CN114574847A - Novel graphene film-forming agent and preparation method and application thereof - Google Patents
Novel graphene film-forming agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN114574847A CN114574847A CN202210355039.XA CN202210355039A CN114574847A CN 114574847 A CN114574847 A CN 114574847A CN 202210355039 A CN202210355039 A CN 202210355039A CN 114574847 A CN114574847 A CN 114574847A
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- Prior art keywords
- agent
- film
- parts
- forming
- coupling agent
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 95
- 239000000080 wetting agent Substances 0.000 claims abstract description 52
- 239000007822 coupling agent Substances 0.000 claims abstract description 25
- 239000007800 oxidant agent Substances 0.000 claims abstract description 24
- 239000002738 chelating agent Substances 0.000 claims abstract description 23
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 63
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 54
- 239000002253 acid Substances 0.000 claims description 25
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 18
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 16
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 16
- 239000000467 phytic acid Substances 0.000 claims description 16
- 229940068041 phytic acid Drugs 0.000 claims description 16
- 235000002949 phytic acid Nutrition 0.000 claims description 16
- -1 rare earth salt Chemical class 0.000 claims description 15
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 14
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 12
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 239000000419 plant extract Substances 0.000 claims description 10
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 10
- 239000004299 sodium benzoate Substances 0.000 claims description 10
- 235000010234 sodium benzoate Nutrition 0.000 claims description 10
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 9
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 9
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 8
- 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 claims description 8
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 7
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 7
- 229910003472 fullerene Inorganic materials 0.000 claims description 7
- 239000004323 potassium nitrate Substances 0.000 claims description 7
- 235000010333 potassium nitrate Nutrition 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 239000000176 sodium gluconate Substances 0.000 claims description 7
- 235000012207 sodium gluconate Nutrition 0.000 claims description 7
- 229940005574 sodium gluconate Drugs 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 5
- 229960005336 magnesium citrate Drugs 0.000 claims description 5
- 239000004337 magnesium citrate Substances 0.000 claims description 5
- 235000002538 magnesium citrate Nutrition 0.000 claims description 5
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 31
- 239000002184 metal Substances 0.000 abstract description 31
- 238000005260 corrosion Methods 0.000 abstract description 21
- 230000007797 corrosion Effects 0.000 abstract description 20
- 239000002699 waste material Substances 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract description 7
- 229910000831 Steel Inorganic materials 0.000 abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010959 steel Substances 0.000 abstract description 6
- 229910052725 zinc Inorganic materials 0.000 abstract description 6
- 239000011701 zinc Substances 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000006386 neutralization reaction Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 47
- 239000002904 solvent Substances 0.000 description 38
- 230000002140 halogenating effect Effects 0.000 description 34
- 238000003756 stirring Methods 0.000 description 29
- 238000000034 method Methods 0.000 description 26
- 239000006185 dispersion Substances 0.000 description 25
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 24
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 22
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 22
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 20
- 229910000077 silane Inorganic materials 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 16
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 14
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 10
- 229910052721 tungsten Inorganic materials 0.000 description 10
- 239000010937 tungsten Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 238000004017 vitrification Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 4
- 235000001014 amino acid Nutrition 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 4
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 4
- 239000001630 malic acid Substances 0.000 description 4
- 235000011090 malic acid Nutrition 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- BJZIJOLEWHWTJO-UHFFFAOYSA-H dipotassium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Zr+4] BJZIJOLEWHWTJO-UHFFFAOYSA-H 0.000 description 3
- 239000003814 drug Substances 0.000 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 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000005254 chromizing Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- WFSPUOYRSOLZIS-UHFFFAOYSA-N silane zirconium Chemical compound [SiH4].[Zr] WFSPUOYRSOLZIS-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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Abstract
The invention relates to a novel graphene film-forming agent, a preparation method and application thereof, wherein the novel graphene film-forming agent comprises the following components in parts by mass: chelating agent: 1-10 parts of film forming agent: 1-450 parts of oxidant: 1-5 parts of film-forming assistant: 1-10 parts of wetting agent: 1-10 parts of coupling agent: 1-10 parts. The corrosion resistance and the adhesive force of the film layer can be enhanced by adding the coupling agent; the special film-forming assistant is added to enable the modified graphene oxide film to be a novel environment-friendly product with high performance and low energy consumption based on the modified graphene oxide, and after the special film-forming assistant is added, a heterozygous and insoluble microcrystalline reticular film can be generated on the surfaces of metal workpieces such as steel, zinc plates, aluminum materials and the like, so that the modified graphene oxide film has excellent corrosion resistance and impact resistance; the waste liquid of the waste liquid is discharged after simple neutralization treatment, so that the cost of waste liquid treatment is saved, and the waste liquid meets the requirement of environmental protection.
Description
Technical Field
The invention relates to the field of new material synthesis and surface treatment, in particular to a novel graphene film-forming agent, and a preparation method and application thereof.
Background
In recent years, new phosphorus-free metal surface treating agents such as zirconium-based, zirconium-titanium-based, silane-based and zirconium-silane-based metal surface treating agents quickly occupy the market, but the performances of the phosphorus-free conversion films are only equivalent to those of the traditional phosphating films, and the phosphorus-free conversion films are not superior, so that the phosphorus-free conversion films cannot meet the coating requirements of high-corrosion-resistance industries such as ships. Meanwhile, with the continuous promotion of the concept of energy conservation, environmental protection and emission reduction, the traditional phosphating process continuously exits the market. Later, some surface treatment methods for the surface of the metal workpiece by adopting a ceramic solvent/ceramic process and a silane solvent/silane process appear in the market, but the surface treatment methods for the metal workpiece by adopting a phosphorization solvent/process, a ceramic solvent/process or a silane solvent/process have the defects of poor corrosion resistance of a bare film, short normal state rust prevention time, poor film coating effect, small treatment area of a medicament and the like, and the performances of the aspects are still to be greatly improved.
