CN109852109A - Not chromyl environment-friendly type coating of a kind of steel plate and preparation method thereof - Google Patents
Not chromyl environment-friendly type coating of a kind of steel plate and preparation method thereof Download PDFInfo
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- CN109852109A CN109852109A CN201811637762.7A CN201811637762A CN109852109A CN 109852109 A CN109852109 A CN 109852109A CN 201811637762 A CN201811637762 A CN 201811637762A CN 109852109 A CN109852109 A CN 109852109A
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- coating
- phosphate
- steel plate
- chromyl
- friendly type
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- 238000000576 coating method Methods 0.000 title claims abstract description 124
- 239000011248 coating agent Substances 0.000 title claims abstract description 123
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 51
- 239000010959 steel Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 36
- 239000010452 phosphate Substances 0.000 claims abstract description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 25
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 20
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910015427 Mo2O3 Inorganic materials 0.000 claims abstract description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004327 boric acid Substances 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 229940075614 colloidal silicon dioxide Drugs 0.000 claims abstract description 11
- CMVOJSWILFNLFI-UHFFFAOYSA-L magnesium;dibromate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-]Br(=O)=O.[O-]Br(=O)=O CMVOJSWILFNLFI-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- 229910052810 boron oxide Inorganic materials 0.000 claims abstract description 10
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims 1
- 150000003016 phosphoric acids Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 238000005260 corrosion Methods 0.000 abstract description 14
- 230000007797 corrosion Effects 0.000 abstract description 14
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000012216 screening Methods 0.000 abstract description 2
- IMHKYSZIYMGMGC-UHFFFAOYSA-K O=[Si+3]=O.[O-]P([O-])([O-])=O Chemical compound O=[Si+3]=O.[O-]P([O-])([O-])=O IMHKYSZIYMGMGC-UHFFFAOYSA-K 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000011651 chromium Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910000976 Electrical steel Inorganic materials 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910000401 monomagnesium phosphate Inorganic materials 0.000 description 2
- 235000019785 monomagnesium phosphate Nutrition 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 210000000981 epithelium Anatomy 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
Abstract
The invention discloses a kind of steel plate environment-friendly type coatings and preparation method thereof, are grouped as by each group: phosphate；Colloidal silicon dioxide；Fe3O4、V2O3、Cr2O3、Mo2O3At least one of；At least one of boron oxide, boric acid and antifungin.One of boron oxide, boric acid and antifungin or it is a variety of be dispersed in silica solution, add Fe3O4、V2O3、Cr2O3And Mo2O3One of powder is a variety of, and stable mixed liquor is formed by way of mechanical dispersion or ultrasonic disperse；Mixed liquor and phosphate are mixed and stirred for forming coating.The purpose of the present invention is to provide a kind of not chromyl coating for the production of grain oriented magnetic steel surface coating, while solving environmental problem, it can solve not chromyl phosphate-silicon dioxide system coating and form existing resistance to hygroscopicity, heat resistance, corrosion resistance and tension bad problem when coating.The coating has good stability and screening characteristics, can satisfy large-scale production requirement.
Description
Technical field
The present invention relates to a kind of coating and its manufacturing method more particularly to a kind of steel plate environment-friendly type coating and its manufacturers
Method.
Background technique
It is phosphate inorganic coating good film-forming property, high temperature resistant, inexpensive and with excellent corrosion resistance and electrical insulating property, it uses extensively
In the insulating coating of manufacture surface of steel plate.Phosphate inorganic coating is mainly made of phosphate, filler and curing agent.Phosphate is logical
It crosses and forms reticular structure during heating, be film forming matter.Filler mainly has silica, aluminium oxide, titanium dioxide etc., rises
To the heat resistance for improving coating and improve crackle effect.Curing agent can reduce the film-forming temperature of phosphatic coating and improve coating
Water resistance.Common curing agent has metal oxide, silicate, boric acid etc., and wherein metal oxide curing agent is to heat
Insoluble phosphate is formed in film forming procedure, plays the role of fixed free phosphorus acid group.
Japanese Patent Publication 56-52117 bulletin document is disclosed with the painting of magnesium dihydrogen phosphate, colloidal silicon dioxide and chromic acid
Material.Japanese Patent Publication 53-28375 bulletin document is disclosed with the coating of aluminium dihydrogen phosphate, colloidal silicon dioxide and chromic acid.Phosphorus
Acid dihydride magnesium and aluminium dihydrogen phosphate are film forming matter, and silica is filler, and chromic acid is curing agent.In grain-oriented magnetic steel sheet table
Face coats above-mentioned coating, and the coating formed at high temperature has low thermal expansion rate and high elastic modulus.It is down to steel plate when room temperature
With the thermal expansion difference of coating tensile stress can be generated to steel plate.Coating is to steel plate tensile stress (σ) expression formula are as follows: σ=E (αFe-αCoating)
Δ T (2d/D), E are coating elasticity modulus, αFeFor the thermal expansion coefficient of steel plate, αCoatingFor the thermal expansion coefficient of coating, Δ T film forming
The difference of temperature and room temperature, d are coating layer thickness, and D is steel plate thickness.The tensile stress that coating directional electromagnetic steel plate assigns can subtract
Few iron loss and the effect for reducing magnetostrictive amount, coating have excellent corrosion resistance, resistance to hygroscopicity, heat resistance and high insulation simultaneously
Property.
