably 0.0001 to 0.5 minutes.
- the actual implementation is completed within a few seconds in the context of the method according to the invention.
- the process according to the invention can alternatively be operated either batchwise or batchwise or else continuously.
- the inventive method can be carried out, for example, in a simple stirred tank.
- a continuous procedure however, the process of the invention in a continuous stirred or tubular reactor, a continuous Rhakkesselkaskade or be carried out in a so-called spinning disk reactor.
- the continuous implementation in a so-called spinning-disk reactor offers the additional advantage of extremely fast conversion due to a very rapid and intensive mixing; for further details of the procedure in a spinning disk reactor, reference may be made, for example, to WO 2006/018622 A1, WO 2006/040566 A1 and WO 2006/008500 A1, the entire disclosure of which is hereby incorporated by reference.
- the method according to the invention can be carried out such that a temporal and / or local separation of the nucleation and growth processes is achieved by regulating temperature and / or volume flows;
- the method according to the invention can be carried out in particular in a so-called microreaction technology system.
- a particular advantage of this procedure is that a particularly uniform morphology and / or monodispersibility of the resulting metal nanoparticles is achieved.
- the reducing agent should be selected such that it is capable of reducing the relevant metal ion to be reduced to elemental metal (i.e., oxidation state: 0).
- the reducing agent in the electrochemical series has a lower normal potential than the metal of the metal ion to be reduced.
- the reducing agent should be selected to be soluble or dispersible in the reaction medium.
- Reducing agents which are suitable according to the invention are in particular selected from the group of inorganic hydrides, such as sodium borohydride or lithium aluminum hydride; inorganic thiosulfates or thiosulfuric acid; inorganic sulfides or hydrogen sulfide; inorganic sulfites; hydrazines; hydroxylamines; Hydrogen (eg gaseous or in situ generated hydrogen or nascent hydrogen); carbon monoxide; Acetylene; Oxalic acid or oxalates; Citric acid or citrates; Tartaric acid or tartrates; monohydric or polyhydric alcohols, e.g.
- inorganic hydrides such as sodium borohydride or lithium aluminum hydride
- inorganic thiosulfates or thiosulfuric acid inorganic sulfides or hydrogen sulfide
- inorganic sulfites inorganic sulfites
- hydrazines
- glycol or else hydroxy-functional polyglycol ethers; Sugar; inorganic phosphides; and mixtures or combinations of at least two of the aforementioned reducing agents.
- inorganic hydrides in particular of the aforementioned type.
- the amount of reducing agent used can likewise vary widely.
- the reducing agent in a ratio of reducing agent to metal ions, calculated as the amount of electrons required for the reduction in the range of 1.05: 1 to 200: 1, in particular 1.1: 1 to 100: 1, preferably 1 , 1: 1 to 50: 1, used.
- the larger the aforementioned ratio the more nuclei are formed and the smaller the nanoparticles are formed.
- the metal is selected from at least one metallic element of groups III A to VA and IB to VIII B of the periodic system of the elements.
- the metal is selected from the group of Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Ru, Os, Se, Te, Cd, Bi, In, Ga, As, Ti, V, W , Mo, Si, Al and / or Sn and mixtures, alloys and mixed crystals of at least two of these elements.
- the metal is selected from the group of Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Ru, Os, Se and / or Te and mixtures, alloys and mixed crystals of at least two of these elements .
- the metal is selected from noble metals, in particular Cu, Ag, Au, Ni, Pd, Pt, Ru, Ir and / or Rh, most preferably Ag, Au, Pd and / or Pt.
- the nanoparticles can be obtained based on at least two metals, in particular of the type CdSe, CdTe, BiTe, GaAs, InAs, AgPd, CoPt and / or AgAu. These are thus at least binary metal nanoparticles.
- Such systems are of interest, for example, for the semiconductor technology and the catalyst technology.
- the metal ions can basically be used in any desired forms. It is possible to use all metal ion sources which are compatible in the context of the process according to the invention, in particular in which the reaction medium is soluble or dispersible.
- the metal ions may be present in particular in the form of metal salts (eg AgNO 3 , Na 2 PtCl 4 , NaAuCl 4 • 2H 2 O etc.), metal acids and their hydrates (eg HAuCl 4 • 3 H 2 O, H 2 PtCl 4 • 6H 2 O, H 2 PtCl 4 etc.), ionic or covalent metal compounds (eg AuCl 3 , PtCl 2 , AgCl etc.), complexed metal ions and / or metal electrodes (eg in electrolysis ), preferably in the form of metal salts.
- metal salts eg AgNO 3 , Na 2 PtCl 4 , NaAuCl 4 • 2H 2 O etc.
- metal acids and their hydrates e
- the amount of metal ions used can likewise vary widely.
- the metal ions based on the total reaction mixture and calculated as metal, in amounts of 0.0001 to 20 wt .-%, in particular 0.001 to 15 wt .-%, preferably 0.005 to 10 wt .-%, particularly preferably 0, 01 to 3 wt .-%, most preferably 0.1 to 2 wt .-%, used.
- the metal nanoparticles obtained can have absolute particle sizes in the range from 0.3 to 1000 nm, in particular 0.5 to 750 nm, preferably 1 to 500 nm, particularly preferably 2 to 100 nm, very particularly preferably 3 to 50 nm.
- the metal nanoparticles obtained have average particle sizes (determined as so-called D50 value) in the range from 1 to 500 nm, in particular 2 to 200 nm, particularly preferably 2 to 100 nm, very particularly preferably 5 to 40 nm.
- the size and shape of the resulting metal nanoparticles can be varied by the corresponding variation of the reaction conditions. For example, by varying the type and / or quantity of the reduction by means of and / or the type and / or amount of the polymeric stabilizer and / or the reaction temperature and / or the addition mode (single addition, stepwise addition, etc.) or the like, the particle size targeted influence or adjust. This is known to the skilled person as such.
- the metal nanoparticles obtained may have a bimodal particle size distribution.
- the average particle diameter (D50) of the two fractions of metal nanoparticles can advantageously not differ by at least 10 nm, in particular at least 25 nm, preferably at least 50 nm, particularly preferably at least 75 nm, very particularly preferably at least 100 nm.