The graphene coating agent can form a conversion coating through vitrification treatment before painting on metal workpieces such as steel and the like, and can be used as a coating bottom layer to enhance the adhesive force and the protective property of the coating and a matrix and improve the coating quality of the steel workpiece, so that the graphene coating agent can be widely applied as a metal surface treating agent. Some solutions prepared based on graphene exist in the market, such as Chinese invention patents with publication number of "CN 108834309A" and patent name of "graphene metallization solution and preparation method and application thereof", wherein although the components of the solution contain graphene or graphene oxide and a film-forming agent, the graphene is also used as a base material, the graphene metallization solution prepared by the formula of the graphene forms a graphene film, and the graphene film cannot form a passivation film; the film forming agent is a polymer, and the film forming effect is relatively common, so that the overall corrosion resistance of the film forming agent is still required to be greatly improved. Meanwhile, the method is used for treating the non-metal surface, and the metal workpieces such as steel cannot be treated.
In addition, the bath solution of the film forming agent, the ceramic solvent or the silane solvent in the current market after processing the workpiece generally contains elements such as phosphorus, zinc, calcium, nickel, manganese, chromium and the like, and carcinogens such as nitrate and the like, so that the direct discharge of the bath solution can pollute the environment, and the discharge cost of enterprises is high because the wastes are required to be specially processed. When the metal workpiece is treated by adopting the existing ceramic process and silane process on the market, the rust on the peracid workpiece cannot be removed, and the bath solution is easy to generate sediment, so that the requirements of coating and environment-friendly production in high-corrosion-resistant industries such as ships cannot be met.
Disclosure of Invention
The invention aims to solve the technical problems that a novel graphene film-forming agent, a preparation method and an application thereof are provided, and the novel graphene film-forming agent effectively solves the problems that when the surface of a metal workpiece is subjected to surface treatment by adopting the existing vitrification agent/vitrification process and silane agent/silane process, a bare film is poor in corrosion resistance, the normal state rust-proof time is short, the film coating effect is poor, the medicament treatment area is small, the environment is not protected, the waste discharge cost is high, the bath solution is poor in stability, the bath solution is easy to generate sediment, the rust floating of the peracid workpiece cannot be removed, and the like. The invention is realized by the following technical scheme:
a novel graphene film-forming agent comprises the following components in parts by mass:
chelating agent: 1-10 parts;
film-forming agent: 1-450 parts;
oxidizing agent: 1-5 parts;
film-forming auxiliary agent: 1-10 parts;
wetting agent: 1-10 parts;
coupling agent: 1-10 parts.
The preparation method of the novel graphene film-forming agent comprises the following steps:
step (1): adding a chelating agent into water for dissolving, and stirring the chelating agent until the chelating agent is completely dissolved; the weight of the water accounts for 50-60% of the weight of the novel graphene film forming agent.
Step (2): adding the film forming agent and the film forming auxiliary agent, and stirring the film forming agent and the film forming auxiliary agent until the film forming agent and the film forming auxiliary agent are completely dissolved.
And (3): adding a coupling agent, and stirring the coupling agent until the coupling agent is completely dissolved; and maintaining the pH of the solution at a value between 3.5 and 5.
And (4): adding the wetting agent, and stirring the wetting agent until the wetting agent is completely dissolved.
And (5): and when the temperature of the solution is reduced to below 40 ℃, carrying out ultrasonic oscillation on the solution by using an ultrasonic oscillator.
And (6): and adding an oxidant after the ultrasonic oscillation machine completes the ultrasonic oscillation until the oxidant is stirred to be completely dissolved, so as to prepare the novel graphene film-forming agent.
The novel graphene film-forming agent prepared by the components and the preparation method does not contain elements such as phosphorus, zinc, calcium, nickel, manganese, chromium and the like and carcinogenic substances such as nitrate and the like, waste liquid generated after metal workpieces are treated by the novel graphene film-forming agent can be discharged after simple neutralization treatment, the novel graphene film-forming agent is very environment-friendly to use, and in addition, the metal workpieces treated by the novel graphene film-forming agent have excellent corrosion resistance and impact resistance, and the adhesive force between the formed film layer and the metal workpieces can be remarkably improved.
In the step (5), the time of ultrasonic oscillation is 1-20 minutes. Preferably, the time of ultrasonic vibration is 1 to 10 minutes.
Preferably, the chelating agent comprises one or more of sodium benzoate, EDTA-4Na, sodium gluconate, sodium citrate, etc.
When the technical scheme is adopted, when the chelating agent comprises more than two of sodium benzoate, EDTA-4Na, sodium gluconate and sodium citrate, the contained components are equal in amount, but the technical scheme is not limited by the content.
Preferably, the film forming agent includes one or a mixture of two or more of fluorozirconic acid, fluorotitanic acid, potassium fluorozirconate, fluoroboric acid, and phytic acid.