The free phosphorus acid group for remaining and decomposing in phosphate coating has hygroscopicity.Chromium and phosphoric acid in foregoing invention coating
Root forms stable compound and can fix in coating from phosphate radical, improves heat resistance when the resistance to hygroscopicity and annealing of coating.
But the Cr VI in coating will cause serious harm to environment and human body, it is necessary to which developing way electromagnetic steel plate, which is used, is free of sexavalence
Chromium coating.
Publication No. " CN101223300A ", publication date is on July 16th, 2008, entitled " to have chromium-free insulation
The Chinese patent literature of the grain-oriented magnetic steel plate and its insulated hull film of epithelium " discloses a kind of chromium-free grain-oriented magnetic steel plate
With insulated hull film, main component is that phosphate, colloidal silicon dioxide and partial size are 15nm Fe, Ni, Co, Cu, Sr, Mo below
Hydroxide colloid substance.
Publication No. " CN101790599A ", publication date are on July 28th, 2010, and entitled " grain-oriented magnetic steel sheet is used
The Chinese patent literature of the manufacturing method of insulating coating treatment liquid and the grain-oriented magnetic steel sheet with insulating coating " discloses
The chelate of a kind of at least one of phosphate containing Mg, Ca, Ba, Sr, Zn, Al and Mn and colloidal silicon dioxide and titanium
The chrome-free insulating coating treatment liquid of directionality electric steel plate.
Publication No. " CN102119239A ", publication date is on July 6th, 2011, entitled " for oriented electrical steel
Chrome-free smears, uses the preparation method of the electric steel plate of the smears and the steel plate at preparation method " Chinese patent literature
Disclose a kind of Chrome-free smears for directionality electric steel plate, which contains phosphate, colloidal silicon dioxide and red
Iron ore colloidal sol.
Publication No. " CN101778964B ", publication date are on March 7th, 2012, and entitled " grain-oriented magnetic steel sheet is with absolutely
The Chinese patent literature of the manufacturing method of edge coating treatment liquid and the grain-oriented magnetic steel sheet with insulating coating " uses water-soluble
Property vfanadium compound substitute Cr VI.
Publication No. " CN103709796A " publication date is on April 9th, 2014, entitled " to improve orientation silicon steel surface
The Chinese patent literature of the Chrome-free stress coat and preparation method of tension " discloses a kind of phosphate containing Zn, Ni, Co at least one
Kind, the silicate of Na, K, Bi, Li are at least one, borate, colloidal silicon dioxide, the chromium-free coating of nitrate and Ce.
It is " a kind of for orientation silicon steel that Publication No. " CN106189459A " publication date is on December 7th, 2016, entitled
The Chinese patent literature of chromium-free environmental-protection insulating paint " discloses a kind of chromium-free environmental-protection insulating paint of orientation silicon steel, consisting of
Tungstates, titanyl sulfate, dihydric phosphate and silica solution.
Publication No. " CN104024443B " publication date is on September 3rd, 2014, entitled " grain-oriented steel of coating "
Chinese patent literature discloses a kind of Chrome-free application of mixture comprising metal phosphate, silicon oxide particle and organosilan.
Publication No. " CN105086778A " publication date is on November 25th, 2015, and entitled " one kind is used for orientation silicon steel
Chrome-free insulation coating and preparation method thereof " Chinese patent literature disclose a kind of Chrome-free insulation coating for orientation silicon steel
Preparation method, insulating coating by organic hybrid resin, silica solution, aluminium dihydrogen phosphate, inorganic buffer agent, silane coupling agent, help
Agent and silane phenol polyvinylether composition.
These technologies solve the hygroscopicity problems that chromium coating is free of for directional electrical magnet steel to a certain extent.But very
It is hard to say to have reached performance similar in Chromium coating and sufficiently solved the problems, such as the actual production without chromium coating.Publication No.