- special effects, in particular surface effects can be achieved, in particular with regard to the mechanical properties, such as mechanical stability, abrasion resistance, surface properties, gloss etc.
- a bimodal particle size distribution can be achieved by deliberate variation or adjustment of the reaction conditions, for example by selecting the ratio of reducing agent to metal ions to be reduced, by the amount of polymeric stabilizer (eg lower or substoichiometric amounts of polymeric Stabilizer), by stepwise and / or repeated addition of the individual reagents etc. This is familiar to the person skilled in the art as such.
- the polymeric stabilizer As far as the polymeric stabilizer is concerned, it can equally be used in wide ranges.
- the polymeric stabilizer may be used in amounts of 1 to 1000% by weight, preferably 5 to 500% by weight, more preferably 10 to 200% by weight, most preferably 20 to 100% by weight, based on the resulting metal nanoparticles are used.
- the polymeric stabilizer As far as the chemical nature of the polymeric stabilizer is concerned, it is in particular a polymeric dispersant or a polymeric wetting agent and / or a surfactant.
- the molecular weight of the polymeric stabilizer used can equally vary within wide ranges.
- the polymeric stabilizer used usually has an average, in particular weight-average molecular weight of at least 1,000 g / mol, preferably at least 1,500 g / mol.
- the polymeric stabilizer has an average, in particular weight-average molecular weight in the range from 1,000 to 1,000,000 g / mol, in particular from 1,250 to 100,000 g / mol, preferably from 1,500 to 75,000 g / mol, particularly preferably from 2,000 to 50,000 g / mol ,
- the polymeric stabilizer is based on a functionalized, in particular acid and / or basic functionalized, polymer, in particular with polar functional groups formed.
- the polymeric stabilizer can be selected from the group of functionalized polyamines, functionalized polyurethanes, functionalized poly (meth) acrylates, functionalized vinyl copolymers, functionalized polyether / polyester copolymers, functionalized polyethers, functionalized polyesters, functionalized fatty acid copolymers, functionalized block copolymers. copolymeric and / or functionalized polyalkoxy laten and mixtures or combinations of at least two of these compounds.
- the polymeric stabilizer may usually be based on a functionalized, especially acid and / or basic functionalized polymer, the polymer containing at least one functional group, which may in particular be selected from the group of hydroxyl (-OH), thiol (-) SH), amine, ammonium, carboxyl, carbonyl, ester, ether, sulfonyl, phosphoric and / or phosphoric acid ester functions, preferably hydroxyl (-OH), thiol (-SH) and / or amine functions.
- a functionalized, especially acid and / or basic functionalized polymer the polymer containing at least one functional group, which may in particular be selected from the group of hydroxyl (-OH), thiol (-) SH), amine, ammonium, carboxyl, carbonyl, ester, ether, sulfonyl, phosphoric and / or phosphoric acid ester functions, preferably hydroxyl (-OH), thiol (-SH) and / or
- the base number of the polymer in question may be at least 10 mg KOH / g, in particular at least 20 mg KOH / g, preferably at least 25 mg KOH / g, and in the case of acidic functionalization, the acid number may be at least 10 mg KOH / g, preferably at least 25 mg KOH / g, more preferably at least 50 mg KOH / g.
- the polymeric stabilizer can be selected from the dispersants and / or wetting agents mentioned below, as described in the publications listed below, whose respective disclosure content is hereby incorporated by reference:
- modified polyurethanes and polyamines according to EP 1 593 700 A; salified polyamines according to EP 0 893 155 A; - Phosphoric acid ester according to EP 0 417 490 A;
- a step of purification may follow the actual production of the metal nanoparticles.
- the purification can be carried out in a manner known per se to those skilled in the art, so that no further relevant embodiment is required.
- the resulting metal nanoparticles can be separated by methods known per se, to which may optionally follow a process step of redispersing (for example in another medium).
- the metal nanoparticle dispersions obtained can also be used as such, ie as they are obtained immediately after the preparation, since the respective metal nanoparticles are present in stable, in particular long-term stable dispersion.
- the process according to the invention for the preparation of metal nanoparticles is associated with a number of advantages, some of which are to be mentioned below in a nonlimiting manner:
- the inventive method works cost-effectively and economically and is also readily Anlagenmotherbar on an industrial or industrial scale.
- the method according to the invention can be configured extremely flexibly with regard to its process control.
- the process of the invention can be operated continuously as a batch. In discontinuous procedure can be moved, for example, in a stirred tank. In a continuous procedure, the reaction can be carried out, for example, in a continuous stirred reactor or tubular reactor, a continuous stirred tank cascade or in a so-called spinning disk reactor.
- the relatively low process temperatures also contribute to process efficiency and process economics and also meet today's environmental requirements.
- the process according to the invention is carried out in purely aqueous media; it is, as it were, a "green process" which, moreover, is flexibly modifiable.
- the process is thus simple, inexpensive and ecologically compatible and largely dispenses with organic solvents.
- the metal nanoparticles obtained in the context of the process according to the invention can readily be isolated from the dispersion. Due to the stability of the dispersions, however, the dispersions can also be used as such without having to carry out a preceding isolation of the metal nanoparticles.
- nanoparticles are achieved in a variety of media (such as water, organic solvents, polymers, waxes, oils, glycols, etc.).
- dispersants or wetting agents used can readily be removed either partially or completely
- the metal nanoparticles obtained by the process according to the invention allow a wide variety of uses, for example as paint and / or plastic additives, as pigments, as catalysts, etc. This is described in detail below.
- the process according to the invention thus provides a purely aqueous synthesis of metal nanoparticles, more preferably noble metal nanoparticles, using suitable polymeric wetting or dispersing agents.
- the synthesis can be flexibly applied to different metals (eg silver, gold, etc.).
- suitable wetting or dispersing agents By using suitable wetting or dispersing agents, the subsequent dispersibility can be controlled in a wide variety of media.