When the above technical solution is adopted, when the film forming agent includes any two or more of fluozirconic acid, fluotitanic acid, potassium fluozirconate, fluoboric acid, and phytic acid, the contained components are equal in amount, but not limited thereto.
Preferably, the oxidizing agent includes one or a mixture of two or more of zirconium nitrate, copper nitrate, potassium nitrate, titanium nitrate, ammonium molybdate, potassium permanganate, and the like.
The oxidizing agent can promote metal and oxidizing substances to generate passivation effect and firmly adsorb on the surface of a metal workpiece to form a very thin and compact passivation film with good covering performance, the film is independent and is a metal oxide compound, and the film can completely separate metal from a corrosion medium to prevent the metal from contacting with the corrosion medium, so that the metal basically stops dissolving to form a passive state, and the corrosion prevention effect is achieved.
When the above technical solution is adopted, when the oxidizing agent includes any two or more of zirconium nitrate, copper nitrate, potassium nitrate, titanium nitrate, ammonium molybdate, potassium permanganate, and the like, the contained components are equal in amount, but not limited thereto.
Preferably, the film forming aid comprises one or more of modified graphene oxide, fullerene, nano rare earth salt, magnesium citrate, hydroxycarboxylic acid, plant extract and the like.
When the above technical scheme is adopted, when the film-forming aid includes any two or more of modified graphene oxide, fullerene, nano rare earth salt, magnesium citrate, hydroxycarboxylic acid, plant extract, and the like, the contained components are equal in amount, but not limited thereto.
Wherein the nano rare earth salt comprises one or more of cerium chloride, cerium nitrate, cerium sulfate and cerium fluoride; the plant extract comprises one or more of resin, amino acid, phytic acid and malic acid.
Wherein, when the nano rare earth salt comprises any two or more of cerium chloride, cerium nitrate, cerium sulfate and cerium fluoride, the contained components are equal, but not limited. When the plant extract includes any two or more of resin, amino acid, phytic acid, malic acid, etc., the contained components are equal in amount, but not limited thereto.
Preferably, the preparation method of the modified graphene oxide comprises the following steps: the method comprises the following steps: weighing 5-20g of graphene oxide and a dispersion solvent, and uniformly stirring.
Step two: adding 1000g-1500g of acetone solution and 500g-1000g of deionized water into the uniformly stirred graphene oxide and the dispersing solvent, and then dispersing and mixing the mixture by using an ultrasonic disperser to obtain a graphene dispersing solution; wherein the processing time of the ultrasonic dispersion instrument is 60-120 min, and the frequency of the ultrasonic wave is set to be 20-25 HZ.
Step three: respectively weighing a tungsten-containing precursor mixture obtained by mixing 90% by mass of ammonium metatungstate and 10% by mass of tungsten carbonyl, then adding 2g-30g of the tungsten-containing precursor mixture into the graphene dispersion solution, uniformly stirring, and continuously dripping a halogenating reagent in the stirring process, wherein the stirring time is as follows: 60-90 min; and after stirring, carrying out suction filtration on the obtained precipitate.
Step four: throwing the graphene dispersion solution with the precipitate filtered into an oven for drying to prepare dry powder, wherein the heating temperature of the oven is set as follows: 100-120 ℃, and the drying time is as follows: 240- > 300 min.
Step five: and placing the obtained dry powder in an alumina crucible, heating to the temperature of 700-900 ℃, preserving heat for a period of time, wherein the preserving heat time is 1-3h, then introducing nitrogen into the alumina crucible, and cooling to room temperature to obtain the modified graphene oxide powder.
In the first step, the addition amount of the dispersion solvent is 10g to 30g, and the dispersion solvent is one or a mixture of two or more selected from dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran and the like. When the dispersion solvent includes a mixture of two or more of dimethylsulfoxide, N-dimethylformamide, N-methylpyrrolidone and tetrahydrofuran, the amount of the components contained is equivalent, but not limited thereto.
The amount of the dispersion solvent added is preferably 30 g.
In the first step, the weight of the acetone solution is preferably 1200g, and the weight of the deionized water is preferably 800 g.
In the third step, the dropping amount of the halogenating agent is 80g-300g, and the halogenating agent is one or more than two of thionyl chloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride and oxalyl chloride. When the halogenating agent is selected from any two of thionyl chloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, oxalyl chloride and the like to be mixed, the weight ratio of the firstly measured/weighed components to the secondly measured/weighed components is 1: 2. For example, when the halogenating agent is selected from the group consisting of thionyl chloride and phosphorus tribromide, the weight ratio of thionyl chloride to phosphorus tribromide is 1: 2; when the halogenating agent is selected from the mixture of phosphorus pentachloride and phosphorus oxychloride, the weight ratio of the phosphorus pentachloride to the phosphorus oxychloride is 1: 2; when the halogenating agent is selected from the mixture of sulfoxide chloride and oxalyl chloride, the weight ratio of sulfoxide chloride to oxalyl chloride is 1: 2, and so on.
