CN108373608A - A kind of environment-friendly water-based chromium-free zinc aluminum conductive coating and its preparation method and application - Google Patents
A kind of environment-friendly water-based chromium-free zinc aluminum conductive coating and its preparation method and application Download PDFInfo
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- CN108373608A CN108373608A CN201611028492.0A CN201611028492A CN108373608A CN 108373608 A CN108373608 A CN 108373608A CN 201611028492 A CN201611028492 A CN 201611028492A CN 108373608 A CN108373608 A CN 108373608A
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- 238000000576 coating method Methods 0.000 title claims abstract description 109
- 239000011248 coating agent Substances 0.000 title claims abstract description 105
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910000611 Zinc aluminium Inorganic materials 0.000 title claims abstract description 41
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000005260 corrosion Methods 0.000 claims abstract description 12
- 230000007797 corrosion Effects 0.000 claims abstract description 12
- 239000006184 cosolvent Substances 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 10
- 239000002562 thickening agent Substances 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003973 paint Substances 0.000 claims abstract description 9
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 8
- 239000007822 coupling agent Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000007921 spray Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 9
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 8
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 8
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 8
- 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 7
- 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 7
- 229940068041 phytic acid Drugs 0.000 claims description 7
- 235000002949 phytic acid Nutrition 0.000 claims description 7
- 239000000467 phytic acid Substances 0.000 claims description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229910052755 nonmetal Inorganic materials 0.000 claims description 5
- 229920002545 silicone oil Polymers 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 229960002645 boric acid Drugs 0.000 claims description 3
- 235000010338 boric acid Nutrition 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 3
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- -1 ion compound Chemical class 0.000 abstract description 8
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 229910052793 cadmium Inorganic materials 0.000 abstract description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052753 mercury Inorganic materials 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 239000004411 aluminium Substances 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 239000011701 zinc Substances 0.000 abstract 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 8
- 238000003618 dip coating Methods 0.000 description 6
- 229910000975 Carbon steel Inorganic materials 0.000 description 5
- 239000010962 carbon steel Substances 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 3
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 description 3
- 229940083037 simethicone Drugs 0.000 description 3
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/103—Anti-corrosive paints containing metal dust containing Al
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to environmentally friendly functional paint field, specially a kind of environment-friendly water-based chromium-free zinc aluminum conductive coating and its preparation method and application.It counts in parts by weight, which includes following components and content：2~10 parts of aluminium powder, 10~30 parts of metal zinc, 0.5~8 part of conducting powder, 0.5~5 part of emulsifier, 5~20 parts of dispersant, 5~15 parts of cosolvent, 5~20 parts of silane coupling agent, 2~10 parts of titanate coupling agent, 0.3~4 part of corrosion inhibiter, 0.05~1 part of thickener, 20~60 parts of deionized water, 0.1~2 part of antifoaming agent.The environment-friendly water-based chromium-free zinc aluminum conductive coating non-hexavalent chromium of the present invention and lead, mercury, cadmium heavy metal ion compound, without the volatility toxic solvent such as benzene, dimethylbenzene, and under conditions of not influencing paint stability and coating salt fog performance, coating has excellent electric conductivity.
Description
Technical Field
The invention relates to the field of environment-friendly functional coatings, in particular to an environment-friendly water-based chromium-free zinc-aluminum conductive coating and a preparation method and application thereof.
Background
The Dacromet coating has the characteristics of corrosion resistance, no hydrogen embrittlement and the like, and is widely applied to the fields of automobiles, household appliances, ships and the like. However, due to environmental protection, Cr in the coating6+Due to the disablement of dacromet, the application of dacromet is increasingly limited, and thus the research and application of environment-friendly chromium-free dacromet are widely concerned and developed. In recent years, there have been two main directions of development for chromium-free dacromet: the first one is a solvent type chromium-free Dacromet coating, which is an anticorrosive coating represented by foreign Delkin and Meili and taking flaky zinc-aluminum powder, resin, an auxiliary agent and the like as film forming substances. The solvent-type chromium-free Dacromet has less Cr6+But still has Volatile Organic Compounds (VOC) emissions, and should not be considered a true environmental protection coating. Secondly, the water-based chromium-free dacrometThe coating is represented by overseas Zernicke and contains no Cr and mainly comprises flaky zinc-aluminum powder, a silane coupling agent, a passivating agent and deionized water6+The novel anticorrosive paint belongs to an environment-friendly chromium-free water-based product, and a chromium-free coating is gradually replacing a chromium coating.