- By adapting the oxidation potential of the reducing agent and choosing a suitable stabilizer it is also possible to produce nanoparticles (oxidation) -sensitive metals.
- the inventive method is also flexible transferable to a variety of metals. With the method according to the invention can be achieve significantly higher concentrations in dispersion of nanoparticles compared to the prior art. In addition, the process according to the invention uses exclusively favorable starting chemicals or educts. In addition, the method according to the invention can also be carried out on an industrial or industrial scale and thus upscalebar. Due to the removability of the wetting or dispersing agents used, no "dead" surfaces are formed on the resulting metal nanoparticles.
- a further subject of the present invention - according to one aspect of the invention - are the metal nanoparticles obtainable by the process according to the invention.
- the present invention relates to metal nanoparticles which comprise on their surface at least one polymeric stabilizer, in particular a polymeric wetting and dispersing agent, or on their surface with at least one polymeric stabilizer, in particular a polymeric wetting agent Dispersants, modified and / or coated.
- the metal nanoparticles according to the invention have an excellent dispersing behavior and can be easily redispersed even after isolation from the reaction mixture.
- the metal nanoparticles according to the invention are dispersible both in aqueous and in organic media.
- the metal nanoparticles according to the invention are dispersible in both polar and non-polar solvents.
- the dispersing properties of the metal nanoparticles according to the invention can be adjusted selectively by the surface modification with the polymeric stabilizer or, so to speak, tailor-made.
- Another object of the present invention - according to a third aspect of the invention - is the inventive use of the metal nanoparticles according to the present invention.
- the metal nanoparticles according to the invention can be used, for example, as additives, pigments or fillers, in particular for paints, coatings and plastics.
- metal nanoparticles according to the invention can be used as or in catalysts or catalyst systems.
- the metal nanoparticles according to the invention can also be used in coating materials and coating systems, in particular paints, inks and the like, in glasses and glassy coatings, in inks and printing inks, in dispersions of all kinds, in plastics, in foams, in cosmetics, in particular nail varnishes , in detergents and impregnating agents, in adhesives, in sealants and in catalysts or catalyst systems, in particular as additives, pigments or fillers.
- coating materials and coating systems in particular paints, inks and the like, in glasses and glassy coatings, in inks and printing inks, in dispersions of all kinds, in plastics, in foams, in cosmetics, in particular nail varnishes , in detergents and impregnating agents, in adhesives, in sealants and in catalysts or catalyst systems, in particular as additives, pigments or fillers.
- the nanoparticles according to the invention can be used in optics and optoelectronics as well as in electronics, electrical engineering and semiconductor technology.
- the metal nanoparticles according to the invention can be used to increase conductivities, in particular of plastics, or else for the production of printable circuits.
- metal nanoparticles according to the invention can also be used in spectroscopy, in particular in Raman spectroscopy, for example for purposes of signal amplification.
- metal nanoparticles of the invention in the glass, ceramic and enamel manufacture, for. As in the manufacture of windows (for example, church windows), in particular as pigments or dyes. Furthermore, it is possible to use the metal nanoparticles according to the invention in textile production, for example, equally as pigments and / or dyes.
- a further subject matter of the present invention - according to one aspect of the invention - are dispersions which contain the metal nanoparticles according to the invention in a carrier or dispersion medium.
- further object of the present invention are coating materials and coating systems, in particular paints, inks and the like, plastics, foams, cosmetics, in particular nail varnishes, adhesives, sealants and catalyst systems comprising the metal nanoparticles according to the invention or the comprising dispersions containing them.
- Gold nanoparticles are prepared according to the method described by Turkevich et al. developed method by citrate synthesis as follows. 10 ml of an aqueous solution of 2.5 - 10 '4 mol / 1 HAuCl 4 • 3 H 2 O are heated to 95 0 C. Subsequently, 417 ⁇ l of a 20 mmol / l trisodium citrate solution are added with vigorous stirring, whereupon the solution slowly changes its color to red. The Au / citrate ratio is 0.3. The solution is left for 15 minutes near the boiling point, then allowed to cool the whole.
- the example is repeated except that 312 ⁇ l of a 20 mmol / l trisodium citrate solution are added, which corresponds to an Au / citrate ratio of 0.4.
- the aforementioned Au / citrate ratios influence the resulting sizes of the Au nanoparticles obtained.
- Example 2 Preparation of Silver Nanoparticles by Two-Phase Synthesis in the Presence of NaBH 4 as Reducing Agent (Comparative, Prior Art) 9 mmol (1.53 g) of silver nitrate are dissolved in 300 ml of water in a 1-liter three-necked flask. 40 mmol (21.86 g) of tetra-n-octylammonium bromide are dissolved in 204 ml of CHCl 3 in a beaker.
- the CHCl 3 solution is added to the silver nitrate solution. After about 1 minute, the N 2 stream is issued. The CHCl 3 phase turns green and becomes cloudy. The water phase becomes milky, but contains no target product.
- the resulting powder must still be washed with ethanol to remove impurities and then be dispersed in nonpolar solvents up to 0.2%.
- the particle size is 10 nm, but has a coarse fraction (10%) of> 100 nm. The reaction is very sensitive and not always reproducible.
- EXAMPLE 3A Preparation of Silver Nanoparticles by the Process According to the Invention (Invention) First, a solution of 3.5 parts by weight of AgNO 3 , 100 parts by weight of water, 7.2 parts by weight of a polymeric wetting or dispersing agent ( z. B. Disperbyk ® 2001, BYK-Chemie GmbH, Wesel, Germany) and optionally 0.6 parts by weight of a defoamer (z. B. BYK028 BYK-Chemie GmbH, Wesel, Germany) ( "solution a”) prepared and stirred at room temperature. The approach is a cloudy mixture.
- a polymeric wetting or dispersing agent z. B. Disperbyk ® 2001, BYK-Chemie GmbH, Wesel, Germany
- a defoamer z. B. BYK028 BYK-Chemie GmbH, Wesel, Germany
- solution B is prepared from 3 parts by weight of NaBH 4 and 50 parts by weight of water. Solution B is slowly added to solution A at room temperature. It creates strong foam and blackening. This results in a dispersion of Ag nanoparticles in water.