When the halogenating agent comprises any three of thionyl chloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride and oxalyl chloride, and the like, the weight ratio of the first measured/weighed component to the second measured/weighed component to the last measured/weighed component is 1: 0.5: 2. For example, when the halogenating agent is selected from the group consisting of sulfoxide chloride, phosphorus tribromide and phosphorus pentachloride, the weight ratio of sulfoxide chloride, phosphorus tribromide and phosphorus pentachloride is 1: 0.5: 2; when the halogenating agent is selected from the mixture of phosphorus pentachloride, phosphorus oxychloride and oxalyl chloride, the weight ratio of the phosphorus pentachloride, the phosphorus oxychloride and the oxalyl chloride is 1: 0.5: 2; when the halogenating agent is selected from the group consisting of phosphorus tribromide, phosphorus pentachloride and phosphorus oxychloride, the weight ratio of phosphorus tribromide, phosphorus pentachloride and phosphorus oxychloride is 1: 0.5: 2, and so on.
In the third step, the tungsten carbonyl can be, but is not limited to, tungsten hexacarbonyl. The continuous dropping of the halogenating agent refers to the uniform dropping of the halogenating agent with a certain time as a gap, and the certain time (t) may be 1 second, 2 seconds, 3 seconds, 4 seconds, 5 seconds … …, or 1 minute, 2 minutes, 3 minutes … …, which is not limited thereto.
As the dropping amount, the dropping amount of the halogenating agent is preferably 220 g.
Preferably, the wetting agent comprises one or more of K12 wetting agent, K14 wetting agent, wetting agent 0S-406, BYK-9076 wetting agent, DC-67 wetting agent, dimethyl polysiloxane and the like.
Wherein, the wetting agent is used for improving the surface tension of the metal, promoting the penetration and uniform distribution of ions on the surface of the metal and being beneficial to the adsorption and oxidation film formation.
When the technical scheme is adopted, when the wetting agent comprises any two or more of a K12 wetting agent, a K14 wetting agent, a wetting agent 0S-406, a BYK-9076 wetting agent, a DC-67 wetting agent and dimethyl polysiloxane, the contained components are equal in amount, but the invention is not limited to the components.
Preferably, the coupling agent includes one or a mixture of two or more of a silane coupling agent KH550, a silane coupling agent KH560, a silane coupling agent KH570, a silane coupling agent KH792, a silane coupling agent DL602, a silane coupling agent DL171, and the like.
Wherein, the coupling agent (mainly referring to silane coupling agent) takes organosilane aqueous solution as main component, and a layer of ultrathin silane organic film is generated in the process of surface treatment of metal or nonmetal materials, and the silane organic film has excellent corrosion resistance and excellent adhesive force to paint.
In the case of adopting the above-mentioned technical means, when the coupling agent includes any two or more of the silane coupling agent KH550, the silane coupling agent KH560, the KH570, the KH792, the DL602, and the silane coupling agent DL171, the amounts of the components contained are equal, but not limited thereto.
In another embodiment, the invention also provides an application principle of the novel graphene film forming agent: the chelating agent, the film forming agent, the oxidant, the film forming assistant, the wetting agent and the coupling agent are compounded, and the chelating agent and the coupling agent are added to form a silane film on the surface of a metal workpiece by utilizing the complexing action of the chelating agent and the adsorption action of the silane coupling agent; the addition of the oxidant can promote the metal workpiece to be firmly adsorbed on the surface of the metal workpiece to form a passivation film when the passivation reaction of the metal workpiece and the oxidizing substance is carried out; the modified graphene film is a heterozygous and insoluble microcrystalline reticular film, namely, the modified graphene film can be formed on the surface of a metal workpiece, namely, the modified graphene film can be formed on the surface of the metal workpiece, namely, the silane film, a passivation film and the modified graphene film, so that the treated metal workpiece has excellent corrosion resistance and impact resistance, and the adhesion force of the coating can be remarkably improved.
Compared with the existing graphene film-forming agent, the graphene film-forming agent has the beneficial effects that: 1. the corrosion resistance and the adhesive force of the film layer can be enhanced by adding the coupling agent; the special film-forming assistant is added, so that the modified graphene oxide film becomes a novel environment-friendly product with high performance and low energy consumption based on the modified graphene oxide, a heterozygous and insoluble microcrystalline reticular film can be generated on the surfaces of metal workpieces such as steel, zinc plates, aluminum materials and the like through chemical treatment after the special film-forming assistant is added, heating is not needed in the generation process of the film, no sediment is generated in bath solution, the corrosion resistance of the film can be further improved, and the filling property of gaps of the film is better; in addition, the modified graphene oxide has the strongest electrical conductivity, so that the modified graphene oxide can better adsorb powder coating when being applied to the electrostatic powder spraying process, the adhesion of the coating can be obviously improved, and the coating has excellent corrosion resistance and impact resistance; in addition, the graphene film-forming agent does not contain elements such as phosphorus, zinc, calcium, nickel, manganese, chromium and the like, and also does not contain carcinogens such as nitrate and the like, the waste liquid of the graphene film-forming agent can be discharged after simple neutralization treatment, the cost for treating the waste liquid is saved, and the use and production of the graphene film-forming agent meet the requirement of environmental protection.
2. The novel graphene film forming agent is stable in performance, accords with ROHS certification, is green and environment-friendly, is strong in salt spray corrosion resistance, is an ideal substitute of traditional phosphating solution, silane vitrification agent, chromizing solution and passivating solution, can form a compact and uniform conversion film or adsorption film on the surfaces of metal materials such as steel, stainless steel 202, stainless steel 304, zinc, aluminum, magnesium, copper, galvanized parts and the like, can remove rust returning and rust coating of acid workpieces, cannot remove rust by using the vitrification agent and the silane agent on the market, does not contain any total phosphorus, slag, rust-proof nitrite, zirconium, rust, molybdenum, mercury and heavy metal, is stable in solution, can be recycled, and further realizes the environment-friendly index of zero discharge of wastewater.