The european 2000/53/EG states that, since 7/1/2003, the hexavalent chromium content of the anticorrosive coatings on each automobile produced and sold in europe should not exceed 2 g, and the technical standards for chromium-free coatings have been established and implemented by automobile companies such as bma, ford, volkswage, general, walvo, etc. Along with the above, in the field of electronic and electric appliances, 13.2.2003, official gazettes of the European Union have published instructions of waste electric and electronic appliances (WEEE) (2002/96/EC) and restriction of use of certain harmful substances in electric and electronic equipment (RoHS) (2002/95/EC), and hexavalent chromium is prohibited from being used in metal anticorrosive coatings of electric appliances from 1.7.2006. The content of 'electronic information product pollution prevention and control management methods' is basically determined by the government of China, wherein the content is clearly specified, and from 7/1/2006, all electronic information products sold in China cannot contain toxic and harmful substances including hexavalent chromium and the like.
At present, the environment-friendly chromium-free zinc-aluminum coating has breakthrough progress, the developed coating has better corrosion resistance, and patent protection is applied. Although a large amount of zinc powder and aluminum powder exist in the coating, most of the zinc powder and aluminum powder are coated by a film forming material in the film forming process, so that the conductivity of the coating is greatly reduced, and the application of the coating to some special parts is seriously influenced, for example, the application of fasteners in industries such as petroleum, chemical engineering, railways, traffic and the like. Static electricity may cause explosion or fire.
Therefore, while the environment-friendly water-based chromium-free zinc-aluminum conductive coating has excellent stability and salt spray resistance, the development of the environment-friendly water-based chromium-free zinc-aluminum conductive coating with good conductivity is awaited.
Disclosure of Invention
Aiming at the problems in the current special field, the invention provides an environment-friendly water-based chromium-free zinc-aluminum conductive coating, and a preparation method and application thereof, wherein the coating has excellent salt spray resistance and stability, and good conductivity.
The technical scheme of the invention is as follows:
the environment-friendly water-based chromium-free zinc-aluminum conductive coating comprises the following components in parts by weight: 2-10 parts of aluminum powder, 10-30 parts of metal zinc powder, 0.5-8 parts of conductive powder, 0.5-5 parts of emulsifier, 5-20 parts of dispersant, 5-15 parts of cosolvent, 5-20 parts of silane coupling agent, 2-10 parts of titanate coupling agent, 0.3-4 parts of corrosion inhibitor, 0.05-1 part of thickener, 20-60 parts of deionized water and 0.1-2 parts of defoamer.
The environment-friendly water-based chromium-free zinc-aluminum conductive coating has flaky aluminum powder, the sheet diameter is 10-25 mu m, and the thickness is 0.1-0.3 mu m.
The environment-friendly water-based chromium-free zinc-aluminum conductive coating is characterized in that the metal zinc powder is flaky, the sheet diameter is 10-20 mu m, and the thickness is 0.1-0.3 mu m.
The environment-friendly water-based chromium-free zinc-aluminum conductive coating is characterized in that the conductive powder is metal powder or/and non-metal powder, the metal powder is one or a mixture of more than two of copper powder and silver powder, and the particle size is 0.1-2 mu m; the non-metal powder is one or more than two mixed powder of carbon black, carbon nanotubes, graphite and graphene, and the particle size is 0.01-1 mu m.