- z. B. be extracted with PMA (methoxypropyl acetate), which leads to nanoparticles of high purity, which z. B. can be used for catalytic purposes, or centrifuged, dried and redispersed (eg in PMA).
- PMA methoxypropyl acetate
- the preceding experiment is repeated, but with the difference that the solution B is rapidly added to the solution A. Rapid addition of solution B to solution A produces smaller nanoparticles. As a result of the rate of addition, the particle size of the resulting nanoparticles can thus be controlled in a targeted manner.
- Example 3B is used: Preparation of silver nanoparticles by the inventive process (invention) Example 3A but with the difference that another wetting agent (Disperbyk ® 194 from BYK-Chemie GmbH, Wesel, Germany concrete) is repeated.
- the resulting Ag nanoparticles are redispersible both in water and in PMA. This dispersion of Ag nanoparticles can thus be used directly as an additive, if appropriate after a corresponding treatment and / or concentration step.
- HAuCl 4 is used instead of AgNO 3 . This results in the corresponding Au nanoparticles.
- Example 3D Reduction of AgNO 3 in Water Without the Presence of a Dispersing Agent (Comparison)
- Example 3A is repeated, but with the difference that no wetting or dispersing agent is used as stabilizer. There is no formation of Ag nanoparticles, but a through-reaction to an Ag sludge.
- the silver particles produced at temperatures up to 40 ° C have much better redispersibilities in polar solvents, such as water and 1,3-propanediol.
- polar solvents such as water and 1,3-propanediol.
- the dispersing behavior in ethyl acetate is initially good in all experiments, but the dispersions of the nanoparticles From 60 0 C lower stability in ethyl acetate, as evidenced by the formation of a silver level on the glass wall. Redispersibility in PMA is equally good at all temperatures.
- the formation of a silver mirror can also be used to advantage for the mirroring or formation of conductive layers.
- the destabilization causes the particles to approach each other and optionally a plasmon transition.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Non-Insulated Conductors (AREA)
- Cosmetics (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Powder Metallurgy (AREA)
- Conductive Materials (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102008061703 | 2008-12-12 | ||
| DE102009015470A DE102009015470A1 (de) | 2008-12-12 | 2009-03-28 | Verfahren zur Herstellung von Metallnanopartikeln und auf diese Weise erhaltene Metallnanopartikel und ihre Verwendung |
| PCT/EP2009/008289 WO2010066335A1 (de) | 2008-12-12 | 2009-11-20 | Verfahren zur herstellung von metallnanopartikeln und auf diese weise erhaltene metallnanopartikel und ihre verwendung |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2358489A1 true EP2358489A1 (de) | 2011-08-24 |
Family
ID=42168810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP09760108A Withdrawn EP2358489A1 (de) | 2008-12-12 | 2009-11-20 | Verfahren zur herstellung von metallnanopartikeln und auf diese weise erhaltene metallnanopartikel und ihre verwendung |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US8870998B2 (ja) |
| EP (1) | EP2358489A1 (ja) |
| JP (1) | JP5833447B2 (ja) |
| KR (1) | KR101278939B1 (ja) |
| CN (1) | CN102245333B (ja) |
| BR (1) | BRPI0923509A2 (ja) |
| DE (1) | DE102009015470A1 (ja) |
| WO (1) | WO2010066335A1 (ja) |
Families Citing this family (71)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8894760B2 (en) * | 2009-11-20 | 2014-11-25 | Rohm And Haas Electronic Materials Llc | Group 3a ink and methods of making and using same |
| DE102010033924A1 (de) * | 2010-08-03 | 2012-02-09 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur Herstellung von Nanopartikeln aus einem Edelmetall und die Verwendung der so hergestellten Nanopartikel |
| TW201219470A (en) * | 2010-11-12 | 2012-05-16 | Univ Nat Taiwan | Oil dispersible composite of metallic nanoparticle and method for synthesizing the same |
| US8308842B2 (en) * | 2010-12-08 | 2012-11-13 | Xerox Corporation | Pyrophoric iron nanoparticles and continuous processes for production thereof |
| CN102179525B (zh) * | 2011-04-15 | 2013-05-08 | 北京航空航天大学 | 一种室温条件制备镍铂双层纳米碗的可控合成方法 |
| US10071174B2 (en) | 2011-06-06 | 2018-09-11 | Portland State University | Bismuth particle X-ray contrast agents |