The technology that " CN101223300A " Chinese patent literature proposes, Fe, Ni, Co, Cu, Sr, Mo hydroxide colloid substance are in phosphoric acid
It is difficult to stablize in salting liquid.The technology that Publication No. " CN101790599A " Chinese patent literature proposes uses the chelate meeting of titanium
Residual organic matter is poor so as to cause coating tension and thermal stability in the coating.Publication No. " CN102119239A " China
The technology that patent document proposes equally exists the problem of phosphate solution is difficult to long-time stable using ruler iron ore colloidal sol.Publication number
The technology proposed for " CN101778964B " Chinese patent literature uses water-soluble vanadium compound, has the residual such as phosphate radical.Together
The decomposition of sulfate radical etc. will also result in coating performance deterioration and environmental pollution when sample is heat-treated.Publication No. " CN103709796A "
The nitrate residual that the technology that Chinese patent literature proposes uses will cause coating performance deterioration in the coating, in the heat treatment time-division
Solution will also result in environmental pollution.The titanyl sulfate that the technology that Publication No. " CN106189459A " Chinese patent literature proposes uses
Discoloration, insulating properties and corrosion resistance etc. when can cause annealing of sulfate radical problem.Publication No. " CN106189459A " and public affairs
The number of holding is the heat resistance that the organic matter that the technology that " CN105086778A " Chinese patent literature proposes uses can reduce coating.
Therefore, it is intended that a kind of not chromyl coating for the production of grain oriented magnetic steel surface coating is obtained, it can be more
Further solve the problems, such as coating performance and productivity.
Summary of the invention
Cr VI is free of for the production of grain oriented magnetic steel surface coating one of the objects of the present invention is to provide a kind of
Coating can solve not chromyl phosphate-silica system coating while solving environmental problem and formed
Existing resistance to hygroscopicity, heat resistance, corrosion resistance and tension bad problem when coating.The coating has good stability and coating
Property, it can satisfy large-scale production requirement.
To achieve the goals above, the present invention is used for the not chromyl painting of grain oriented magnetic steel surface coating production
Material, is made of following ingredients:
Phosphate；
Colloidal silicon dioxide；
Fe3O4、V2O3、Cr2O3、Mo2O3At least one of；
At least one of boron oxide, boric acid and antifungin.
In above-mentioned technical proposal, phosphate is main film forming substance.Colloidal silicon dioxide is filler, can improve coating
Paintability improves the heat resistance of resistance to coating and increases tension effect.In order to fix the free phosphoric acid of unreacted or heat resolve
Root, the coating of the present invention for the production of grain-oriented magnetic steel sheet surface covering, contains Fe3O4、V2O3、Cr2O3And Mo2O3
In it is at least one of.Fe during heat treatment3O4、V2O3、Cr2O3And Mo2O3Insoluble matter can be formed with phosphate radical, thus
Play the role of fixed phosphate radical, improves the heat resistance of insulating coating and resistance to hygroscopic.Boron oxide, boric acid in coating to addition
And at least one of antifungin can promote coating to be sintered, and improve coating compactness, improvement is caused because adding oxide powder
Sintering is bad and tension declines problem.
Further, in the not chromyl coating of the present invention for the production of grain oriented magnetic steel surface coating
In, contained phosphate is at least one of the phosphate of Mg, Ca, Zn, Al and Mn.
Further, based on 100g phosphate radical in the phosphate, the colloidal silica of 60~120g is contained in coating
Silicon.The paintability decline of coating, coating tension reduce when colloidal silicon dioxide is lower than 60g；Coating production is split when higher than 120g
Line.
Further, based on 100g phosphate radical in the phosphate, the Fe of 1~10g is contained in coating3O4、V2O3、
Cr2O3And Mo2O3At least one of, moisture-proof reduces when being lower than 1g, and the sintering character that coating is influenced when higher than 10g causes
Tension decline.
Further, based on 100g phosphate radical in the phosphate, containing in boron oxide, boric acid and antifungin in coating
One or more quality be 2-40g.Lower than fine and close low, the tension cracking of 2g coating；, coating unstable higher than 40g coating
Poor heat resistance.
In technical solutions according to the invention, in order to reach better tension effect and surface characteristic, colloidal state two is controlled
The size of silica is 5-50nm.
In technical solutions according to the invention, in order to achieve the purpose that effectively to fix free phosphorus acid group, the Fe3O4、
V2O3、Cr2O3And Mo2O3For powder, powder predecessor is having a size of 100nm or less.
In technical solutions according to the invention, a kind of not chromyl environment friendly coated preparation method for material of steel plate should
Method the following steps are included: one of boron oxide, boric acid and antifungin or it is a variety of be dispersed in silica solution, add Fe3O4、
V2O3、Cr2O3And Mo2O3One of powder is a variety of, and stable hang is formed by way of mechanical dispersion or ultrasonic disperse
Supernatant liquid.Suspension and silica solution and phosphate are mixed and stirred for forming coating.
Coating and its manufacturing method of the present invention for grain-oriented magnetic steel sheet compared with prior art, has such as
It is lower the utility model has the advantages that
(1) coating of the present invention for grain-oriented magnetic steel sheet is free of Cr VI, to caused by surrounding enviroment
It pollutes small.