The environment-friendly water-based chromium-free zinc-aluminum conductive coating comprises an emulsifier OP-10 or NP-9, a dispersant which is one or more than two of ethanol, methanol, ethylene glycol, propylene glycol, polyethylene glycol and dipropylene glycol, a cosolvent which is one or more than two of ethylene glycol butyl ether, ethylene glycol methyl ether, propylene glycol ethyl ether and propylene glycol methyl ether, a corrosion inhibitor which is one or more than two of sodium molybdate, phytic acid, boric acid, salicylic acid and salicylaldehyde, a thickening agent which is one or more than two of hydroxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose, and a defoaming agent which is dimethyl silicone oil.
The preparation method of the environment-friendly water-based chromium-free zinc-aluminum conductive coating comprises the following steps:
(1) step A, dispersing aluminum powder, metal zinc powder and conductive powder in a dispersing agent and a cosolvent, uniformly stirring, adding a silane coupling agent, a titanate coupling agent and a defoaming agent, and mixing and stirring for 2-5 hours;
(2) and step B, dispersing the emulsifier and the corrosion inhibitor in deionized water for 20-60 min;
(3) and mixing the substances prepared in the step A and the step B, adding a thickening agent, and stirring for 8-15 hours to obtain the final environment-friendly water-based chromium-free zinc-aluminum conductive coating.
The application of the environment-friendly water-based chromium-free zinc-aluminum conductive coating is to centrifugally dip-coat the prepared environment-friendly water-based chromium-free zinc-aluminum conductive coating into a bolt fastener, and then the bolt fastener is coated twice and dried: the thickness of the obtained coating is 8-10 mu m at low temperature of 70-110 ℃ for 15-40 min and high temperature of 250-350 ℃ for 30-50 min, the stability of the coating reaches 6-8 months, and the salt spray performance of the coating reaches 500 h.
The design idea of the invention is as follows:
the environment-friendly water-based chromium-free zinc-aluminum conductive coating disclosed by the invention contains chromium, lead, mercury and cadmium heavy metal ion compounds, does not contain volatile toxic solvents such as benzene and dimethylbenzene, and the conductive powder in the coating greatly improves the conductive performance of the coating, and meanwhile, the stability of the coating and the salt spray resistance of the coating are not influenced.
The invention has the advantages and beneficial effects that:
1. the coating provided by the invention is green and environment-friendly, has no pollution to the environment, is nuisance-free, and has excellent stability.
2. The coating disclosed by the invention has excellent salt spray performance and excellent conductivity.
3. The paint can be stored for 6-8 months in an environment of 5-30 ℃.
4. The invention provides a preparation method of an environment-friendly water-based chromium-free zinc-aluminum conductive coating, which is simple in preparation process and is used for large-scale industrial production.
Detailed Description
In the specific implementation process, the environment-friendly water-based chromium-free zinc-aluminum conductive coating comprises the following components in parts by weight: 2-10 parts (preferably 5-8 parts) of aluminum powder, 10-30 parts (preferably 15-25 parts) of metal zinc powder, 0.5-8 parts (preferably 1-4 parts) of conductive powder, 0.5-5 parts of emulsifier, 5-20 parts of dispersant, 5-15 parts of cosolvent, 5-20 parts (preferably 5-10 parts) of silane coupling agent, 2-10 parts (preferably 3-6 parts) of titanate coupling agent, 0.3-4 parts of corrosion inhibitor, 0.05-1 part of thickener, 20-60 parts of deionized water and 0.1-2 parts of defoaming agent. Wherein,
the aluminum powder is flaky, the flake diameter is 10-25 μm, and the thickness is 0.1-0.3 μm. The metallic zinc powder is flaky, the diameter of the flake is 10-20 μm, and the thickness of the flake is 0.1-0.3 μm. The particle size of the metal powder conductive powder is 0.1-2 μm, and the particle size of the nonmetal powder conductive powder is 0.01-1 μm. The emulsifier is OP-10 (condensate of alkylphenol and ethylene oxide) or NP-9 (nonylphenol polyoxyethylene ether). The dispersant is one or more of ethanol, methanol, ethylene glycol, propylene glycol, polyethylene glycol and dipropylene glycol. The cosolvent is one or more of ethylene glycol butyl ether, ethylene glycol methyl ether, propylene glycol ethyl ether and propylene glycol methyl ether. The silane coupling agent is one or more than two of tetraethyl silicate, KH550 (gamma-aminopropyltriethoxysilane), KH560 (gamma-glycidoxypropyltrimethoxysilane), KH570 (gamma- (methacryloyloxy) propyltrimethoxysilane), KH578 (gamma-glycidoxypropylmethyldiethoxysilane) and KH566(2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane). The titanate coupling agent is one or more than two of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate, di (dioctyl phosphite) tetra-isopropyl titanate, butyl titanate, ethyl titanate and tetra-isopropyl titanate. The corrosion inhibitor is one or more than two of sodium molybdate, phytic acid, boric acid, salicylic acid and salicylaldehyde. The thickener is one or more of hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose. The defoaming agent is dimethyl silicone oil.