3. The chelating agent, the film forming agent, the oxidant, the special film forming assistant, the wetting agent and the coupling agent are compounded, so that the copper sulfate drip test time of a naked film formed on the surface of a metal workpiece by the prepared graphene film forming agent can be as high as 60s at most, the soaking time of the naked film in a 3.5% NaCl solution can be as long as 60min at most, the neutral salt spray time test of the naked film can be prolonged to about 90min, the normal penetration removal time can be prolonged to about 6 months, the coating cross salt spray time can be as high as 700h at most, the impact resistance test can be more than 50KG, and the unit medicament treatment area can be enlarged to 200-300m2KG, whichAll the performances are obviously improved.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1:
the embodiment discloses a novel graphene film-forming agent, which comprises the following components in parts by mass:
chelating agent: 10 parts of a binder;
film-forming agent: 450 parts of a mixture;
oxidizing agent: 5 parts of a mixture;
film-forming auxiliary agent: 10 parts of (A);
wetting agent: 10 parts of (A);
coupling agent: 10 parts.
The chelating agent is a mixture of sodium benzoate, EDTA-4Na, sodium gluconate and sodium citrate, and the weight ratio of the sodium benzoate, the EDTA-4Na, the sodium gluconate and the sodium citrate is 1: 1.
Wherein the film forming agent comprises the mixture of fluozirconic acid, fluotitanic acid, potassium fluozirconate, fluoboric acid and phytic acid, and the weight ratio of the fluozirconic acid to the fluotitanic acid to the potassium fluozirconate to the fluoboric acid to the phytic acid is 1: 1.
Wherein the oxidant comprises the mixture of zirconium nitrate, cupric nitrate, potassium nitrate, titanium nitrate, ammonium molybdate and potassium permanganate, and the weight ratio of the zirconium nitrate, the cupric nitrate, the potassium nitrate, the titanium nitrate, the ammonium molybdate and the potassium permanganate is 1: 1.
The film-forming auxiliary agent is modified graphene oxide.
Wherein the wetting agent is dimethyl polysiloxane.
Wherein the coupling agent comprises a silane coupling agent KH550, a silane coupling agent KH560, a KH570 silane coupling agent, a KH792 silane coupling agent, a mixture of a DL602 silane coupling agent and a silane coupling agent DL171, and the weight ratio of the silane coupling agent KH550, the silane coupling agent KH560, the KH570 silane coupling agent, the KH792 silane coupling agent, the DL602 silane coupling agent and the silane coupling agent DL171 is 1: 1.
The preparation method of the modified graphene oxide comprises the following steps: the method comprises the following steps: weighing 10g of graphene oxide and a dispersing solvent, and uniformly stirring; the amount of the dispersion solvent added was 30g, the dispersion solvent comprised a mixture of dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and tetrahydrofuran, and the amounts of dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone and tetrahydrofuran added were 7.5g, respectively.
Step two: adding 1200g of acetone solution and 800g of deionized water into the uniformly stirred graphene oxide and the dispersing solvent, and then dispersing and mixing the mixture by using an ultrasonic disperser to obtain a graphene dispersing solution; wherein the processing time of the ultrasonic dispersion instrument is 68min, and the frequency of the ultrasonic wave is set to be 25 HZ;
step three: weighing a precursor mixture containing tungsten obtained by mixing 90% of ammonium metatungstate and 10% of tungsten carbonyl in percentage by mass respectively, then adding 30g of the precursor mixture containing tungsten into the graphene dispersion solution, uniformly stirring, continuously dropping a halogenating reagent into the stirring process, wherein the stirring time is as follows: 70 min; after stirring, carrying out suction filtration on the obtained precipitate; wherein the total dropping amount of the halogenating agent is 210 g; the continuous dropping of the halogenating reagent refers to the constant dropping of the halogenating reagent with a time interval of 3 min. The halogenating agent is selected from the mixture of thionyl chloride, phosphorus oxychloride and oxalyl chloride, and the weight ratio of the thionyl chloride, the phosphorus oxychloride and the oxalyl chloride is 1: 0.5: 2. Tungsten carbonyl can be used but is not limited to tungsten hexacarbonyl.
Step four: throwing the graphene dispersion solution with the precipitate filtered into an oven for drying to prepare dry powder, wherein the heating temperature of the oven is set as follows: and at 114 ℃, the drying time is as follows: the time of the air flow is 262min,
step five: and (3) placing the obtained dry powder in an alumina crucible, heating to 886 ℃, then preserving heat for a period of time, wherein the heat preservation time is 1.5h, then introducing nitrogen into the alumina crucible, and cooling to room temperature to obtain the modified graphene oxide powder.
Example 2:
the embodiment discloses a novel graphene film-forming agent, which comprises the following components in parts by mass:
chelating agent: 7 parts;
film-forming agent: 415 parts of a mixture;
oxidizing agent: 4 parts of a mixture;
film-forming auxiliary agent: 9 parts of (1);
wetting agent: 8 parts of a mixture;
coupling agent: 8 parts.
Wherein the chelating agent is sodium benzoate.
Wherein the film forming agent comprises potassium fluorozirconate, a mixture of fluoroboric acid and phytic acid, and the weight ratio of the potassium fluorozirconate to the fluoroboric acid to the phytic acid is 1: 1.