| JP5140187B1 (ja) * | 2011-09-27 | 2013-02-06 | 田中貴金属工業株式会社 | 導電粒子及び金属ペースト並びに電極 |
| CN102528070B (zh) * | 2012-01-09 | 2014-01-01 | 苏州银瑞光电材料科技有限公司 | 利用高速射流生产纳米银粉的方法和装置 |
| CN102554219B (zh) * | 2012-01-31 | 2014-03-26 | 云南云天化股份有限公司 | 铜锡核壳结构的纳米粒子及其制备方法 |
| CN102649035A (zh) * | 2012-02-06 | 2012-08-29 | 京东方科技集团股份有限公司 | 一种电泳粒子及其制作方法、电泳微胶囊 |
| KR101279459B1 (ko) * | 2012-04-19 | 2013-06-26 | 서울과학기술대학교 산학협력단 | 화학적 환원 합성법을 이용한 주석계 솔더 페이스트 제조 방법 |
| CN103624265A (zh) * | 2012-08-21 | 2014-03-12 | 国家纳米科学中心 | 一种纳米金颗粒及其制备方法 |
| CN103658672B (zh) * | 2012-09-11 | 2015-10-21 | 中国科学院大连化学物理研究所 | 一种金属纳米粒子的水相制备方法 |
| CN104797363B (zh) | 2012-09-27 | 2018-09-07 | 罗地亚经营管理公司 | 制造银纳米结构的方法和可用于此方法的共聚物 |
| FR2997101B1 (fr) * | 2012-10-18 | 2015-01-02 | Holding Textile Hermes | Procede de fabrication d'un textile a effet de coloration variable contenant de l'or ou au moins un alliage contenant de l'or sous forme de particules et textile a effet de coloration variable. |
| KR102675888B1 (ko) * | 2012-10-29 | 2024-06-14 | 알파 어셈블리 솔루션스 인크. | 소결 분말 |
| CN103056388B (zh) * | 2013-01-22 | 2015-07-22 | 西南科技大学 | 液相化学还原法制备包覆有分散稳定剂的铝纳米粒子的方法 |
| CN103970375A (zh) * | 2013-01-29 | 2014-08-06 | 华为终端有限公司 | 指甲油、指甲装饰物及触控屏幕的操作方法 |
| CN103157808B (zh) * | 2013-02-01 | 2015-04-01 | 天津商业大学 | 一种金铂钌合金纳米粒子及其胶体分散体系的制备方法 |
| CN103149194B (zh) * | 2013-02-28 | 2015-08-26 | 西安交通大学 | 一种表面增强拉曼散射基体的制备方法 |
| EP2781562B1 (en) * | 2013-03-20 | 2016-01-20 | Agfa-Gevaert | A method to prepare a metallic nanoparticle dispersion |
| CN105307804B (zh) * | 2013-06-07 | 2018-02-02 | Lg化学株式会社 | 制造金属纳米粒子的方法 |
| CN105324851B (zh) * | 2013-08-01 | 2017-03-22 | 株式会社Lg化学 | 用于制造太阳能电池光吸收层的聚集前驱体及其制造方法 |
| CN103433044B (zh) * | 2013-08-27 | 2015-05-13 | 安徽大学 | 一种钴-镍双金属氢氧化物纳米复合物的制备方法 |
| AU2014343178A1 (en) * | 2013-11-01 | 2016-05-26 | Council Of Scientific And Industrial Research | A process for the preparation of metal nanoparticles |
| CN103752846A (zh) * | 2014-01-17 | 2014-04-30 | 昆明理工大学 | 一种微通道连续快速制备纳米铜的方法 |
| CN103990810A (zh) * | 2014-05-30 | 2014-08-20 | 洛阳理工学院 | 一种纳米铟粉的制备工艺 |
| KR101689679B1 (ko) * | 2014-05-30 | 2016-12-26 | 한국화학연구원 | 금속 나노입자 및 이의 제조방법 |
| CN104130629B (zh) * | 2014-07-30 | 2016-01-20 | 深圳市宇顺电子股份有限公司 | 导电墨水及其制备方法 |
| CN104128616B (zh) * | 2014-08-12 | 2016-03-23 | 苏州思美特表面材料科技有限公司 | 一种金属粉末的制备方法 |
| CZ307129B6 (cs) * | 2014-09-24 | 2017-12-27 | Univerzita Pardubice | Způsob přípravy bimodální směsi nanočástic a mikročástic mědi s polymerní ochrannou vrstvou |
| CN104475751A (zh) * | 2014-12-05 | 2015-04-01 | 山东理工大学 | 一种制备两亲性纳米银粒子的新方法 |
| CN105732918A (zh) * | 2014-12-12 | 2016-07-06 | 中国石油天然气股份有限公司 | 一种有机硅改性的丙烯酸酯/银纳米复合材料及其制备方法 |
| CN105798320B (zh) * | 2014-12-31 | 2018-05-04 | 中国科学院化学研究所 | 一种低温制备纳米铜粉的方法 |
| CN104624204B (zh) * | 2015-02-06 | 2017-02-01 | 中国科学院上海高等研究院 | 用于co选择性加氢的催化剂及其制法和应用 |
| CN104841932A (zh) * | 2015-06-04 | 2015-08-19 | 山东理工大学 | 制备核壳型聚苯乙烯包覆纳米银复合粒子的新方法 |
| CN105056997B (zh) * | 2015-08-20 | 2017-08-11 | 郑州大学 | 一种对苯二甲酸选择性加氢制1,4‑环己烷二甲酸用催化剂及其制备方法、使用方法 |
| CN105080603B (zh) * | 2015-08-20 | 2017-05-17 | 郑州大学 | 一种硝基苯选择性加氢制苯胺用催化剂及其制备方法、使用方法 |
| CN105056996B (zh) * | 2015-08-20 | 2017-05-17 | 郑州大学 | 对苯二甲酸二甲酯选择性加氢制1,4‑环己烷二甲酸二甲酯用催化剂及其制备方法、使用方法 |
| CN105149609A (zh) * | 2015-09-07 | 2015-12-16 | 昆明仁旺科技有限公司 | 一种制备贵金属粉体的方法 |
| CN105127413B (zh) * | 2015-09-18 | 2017-07-21 | 温州大学 | 贵金属纳米环及其制备方法 |
| CN105153401B (zh) * | 2015-10-13 | 2017-11-17 | 厦门大学 | 荧光金纳米团簇及其水性聚氨酯模板法制备方法 |
| DE102015221529A1 (de) | 2015-11-03 | 2017-05-04 | Cht R. Beitlich Gmbh | Kontinuierliches Verfahren für Reaktionen mit feinteiligen Alkalimetall-Dispersionen |
| CN106807952B (zh) * | 2015-12-01 | 2019-05-07 | 中国科学院大连化学物理研究所 | 一种合成Au25纳米球的方法及Au25纳米球 |
| US11162161B2 (en) * | 2015-12-21 | 2021-11-02 | Sandvik Intellectual Property Ab | Cutting tool |
| CL2015003794A1 (es) * | 2015-12-30 | 2016-07-29 | Univ Chile | Método de obtención de nano partículas de cobre y uso de dichas partículas |
| CN109070208B (zh) * | 2016-04-22 | 2020-09-25 | Dic株式会社 | 金属纳米粒子水分散液 |
| CN105834450B (zh) * | 2016-05-13 | 2019-03-19 | 浙江光达电子科技有限公司 | 银粉的制备方法 |
| CN107520459A (zh) * | 2016-06-21 | 2017-12-29 | 张家港市山牧新材料技术开发有限公司 | 铜纳米颗粒的制备方法和抗菌塑料 |
| CN109844043A (zh) * | 2016-09-30 | 2019-06-04 | 南洋理工大学 | 油墨组合物、形成导电元件的方法及导电设备 |
| JP6849374B2 (ja) * | 2016-10-06 | 2021-03-24 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | 接合用の導電性ペースト |