The preparation method of the environment-friendly water-based chromium-free zinc-aluminum conductive coating comprises the following steps:
(1) step A, dispersing aluminum powder, metal zinc powder and conductive powder in a dispersing agent and a cosolvent, uniformly stirring, adding a silane coupling agent, a titanate coupling agent and a defoaming agent, and mixing and stirring for 2-5 hours;
(2) and step B, dispersing the emulsifier and the corrosion inhibitor in deionized water for 20-60 min;
(3) and mixing the substances prepared in the step A and the step B, adding a thickening agent, and stirring for 8-15 hours to obtain the final environment-friendly water-based chromium-free zinc-aluminum conductive coating.
Centrifugally dip-coating the prepared environment-friendly water-based chromium-free zinc-aluminum conductive coating into a bolt fastener, and coating and baking for two times: the thickness of the obtained coating is 8-10 mu m at low temperature of 70-110 ℃ for 15-40 min and high temperature of 250-350 ℃ for 30-50 min, the stability of the coating reaches 6-8 months, the salt spray performance of the coating reaches 500h, and the coating has excellent conductivity.
The present invention will be described in further detail below by way of examples.
Example 1:
in this embodiment, the preparation method of the environment-friendly water-based chromium-free zinc-aluminum conductive coating is as follows:
1. dispersing 70g of aluminum powder, 200g of metal zinc powder and 20g of carbon nano-tubes in 150g of polyethylene glycol and 70g of butyl glycol ether, uniformly stirring, adding a silane coupling agent KH560(60g), 30g of butyl titanate and 5g of dimethyl silicone oil, mixing and stirring for 3 hours;
2. OP-10(10g) and phytic acid 4g are dispersed in deionized water 400g for 30 min;
3. and (3) mixing the step (1) and the step (2), adding 1g of hydroxyethyl cellulose, and stirring for 10 hours to obtain the final zinc-aluminum-silicon coating.
Centrifugally dip-coating the prepared coating on 5 bolt fasteners, spraying 1 piece of carbon steel, coating and baking for two times (low temperature 80 ℃, 20 minutes, high temperature 330 ℃, 40 minutes), wherein the thickness of the coating is 8-10 mu m, the resistivity of the coating is 0.21 omega-cm, and the coating does not generate red rust after a 500-hour neutral salt spray test. The paint can be stored for 6 months at normal temperature.
Example 2:
in this embodiment, the preparation method of the environment-friendly water-based chromium-free zinc-aluminum conductive coating is as follows:
1. dispersing 60g of aluminum powder, 210g of metal zinc powder and 30g of graphene in 150g of ethylene glycol and 100g of ethylene glycol monomethyl ether, uniformly stirring, adding a silane coupling agent KH550(80g), 50g of ethyl titanate and 4g of simethicone, mixing and stirring for 4 hours;
2. OP-10(16g) and 4g of sodium molybdate are dispersed in 325g of deionized water for 20 min;
3. and (3) mixing the step (1) and the step (2), adding 1g of hydroxyethyl cellulose, and stirring for 8 hours to obtain the final zinc-aluminum-silicon coating.