Wherein the oxidant comprises zirconium nitrate, copper nitrate, titanium nitrate and ammonium molybdate in a weight ratio of 1: 1.
The film-forming aid is a mixture of modified graphene oxide, fullerene, nano rare-earth salt, magnesium citrate, hydroxycarboxylic acid and a plant extract, and the weight ratio of the modified graphene oxide, the fullerene, the nano rare-earth salt, the magnesium citrate, the hydroxycarboxylic acid and the plant extract is 1: 1. The nano rare earth salt is a mixture of cerium chloride, cerium nitrate, cerium sulfate and cerium fluoride, and the weight ratio of the cerium chloride, the cerium nitrate, the cerium sulfate and the cerium fluoride is 1: 1. The plant extract is a mixture of resin, amino acid, phytic acid and malic acid, and the weight ratio of the resin, the amino acid, the phytic acid and the malic acid is 1: 1.
Wherein the wetting agent is a mixture of a K12 wetting agent, a K14 wetting agent, a wetting agent 0S-406, a BYK-9076 wetting agent, a DC-67 wetting agent and dimethyl polysiloxane, and the weight ratio of the K12 wetting agent, the K14 wetting agent, the wetting agent 0S-406, the BYK-9076 wetting agent, the DC-67 wetting agent and the dimethyl polysiloxane is 1: 1.
Wherein the coupling agent is a mixture of a silane coupling agent KH550, a silane coupling agent KH560 and a KH570 silane coupling agent, and the weight ratio of the silane coupling agent KH550 to the silane coupling agent KH560 to the KH570 silane coupling agent is 1: 1.
The preparation method of the modified graphene oxide comprises the following steps: the method comprises the following steps: weighing 20g of graphene oxide and a dispersing solvent, and uniformly stirring; the amount of the dispersion solvent added was 25g, the dispersion solvent comprised a mixture of dimethylsulfoxide, N-methylpyrrolidone and tetrahydrofuran, and the amounts of dimethylsulfoxide, N-methylpyrrolidone and tetrahydrofuran added were 8.33g, respectively.
Step two: 1180g of acetone solution and 870g of deionized water are added into the uniformly stirred graphene oxide and the dispersing solvent, and then an ultrasonic wave dispersing instrument is adopted to disperse and mix the acetone solution and the deionized water to obtain a graphene dispersing solution; wherein the treatment time of the ultrasonic disperser is 115min, and the frequency of the ultrasonic wave is set to 20 HZ.
Step three: weighing a precursor mixture containing tungsten obtained by mixing 90% of ammonium metatungstate and 10% of tungsten carbonyl in percentage by mass respectively, adding 25g of the precursor mixture containing tungsten into the graphene dispersion solution, uniformly stirring, continuously dropping a halogenating reagent into the stirring process, wherein the stirring time is as follows: 75 min; and after stirring, carrying out suction filtration on the obtained precipitate. Wherein the total dropping amount of the halogenating agent is 180g, and the continuously dropping of the halogenating agent means that the halogenating agent is dropped at a constant speed with a time interval of 2.4 min. The halogenating agent is selected from the group consisting of thionyl chloride, phosphorus tribromide and phosphorus pentachloride in a weight ratio of 1: 0.5: 2. Tungsten carbonyl can be used but is not limited to tungsten hexacarbonyl.
Step four: throwing the graphene dispersion solution with the precipitate filtered into an oven for drying to prepare dry powder, wherein the heating temperature of the oven is set as follows: and (3) drying at the temperature of 120 ℃ for: and 240 min.
Step five: and (3) placing the obtained dry powder in an alumina crucible, heating to 768 ℃, then preserving heat for a period of time, wherein the preserving heat time is 2 hours, then introducing nitrogen into the alumina crucible, and cooling to room temperature to obtain the modified graphene oxide powder.
Example 3:
the embodiment discloses a novel graphene film-forming agent, which comprises the following components in parts by mass:
chelating agent: 8 parts of a mixture;
film-forming agent: 332 parts of (a);
oxidizing agent: 3 parts of a mixture;
film-forming auxiliary agent: 8 parts;
wetting agent: 7 parts;
coupling agent: 9 parts of.
Wherein the chelating agent is a mixture of sodium benzoate and EDTA-4Na, and the weight ratio of the sodium benzoate to the EDTA-4Na is 1: 1.
Wherein the film forming agent comprises a mixture of fluozirconic acid and fluotitanic acid, and the weight ratio of the fluozirconic acid to the fluotitanic acid is 1: 1.
Wherein the oxidant comprises a mixture of potassium nitrate, potassium permanganate and titanium nitrate, and the weight ratio of the potassium nitrate to the potassium permanganate to the titanium nitrate is 1: 1.
The film-forming assistant is a mixture of modified graphene oxide, fullerene, nano rare-earth salt and a plant extract, and the weight ratio of the modified graphene oxide, the fullerene, the nano rare-earth salt and the plant is 1: 1. The nano rare earth salt is a mixture of cerium chloride and cerium fluoride, and the weight ratio of the cerium chloride to the cerium fluoride is 1: 1. The plant extract is a mixture of resin and phytic acid, and the weight ratio of the resin to the phytic acid is 1: 1.
Wherein the wetting agent is a mixture of a K12 wetting agent, a K14 wetting agent and dimethyl polysiloxane, and the weight ratio of the K12 wetting agent to the K14 wetting agent to the dimethyl polysiloxane is 1: 1.