| US9975110B1 (en) | 2016-11-23 | 2018-05-22 | Honda Motor Co., Ltd. | Method for producing metal catalyst nanoparticles |
| KR101874623B1 (ko) * | 2016-11-29 | 2018-08-02 | 주식회사 나노뉴텍 | 우수한 항균 효과를 갖는 고급 함침재 및 이를 구비한 화장품 |
| CN108161020A (zh) * | 2016-12-13 | 2018-06-15 | 中国科学院光电技术研究所 | 一种金纳米八面体的制备方法 |
| JP7132695B2 (ja) | 2016-12-20 | 2022-09-07 | Ｔｏｍａｔｅｃ株式会社 | 金属微粒子、金属微粒子含有分散液及びその製造方法 |
| CN106984804A (zh) * | 2017-05-10 | 2017-07-28 | 哈尔滨工程大学 | 一种纳米铝粉包覆方法 |
| WO2019049172A1 (en) * | 2017-09-06 | 2019-03-14 | Council Of Scientific And Industrial Research | CONTINUOUS FLOW PRODUCTION OF METALLIC NANOWELS |
| KR102067819B1 (ko) * | 2017-10-31 | 2020-02-11 | 영남대학교 산학협력단 | 나노 구조체의 안정화 방법 |
| CN108284232B (zh) * | 2018-01-26 | 2021-07-20 | 上海应用技术大学 | 一种银纳米粒子的制备方法 |
| EP3656825B1 (en) | 2018-11-22 | 2021-04-28 | Société BIC | Process for preparing aqueous gel inks with variable color, and aqueous gel inks thereof |
| CN109746457A (zh) * | 2018-11-28 | 2019-05-14 | 石河子大学 | 一种纳米金的制备方法 |
| CN109848438B (zh) * | 2019-03-25 | 2022-02-25 | 珠海纳金科技有限公司 | 一种双模粒径纳米银颗粒及其制备方法 |
| US11820905B2 (en) | 2019-08-29 | 2023-11-21 | Societe Bic | Process of preparation of an aqueous gel ink with fixed color comprising gold nanoparticles |
| CN110480004B (zh) * | 2019-08-29 | 2021-11-09 | 南京理工大学 | 水热法制备碳包覆纳米铝粉的方法 |
| KR20220053593A (ko) | 2019-08-29 | 2022-04-29 | 소시에떼 빅 | 은 또는 금 나노입자를 포함하는 고정 색을 갖는 수성 겔 잉크의 제조 방법 |
| CN114450357B (zh) * | 2019-08-29 | 2023-09-19 | 法国比克公司 | 制备包括银纳米颗粒的具有可变颜色的水性凝胶油墨的方法 |
| CN111592788B (zh) * | 2020-05-29 | 2022-09-16 | 合肥福纳科技有限公司 | 量子点发光二极管、量子点墨水及其制作方法 |
| CN111975011B (zh) * | 2020-07-20 | 2022-01-18 | 华南理工大学 | 一种芯片无压烧结互连用纳米铜浆及其制备方法与应用 |
| CN114316666A (zh) * | 2022-01-06 | 2022-04-12 | 渭南市瑞梦印务有限责任公司 | 一种专色油墨配方及其加工工艺 |
| CN114833334B (zh) * | 2022-04-02 | 2023-08-15 | 有研工程技术研究院有限公司 | 可连续制备微米级球形金粉的方法 |
| DE102023101927A1 (de) * | 2023-01-26 | 2024-08-01 | Karlsruher Institut für Technologie, Körperschaft des öffentlichen Rechts | Verfahren zur kontinuierlichen Cluster- und Nanopartikelsynthese |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006072959A1 (en) * | 2005-01-10 | 2006-07-13 | Yissum Research Development Company Of The Hebrew University Of Jerusalem | Aqueous-based dispersions of metal nanoparticles |
| US20070190323A1 (en) * | 2006-02-15 | 2007-08-16 | Samsung Electro-Mechanics Co., Ltd. | Method of producing metal nanoparticles |
| US20070207335A1 (en) * | 2004-07-30 | 2007-09-06 | Karandikar Bhalchandra M | Methods and compositions for metal nanoparticle treated surfaces |
Family Cites Families (47)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3465599D1 (en) | 1984-01-27 | 1987-10-01 | Byk Chemie Gmbh | Addition compounds suited as dispersing agents, process for their preparation, their use and solid materials coated with them |
| DE3641581C3 (de) | 1986-12-05 | 1996-08-01 | Byk Chemie Gmbh | Verfahren zur Herstellung von Dispergiermitteln und deren Salzen und ihre Verwendung |
| US4942213A (en) | 1987-12-04 | 1990-07-17 | Byk-Chemie Gmbh | Addition compounds useful as dispersing agents and dispersion stabilizers, process for producing them, their use and solids coated therewith |
| DE3930687A1 (de) | 1989-09-14 | 1991-04-11 | Byk Chemie Gmbh | Phosphorsaeureester, verfahren zu deren herstellung und deren verwendung als dispergiermittel |
| DE19721728C2 (de) | 1997-05-24 | 2001-07-12 | Byk Chemie Gmbh | Dispergiermittel für Pigmente oder Füllstoffe auf der Basis von Acrylsäurealkylester-Polymeren, Verwendung und Verfahren zur Herstellung |
| JP3594803B2 (ja) * | 1997-07-17 | 2004-12-02 | 日本ペイント株式会社 | 貴金属又は銅のコロイド溶液及びその製造方法並びに塗料組成物及び樹脂成型物 |
| DE19732251B4 (de) | 1997-07-26 | 2004-07-29 | Byk-Chemie Gmbh | Versalzungsprodukte von Polyaminen und deren Einsatz als Dispergiermittel für Pigmente und Füllstoffe |
| DE19745904A1 (de) * | 1997-10-17 | 1999-04-22 | Hoechst Ag | Polymerstabilisierte Metallkolloid-Lösungen, Verfahren zu ihrer Herstellung und ihre Verwendung als Katalysatoren für Brennstoffzellen |
| JP3650582B2 (ja) * | 1998-11-30 | 2005-05-18 | ナノスフェアー インコーポレイテッド | ポリマー−ナノ粒子ハイブリッド粒子 |
| DE19941031A1 (de) | 1999-08-28 | 2001-03-01 | Byk Chemie Gmbh | Verzweigte, Imidazolgruppen enthaltende Polymere, sowie deren Herstellung und Verwendung |
| JP2002285207A (ja) * | 2001-03-23 | 2002-10-03 | Nippon Paint Co Ltd | 白金コロイド水溶液、その製造方法及び白金の担持方法 |