Centrifugally dip-coating the prepared coating on 5 bolt fasteners, spraying 1 piece of carbon steel, coating and baking for two times (low temperature 90 ℃, 20 minutes, high temperature 330 ℃, 40 minutes), wherein the thickness of the coating is 8-10 mu m, the resistivity of the coating is 0.19 omega-cm, and the coating does not generate red rust after 480h neutral salt spray test. The paint can be stored for 7 months at normal temperature.
Example 3:
in this embodiment, the preparation method of the environment-friendly water-based chromium-free zinc-aluminum conductive coating is as follows:
1. dispersing 60g of aluminum powder, 210g of metal zinc powder, 5g of copper powder and 10g of carbon nano-tubes in 160g of ethanol and 111g of ethylene glycol monobutyl ether, uniformly stirring, adding a silane coupling agent KH560(70g), 60g of di (dioctyl phosphite) tetraisopropyl titanate and 4g of dimethyl silicone oil, mixing and stirring for 4 hours;
2. dispersing NP-9(20g) and phytic acid 4g in 300g of deionized water for 20 min;
3. and (3) mixing the step (1) and the step (2), adding 1g of hydroxyethyl cellulose, and stirring for 12 hours to obtain the final zinc-aluminum-silicon coating.
Centrifugally dip-coating the prepared coating on 5 bolt fasteners, spraying 1 piece of carbon steel, coating and baking for two times (low temperature 90 ℃, 20 minutes, high temperature 330 ℃, 40 minutes), wherein the thickness of the coating is 8-10 mu m, the resistivity of the coating is 0.15 omega-cm, the coating does not generate red rust after a 500-hour neutral salt spray test, and the coating is stored for 8 months at normal temperature.
Example 4:
in this embodiment, the preparation method of the environment-friendly water-based chromium-free zinc-aluminum conductive coating is as follows:
1. dispersing 60g of aluminum powder, 196g of metal zinc powder and 30g of graphene in 160g of methanol and 125g of propylene glycol ether, uniformly stirring, adding a silane coupling agent KH578(70g), 60g of bis (dioctyl phosphite) tetraisopropyl titanate and 4g of simethicone, mixing and stirring for 4 hours;
2. dispersing NP-9(20g) and phytic acid 4g in 300g of deionized water for 20 min;
3. and (3) mixing the step (1) and the step (2), adding 1g of hydroxyethyl cellulose, and stirring for 12 hours to obtain the final zinc-aluminum-silicon coating.
Centrifugally dip-coating the prepared coating on 5 bolt fasteners, spraying 1 piece of carbon steel, coating and baking for two times (low temperature 90 ℃, 20 minutes, high temperature 340 ℃, 40 minutes), wherein the thickness of the coating is 8-10 mu m, the resistivity of the coating is 0.14 omega-cm, and the coating does not generate red rust after 470h neutral salt spray test. The paint can be stored for 7 months at normal temperature.
Example 5:
in this embodiment, the preparation method of the environment-friendly water-based chromium-free zinc-aluminum conductive coating is as follows:
1. dispersing 50g of aluminum powder, 200g of metal zinc powder and 30g of carbon nano-tubes in 170g of methanol and 125g of propylene glycol ether, uniformly stirring, adding a silane coupling agent KH566(50g), 60g of butyl titanate and 4g of simethicone, mixing and stirring for 4 hours;
2. dispersing NP-9(10g) and phytic acid 4g in deionized water 326g for 30 min;
3. and (3) mixing the step (1) and the step (2), adding 1g of hydroxyethyl cellulose, and stirring for 10 hours to obtain the final zinc-aluminum-silicon coating.
Centrifugally dip-coating the prepared coating on 5 bolt fasteners, spraying 1 piece of carbon steel, coating and baking for two times (low temperature 90 ℃, 20 minutes, high temperature 330 ℃, 40 minutes), wherein the thickness of the coating is 8-10 mu m, the resistivity of the coating is 0.15 omega-cm, and the coating does not generate red rust after a neutral salt spray test for 450 h. The paint can be stored for 7 months at normal temperature.