Wherein the coupling agent is a mixture of KH792 silane coupling agent, DL602 silane coupling agent and silane coupling agent DL171, and the weight ratio of KH792 silane coupling agent, DL602 silane coupling agent and silane coupling agent DL171 is 1: 1.
The preparation method of the modified graphene oxide comprises the following steps: the method comprises the following steps: weighing 14g of graphene oxide and a dispersing solvent, and uniformly stirring; the amount of the dispersion solvent added was 20g, and the dispersion solvent comprised a mixture of N, N-dimethylformamide, N-methylpyrrolidone and tetrahydrofuran, and the amounts of N, N-dimethylformamide, N-methylpyrrolidone and tetrahydrofuran added were 6.66g, respectively.
Step two: adding 1340g of acetone solution and 1000g of deionized water into the uniformly stirred graphene oxide and the dispersing solvent, and then dispersing and mixing the mixture by using an ultrasonic disperser to obtain a graphene dispersing solution; wherein the processing time of the ultrasonic dispersion instrument is 100min, and the frequency of the ultrasonic wave is set to be 22 HZ;
step three: weighing a precursor mixture containing tungsten obtained by mixing 90% of ammonium metatungstate and 10% of tungsten carbonyl in percentage by mass respectively, then adding 20g of the precursor mixture containing tungsten into the graphene dispersion solution, uniformly stirring, continuously dropping a halogenating reagent into the stirring process, wherein the stirring time is as follows: 80 min; and after stirring, carrying out suction filtration on the obtained precipitate. Wherein the total dropping amount of the halogenating agent is 150g, the halogenating agent is selected from the mixture of thionyl chloride and oxalyl chloride, and the weight ratio of the thionyl chloride to the oxalyl chloride is 1: 2. Tungsten carbonyl can be used but is not limited to tungsten hexacarbonyl. The continuous dropping of the halogenating agent means that the halogenating agent is dropped at a constant speed at a certain time interval.
Step four: throwing the graphene dispersion solution after the precipitate suction filtration is finished into an oven for drying, and then preparing dry powder, wherein the heating temperature of the oven is set as follows: the drying time at 100 ℃ is as follows: and (5) 300 min.
Step five: and (3) placing the obtained dry powder in an alumina crucible, heating to 900 ℃, then preserving heat for a period of time, wherein the heat preservation time is 1h, then introducing nitrogen into the alumina crucible, and cooling to room temperature to obtain the modified graphene oxide powder.
Example 4:
the embodiment discloses a novel graphene film-forming agent, which comprises the following components in parts by mass:
chelating agent: 9 parts of (1);
film-forming agent: 279 parts of a solvent;
oxidizing agent: 2 parts of (1);
film-forming auxiliary agent: 6 parts of (1);
wetting agent: 5 parts of a mixture;
coupling agent: 7 parts.
Wherein the chelating agent is sodium citrate.
Wherein the film forming agent is phytic acid.
Wherein the oxidant is titanium nitrate.
The film-forming assistant is a mixture of modified graphene oxide and nano rare earth salt, and the weight ratio of the modified graphene oxide to the nano rare earth salt is 1: 1; and the nano rare earth salt is cerium fluoride.
Wherein the wetting agent is a K12 wetting agent.
Wherein the coupling agent is a silane coupling agent KH 550.
The preparation method of the modified graphene oxide comprises the following steps: the method comprises the following steps: weighing 14g of graphene oxide and a dispersing solvent, and uniformly stirring; the amount of the dispersion solvent added was 18g, and the dispersion solvent was dimethyl sulfoxide.
Step two: adding 1050g of acetone solution and 600g of deionized water into the uniformly stirred graphene oxide and dispersion solvent, and then dispersing and mixing the mixture by using an ultrasonic disperser to obtain a graphene dispersion solution; wherein the processing time of the ultrasonic dispersion instrument is 92min, and the frequency of the ultrasonic wave is set to be 24 HZ;
step three: weighing a precursor mixture containing tungsten obtained by mixing 90% of ammonium metatungstate and 10% of tungsten carbonyl in percentage by mass respectively, adding 27g of the precursor mixture containing tungsten into the graphene dispersion solution, uniformly stirring, continuously dropping a halogenating reagent into the stirring process, wherein the stirring time is as follows: 60 min; and after stirring, carrying out suction filtration on the obtained precipitate. Wherein the total dropping amount of the halogenating agent is 120g, and the continuous dropping of the halogenating agent means that the halogenating agent is dropped at a constant speed with a time interval of 2 min. The halogenating agent is selected from a mixture of phosphorus tribromide and phosphorus pentachloride, and the weight ratio of phosphorus tribromide to phosphorus pentachloride is 1: 2. Tungsten carbonyl can be used but is not limited to tungsten hexacarbonyl.
Step four: throwing the graphene dispersion solution with the precipitate filtered into an oven for drying to prepare dry powder, wherein the heating temperature of the oven is set as follows: drying time at 105 ℃ is as follows: and (8) 280 min.
Step five: and (3) placing the obtained dry powder in an alumina crucible, heating to 700 ℃, then preserving heat for a period of time, wherein the heat preservation time is 3h, then introducing nitrogen into the alumina crucible, and cooling to room temperature to obtain the modified graphene oxide powder.
Example 5:
the embodiment discloses a novel graphene film-forming agent, which comprises the following components in parts by mass:
chelating agent: 10 parts of a binder;
film-forming agent: 430 parts of;
wetting agent: 9 parts of (1);
coupling agent: 5 parts of the raw materials.