| WO2002087749A1 (en) | 2001-04-30 | 2002-11-07 | Postech Foundation | Colloid solution of metal nanoparticles, metal-polymer nanocomposites and methods for preparation thereof |
| JP4094277B2 (ja) * | 2001-11-09 | 2008-06-04 | 独立行政法人科学技術振興機構 | シェル架橋型ミセルを鋳型とする金属ナノ粒子の調製 |
| US7138468B2 (en) | 2002-03-27 | 2006-11-21 | University Of Southern Mississippi | Preparation of transition metal nanoparticles and surfaces modified with (CO)polymers synthesized by RAFT |
| JP2004033901A (ja) * | 2002-07-03 | 2004-02-05 | Nippon Paint Co Ltd | 金属コロイド溶液の製造方法 |
| DE10236133A1 (de) | 2002-08-07 | 2004-02-26 | Byk-Chemie Gmbh | Verwendung von Gradientencopolymeren als Dispergiermittel zur Behandlung von Pigmenten und Feststoffen |
| JP4448962B2 (ja) * | 2003-01-14 | 2010-04-14 | Ｄｏｗａエレクトロニクス株式会社 | ニッケル被覆微粒子銅粉の製法 |
| WO2004081111A1 (en) * | 2003-03-11 | 2004-09-23 | Dow Global Technologies Inc. | High dielectric constant composites |
| US6992039B2 (en) | 2003-03-13 | 2006-01-31 | General Motors Corporation | Method for making monodispersed noble metal nanoparticles supported on oxide substrates |
| DE10326147A1 (de) | 2003-06-06 | 2005-03-03 | Byk-Chemie Gmbh | Epoxid-Addukte und deren Salze als Dispergiermittel |
| US20060266157A1 (en) | 2003-09-05 | 2006-11-30 | Dai Nippon Toryo Co., Ltd. | Metal fine particles, composition containing the same, and production method for producing metal fine particles |
| JP4973186B2 (ja) | 2004-03-10 | 2012-07-11 | 旭硝子株式会社 | 金属含有微粒子、金属含有微粒子分散液および導電性金属含有材料 |
| DE102004016479B4 (de) | 2004-03-31 | 2007-03-15 | Byk-Chemie Gmbh | Verwendung von Polyestern als Dispergiermittel und Polyester enthaltende Masterbatches |
| DE102004022753B3 (de) | 2004-05-07 | 2006-02-16 | Byk-Chemie Gmbh | Als Dispergiermittel und Dispersionsstabilisatoren geeignete Additionsverbindungen |
| US7718094B2 (en) * | 2004-06-18 | 2010-05-18 | The Research Foundation Of State University Of New York | Preparation of metallic nanoparticles |
| GB2416316A (en) | 2004-07-20 | 2006-01-25 | Protensive Ltd | Spinning disc reactor with spiral passageway for heat transfer fluid |
| GB2417215B (en) | 2004-08-18 | 2009-06-10 | Protensive Ltd | Spinning disc reactor with enhanced spreader plate features |
| DE102004044879A1 (de) | 2004-09-14 | 2006-03-30 | Byk-Chemie Gmbh | Copolymerisate, deren Herstellung und Verwendung als Netz- und Dispergiermittel |
| GB2419100A (en) | 2004-10-15 | 2006-04-19 | Protensive Ltd | Spinning disc reactor with cross-flow filtration or solvation |
| DE102004050955A1 (de) | 2004-10-20 | 2006-04-27 | Byk-Chemie Gmbh | Alkoxylierte Epoxyd-Amin-Addukte und deren Verwendung |
| US20060090597A1 (en) | 2004-10-29 | 2006-05-04 | Goia Dan V | Polyol-based method for producing ultra-fine metal powders |
| WO2006050251A2 (en) * | 2004-10-29 | 2006-05-11 | Nanodynamics, Inc. | Polyol-based method for producing ultra-fine metal powders |
| WO2006053225A2 (en) | 2004-11-12 | 2006-05-18 | Board Of Regents, The University Of Texas System | Protein-noble metal nanoparticles |
| US7749299B2 (en) | 2005-01-14 | 2010-07-06 | Cabot Corporation | Production of metal nanoparticles |
| US7824466B2 (en) * | 2005-01-14 | 2010-11-02 | Cabot Corporation | Production of metal nanoparticles |
| DE102005006870A1 (de) | 2005-02-14 | 2006-08-24 | Byk-Chemie Gmbh | Oberflächenmodifizierte Nanopartikel, Verfahren zu ihrer Herstellung und ihre Verwendung |
| JP2006252976A (ja) * | 2005-03-11 | 2006-09-21 | Nippon Paint Co Ltd | 金属ナノ粒子ペーストおよびその製造方法 |
| US7291292B2 (en) * | 2005-08-26 | 2007-11-06 | E.I. Du Pont De Nemours And Company | Preparation of silver particles using thermomorphic polymers |
| JP5252919B2 (ja) | 2005-09-16 | 2013-07-31 | 富士フイルム株式会社 | 感光性転写材料 |
| EP1952918B1 (en) * | 2005-10-14 | 2013-05-22 | Toyo Ink Mfg. Co., Ltd | Method for producing metal particle dispersion, conductive ink using metal particle dispersion produced by such method, and conductive coating film |
| JP2007301461A (ja) * | 2006-05-10 | 2007-11-22 | Nippon Paint Co Ltd | 金属コロイド溶液の製造方法及び金属コロイド溶液 |
| KR100790948B1 (ko) * | 2006-05-25 | 2008-01-03 | 삼성전기주식회사 | 금속 나노입자의 제조방법 및 이에 의해 제조되는 금속나노입자 |
| TW200806408A (en) * | 2006-06-27 | 2008-02-01 | Ishihara Sangyo Kaisha | Nickel fine particles, method for preparing the same and fluid composition comprising the same |
| GB0621050D0 (en) * | 2006-10-23 | 2006-11-29 | Univ Strathclyde | Functionalised polymers for labelling metal surfaces |