The results of the examples show that the environment-friendly water-based chromium-free zinc-aluminum conductive coating disclosed by the invention does not contain hexavalent chromium, lead, mercury, cadmium heavy metal ion compounds, benzene, xylene and other volatile toxic solvents, and the coating has excellent conductivity under the condition that the stability of the coating and the salt spray performance of the coating are not influenced.
Claims (7)
1. The environment-friendly water-based chromium-free zinc-aluminum conductive coating is characterized by comprising the following components in parts by weight: 2-10 parts of aluminum powder, 10-30 parts of metal zinc powder, 0.5-8 parts of conductive powder, 0.5-5 parts of emulsifier, 5-20 parts of dispersant, 5-15 parts of cosolvent, 5-20 parts of silane coupling agent, 2-10 parts of titanate coupling agent, 0.3-4 parts of corrosion inhibitor, 0.05-1 part of thickener, 20-60 parts of deionized water and 0.1-2 parts of defoamer.
2. The environment-friendly water-based chromium-free zinc-aluminum conductive coating as claimed in claim 1, wherein the aluminum powder is flaky, the diameter of the flaky is 10-25 μm, and the thickness of the flaky is 0.1-0.3 μm.
3. The environment-friendly water-based chromium-free zinc-aluminum conductive coating as claimed in claim 1, wherein the metallic zinc powder is in a flake shape, the flake diameter is 10-20 μm, and the thickness is 0.1-0.3 μm.
4. The environment-friendly water-based chromium-free zinc-aluminum conductive coating as claimed in claim 1, wherein the conductive powder is metal powder or/and non-metal powder, the metal powder is one or a mixture of more than two of copper powder and silver powder, and the particle size is 0.1-2 μm; the non-metal powder is one or more than two mixed powder of carbon black, carbon nanotubes, graphite and graphene, and the particle size is 0.01-1 mu m.
5. The environment-friendly aqueous chromium-free zinc-aluminum conductive paint as defined in claim 1, wherein the emulsifier is OP-10 or NP-9, the dispersant is one or more selected from ethanol, methanol, ethylene glycol, propylene glycol, polyethylene glycol and dipropylene glycol, the cosolvent is one or more selected from ethylene glycol butyl ether, ethylene glycol methyl ether, propylene glycol ethyl ether and propylene glycol methyl ether, the corrosion inhibitor is one or more selected from sodium molybdate, phytic acid, boric acid, salicylic acid and salicylaldehyde, the thickener is one or more selected from hydroxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose, and the defoaming agent is dimethyl silicone oil.
6. The preparation method of the environment-friendly water-based chromium-free zinc-aluminum conductive coating of claim 1, which is characterized by comprising the following steps:
(1) step A, dispersing aluminum powder, metal zinc powder and conductive powder in a dispersing agent and a cosolvent, uniformly stirring, adding a silane coupling agent, a titanate coupling agent and a defoaming agent, and mixing and stirring for 2-5 hours;
(2) and step B, dispersing the emulsifier and the corrosion inhibitor in deionized water for 20-60 min;
(3) and mixing the substances prepared in the step A and the step B, adding a thickening agent, and stirring for 8-15 hours to obtain the final environment-friendly water-based chromium-free zinc-aluminum conductive coating.
7. The application of the environment-friendly water-based chromium-free zinc-aluminum conductive coating of claim 1 or 6, which is characterized in that the prepared environment-friendly water-based chromium-free zinc-aluminum conductive coating is centrifugally dip-coated on a bolt fastener, and the bolt fastener is subjected to two-coating and two-baking: the thickness of the obtained coating is 8-10 mu m at low temperature of 70-110 ℃ for 15-40 min and high temperature of 250-350 ℃ for 30-50 min, the stability of the coating reaches 6-8 months, and the salt spray performance of the coating reaches 500 h.
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