The chelating agent is a mixture of sodium benzoate, EDTA-4Na, sodium gluconate and sodium citrate, and the weight ratio of the sodium benzoate, the EDTA-4Na, the sodium gluconate and the sodium citrate is 1: 1.
Wherein the film forming agent comprises the mixture of fluozirconic acid, fluotitanic acid, potassium fluozirconate, fluoboric acid and phytic acid, and the weight ratio of the fluozirconic acid to the fluotitanic acid to the potassium fluozirconate to the fluoboric acid to the phytic acid is 1: 1.
Wherein the wetting agent is dimethyl polysiloxane.
Wherein the coupling agent comprises a silane coupling agent KH550, a silane coupling agent KH560, a KH570 silane coupling agent, a KH792 silane coupling agent, a mixture of a DL602 silane coupling agent and a silane coupling agent DL171, and the weight ratio of the silane coupling agent KH550, the silane coupling agent KH560, the KH570 silane coupling agent, the KH792 silane coupling agent, the DL602 silane coupling agent and the silane coupling agent DL171 is 1: 1.
The graphene film-forming agent prepared in the mass parts of the embodiments 1 to 5 and the common phosphating solvent, the vitrification solvent and the silane solvent in the current market are respectively adopted to carry out surface treatment on eight same metal workpieces, and the results of various performance tests are as follows:
from the above table data canIt is shown that the mass parts in the examples 1-4 of the present invention are all within the required range of the novel graphene film forming agent disclosed in the present invention, the composition in the example 5 does not contain an oxidizing agent and a special film forming aid, and the phosphatization, vitrification and silane solvents/solutions are all existing products, the test time of copper sulfate drop in the bare film experiment in the examples 1-4 of the present invention can be as high as 60s, the soaking time of the bare film in 3.5% NaCl can be as high as 60min, and the average value of the test time of neutral salt spray in the bare film experiment is about 90min, all of the above three items are to test the corrosion resistance/corrosion resistance of the bare film, compared with the test time of copper sulfate drop in the bare film of the existing phosphatization, vitrification and silane solvents/solutions being not more than 20s, the soaking time in 3.5% NaCl being not more than 40min and the test time of neutral salt spray being not more than 40min, the corrosion resistance/corrosion resistance of the bare film formed by the invention is obviously improved. Even though the oxidant and the special film-forming additive (not containing the modified graphene oxide) are removed, the corrosion resistance/corrosion resistance of the bare film of the component in the embodiment 5 is improved to a certain extent compared with the existing phosphated, vitrified and silane solvents/solutions. Meanwhile, compared with the existing phosphating, vitrification and silane solvents/solutions, the normal state rust-proof time of the coating composition of examples 1-4 of the invention can be improved from about half a month to 180 days, the salt spray time of the coating fork can be improved from 360h to 700h, and the impact force test can be improved from 50KG to 75KG, unit (m)2KG) can be from 50 to 60m2Lifting the KG to 200-300m2KG, i.e. the normal rust protection time, the salt spray time of the coating fork, the impact force test and the unit (m) of the invention2KG) is also obviously improved; the composition of example 5 had the normal rust-proof time, coating cross-cut salt spray time, impact force test and unit (m) of the composition even when the oxidizing agent and the special film-forming assistant (not containing the modified graphene oxide) were removed2KG) is also superior to existing phosphated, vitrified and silane solvents/solutions.
The present invention is not limited to the above-mentioned preferred embodiments, and any other products similar or identical to the present invention, which can be obtained by anyone based on the teaching of the present invention, fall within the protection scope of the present invention.
Claims (7)
1. A novel graphene film-forming agent is characterized in that: the graphene film-forming agent comprises the following components in parts by mass:
chelating agent: 1-10 parts;
film-forming agent: 1-450 parts;
oxidizing agent: 1-5 parts;
film-forming auxiliary agent: 1-10 parts;
wetting agent: 1-10 parts;
coupling agent: 1-10 parts.
2. The novel graphene film-forming agent according to claim 1, wherein: the chelating agent comprises one or more of sodium benzoate, EDTA-4Na, sodium gluconate and sodium citrate.
3. The novel graphene film-forming agent according to claim 1, wherein: the film forming agent comprises one or the mixture of more than two of fluozirconic acid, fluotitanic acid, potassium fluozirconate, fluoboric acid and phytic acid.
4. The novel graphene film-forming agent according to claim 1, wherein: the oxidant comprises one or more of zirconium nitrate, cupric nitrate, potassium nitrate, titanium nitrate, ammonium molybdate and potassium permanganate.
5. The novel graphene film-forming agent according to claim 1, wherein: the film forming assistant comprises one or more of modified graphene oxide, fullerene, nano rare earth salt, magnesium citrate, hydroxycarboxylic acid and plant extract.
6. The novel graphene film former according to claim 1, wherein: the wetting agent comprises one or more of K12 wetting agent, K14 wetting agent, wetting agent 0S-406, BYK-9076 wetting agent, DC-67 wetting agent and dimethyl polysiloxane.
7. The novel graphene film former according to claim 1, wherein: the coupling agent comprises one or more of a silane coupling agent KH550, a silane coupling agent KH560, a KH570 silane coupling agent, a KH792 silane coupling agent, a DL602 silane coupling agent and a silane coupling agent DL 171.
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