| DE102006055218A1 (de) | 2006-11-21 | 2008-05-29 | Bayer Technology Services Gmbh | Kontinuierliches Verfahren zur Synthese von nanoskaligen metallhaltigen Nanopartikel und Nanopartikeldispersion |
| US20080272344A1 (en) * | 2007-03-23 | 2008-11-06 | Georgia Tech Research Corporation | Conductive polymer composites |
| JP5026303B2 (ja) * | 2007-03-30 | 2012-09-12 | Ｄｏｗａエレクトロニクス株式会社 | 銀粉の製造方法 |
-
2009
- 2009-03-28 DE DE102009015470A patent/DE102009015470A1/de not_active Withdrawn
- 2009-11-20 US US13/139,366 patent/US8870998B2/en not_active Expired - Fee Related
- 2009-11-20 CN CN2009801499743A patent/CN102245333B/zh not_active Expired - Fee Related
- 2009-11-20 WO PCT/EP2009/008289 patent/WO2010066335A1/de active Application Filing
- 2009-11-20 JP JP2011539917A patent/JP5833447B2/ja not_active Expired - Fee Related
- 2009-11-20 BR BRPI0923509A patent/BRPI0923509A2/pt not_active IP Right Cessation
- 2009-11-20 EP EP09760108A patent/EP2358489A1/de not_active Withdrawn
- 2009-11-20 KR KR1020117016016A patent/KR101278939B1/ko not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070207335A1 (en) * | 2004-07-30 | 2007-09-06 | Karandikar Bhalchandra M | Methods and compositions for metal nanoparticle treated surfaces |
| WO2006072959A1 (en) * | 2005-01-10 | 2006-07-13 | Yissum Research Development Company Of The Hebrew University Of Jerusalem | Aqueous-based dispersions of metal nanoparticles |
| US20070190323A1 (en) * | 2006-02-15 | 2007-08-16 | Samsung Electro-Mechanics Co., Ltd. | Method of producing metal nanoparticles |
Non-Patent Citations (1)
| Title |
|---|
| See also references of WO2010066335A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20110099731A (ko) | 2011-09-08 |
| KR101278939B1 (ko) | 2013-06-28 |
| DE102009015470A1 (de) | 2010-06-17 |
| US20120037041A1 (en) | 2012-02-16 |
| JP5833447B2 (ja) | 2015-12-16 |
| CN102245333A (zh) | 2011-11-16 |
| US8870998B2 (en) | 2014-10-28 |
| BRPI0923509A2 (pt) | 2019-09-24 |
| JP2012511627A (ja) | 2012-05-24 |
| WO2010066335A1 (de) | 2010-06-17 |
| CN102245333B (zh) | 2013-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2010066335A1 (de) | Verfahren zur herstellung von metallnanopartikeln und auf diese weise erhaltene metallnanopartikel und ihre verwendung | |
| KR100754326B1 (ko) | 금속 나노입자의 제조방법 | |
| US20070275259A1 (en) | Method of producing metal nanoparticles and metal nanoparticles produced thereby | |
| CN101357403B (zh) | 用于制造金属纳米颗粒的方法 | |
| CN101161380B (zh) | 用于制备铜纳米颗粒的方法 | |
| KR100716201B1 (ko) | 금속 나노 입자 및 이의 제조방법 | |
| DE112011103233T5 (de) | Feine, beschichtete Kupferpartikeln und Verfahren zur Herstellung derselben | |
| KR100790457B1 (ko) | 금속 나노입자의 제조방법 | |
| US20080207934A1 (en) | Method for producing metal nanoparticles and metal nanoparticles produced thereby | |
| DE102006017696A1 (de) | Verfahren zur Herstellung von Metallpartikeln, hieraus hergestellte Metallpartikel und deren Verwendung | |
| EP1133447B1 (de) | Wasserlösliche nanostrukturierte metalloxid-kolloide und verfahren zu ihrer herstellung | |
| JP2007031835A (ja) | 金属ナノ粒子およびその製造方法並びに導電性インク | |
| DE102010062093A1 (de) | Ultra niedrig schmelzende Metallnanopartikelzusammensetzung für Dickfilm-Anwendungen | |
| US20160121402A1 (en) | Method for preparing metal nanoparticles using a multi-functional polymer and a reducing agent | |
| WO2018206645A1 (de) | Verfahren und zusammensetzung zur herstellung von siliciumcarbidhaltigen dreidimensionalen objekten | |
| Kumar et al. | Phase transfer of platinum nanoparticles from aqueous to organic solutions using fatty amine molecules | |
| Orel et al. | Conversion of uniform colloidal Cu2O spheres to copper in polyols | |
| JP2011195951A (ja) | 金属ナノ粒子の製造方法、これを用いたインク組成物及びその製造方法 | |
| WO2015018897A1 (de) | Oberflächenmodifizierte metallkolloide und ihre herstellung | |
| DE102010034293B4 (de) | Verfahren zur Herstellung einer Dispersion von Nanopartikeln | |
| JP5210467B2 (ja) | 金属微粒子分散液の製造方法 | |
| DE102006013794A1 (de) | Verfahren zur Herstellung kolloidaler Nanokatalysatoren |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 20110526 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
| AX | Request for extension of the european patent |
Extension state: AL BA RS |
|
| 17Q | First examination report despatched |
Effective date: 20140321 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
| 18D | Application deemed to be withdrawn |
Effective date: 20170601 |