(2) coating of the present invention for grain-oriented magnetic steel sheet is with good stability and screening characteristics, can be with
Realize industrialized production and use.
(3) coating of the coating preparation of the present invention for grain-oriented magnetic steel sheet has good resistance to hygroscopicity
Energy, corrosion resistance, heat resistance and tension effect.
Specific embodiment
Below in conjunction with specific embodiments to a kind of steel plate environment-friendly type coating of the present invention and its manufacturing method
It makes further explanation, however should explanation and description do not unduly limit the technical scheme of the present invention.
Coating of the invention is coated in grain-oriented magnetic steel sheet surface, in 750-900 DEG C of condition in heat treatment 10s after drying
More than, single side dry film amount is 2-10g/m2。
Embodiment 1
Using the high magnetic strength grain-oriented magnetic steel sheet with a thickness of 0.23mm with glass film bottom, in 3%H after shearing2SO4Water
It is stand-by after the light pickling for carrying out 10s at 80~85 DEG C in solution.At least one of boron oxide, boric acid and antifungin (are denoted as and are added
Add agent A) it is added in silica solution, add Fe3O4、V2O3、 Cr2O3And Mo2O3At least one of powder (being denoted as additive B) carries out
It stirs and ultrasonic disperse forms stable suspension, then be mixed and stirred for forming coating with phosphate, relative to the phosphate
Middle 100g phosphate radical meter, coating composition content are shown in Table 1.Coating is coated in surface of steel plate by the way of roller coating, is then dried
And the sintering heat treatment of 850 DEG C × 30s is carried out, sintered coating single side amount is 5.0g/m2.The performance investigation result of coating is converged
Always in table 1.
Table 1
Note: coating physical property assesses ◎: it is excellent, zero: good, ◇: general, ╳: poor
The evaluation of (* 1) moisture-proof: band coating grain-oriented magnetic steel sheet is boiled in 100 DEG C of pure water, comments appearance of coat
Variation and dissolution phosphorus content.
(* 2) Evaluation of Corrosion Resistance: assessing the corrosion resistance of coating by salt spray test, and salt spray test solution is that 5%NaCl is molten
Liquid, test temperature are 35 DEG C, testing time 10h.
(* 3) Evaluation of Heat Tolerance: the grain-oriented magnetic steel sheet of testing coating insulating coating after stress relief annealing is handled
Tension degradation and insulating properties degradation, wherein stress relief annealing processing process conditions be at 850 DEG C,
100%N24h is kept the temperature in gas.
It can be seen that being described above in coating is Fe3O4、V2O3、Cr2O3And Mo2O3One of powder or it is a variety of can
With the moisture-proof, corrosion resistance and heat resistance of coating, the boric acid in coating can significantly improve the corrosion resistance and tension effect of coating
Fruit.
Embodiment 2
Using the high magnetic strength grain-oriented magnetic steel sheet with a thickness of 0.23mm with glass film bottom, in 3%H after shearing2SO4Water
It is stand-by after the light pickling for carrying out 10s at 80~85 DEG C in solution.By a kind of boron compound of 5g boron oxide, boric acid or antifungin
It is to add the Fe of 5g in 10nm silica solution that 90g partial size, which is added, in (being denoted as additive A)3O4、V2O3、Cr2O3And Mo2O3In powder
A kind of additive, is stirred and ultrasonic disperse forms stable suspension, then is mixed and stirred for being formed with magnesium dihydrogen phosphate
Coating, phosphorous acid group 100g in coating, coating composition are shown in Table 2.Coating is coated in surface of steel plate by the way of roller coating, then
The sintering heat treatment of 850 DEG C × 30s is dried and carries out, sintered coating single side amount is 5.0g/m2.The performance of coating investigates knot
Fruit is summarized in table 2.
Table 2
Note: coating physical property assesses ◎: it is excellent, zero: good, ◇: general, ╳: poor
The evaluation of (* 1) moisture-proof: band coating grain-oriented magnetic steel sheet is boiled in 100 DEG C of pure water, comments appearance of coat
Variation and dissolution phosphorus content.
(* 2) Evaluation of Corrosion Resistance: assessing the corrosion resistance of coating by salt spray test, and salt spray test solution is that 5%NaCl is molten
Liquid, test temperature are 35 DEG C, testing time 10h.
(* 3) Evaluation of Heat Tolerance: the grain-oriented magnetic steel sheet of testing coating insulating coating after stress relief annealing is handled
Tension degradation and insulating properties degradation, wherein stress relief annealing processing process conditions be at 850 DEG C,
100%N24h is kept the temperature in gas.
It can be seen that the Fe in coating3O4、V2O3、Cr2O3And Mo2O3The moisture-proof of coating, corrosion resistance and heat-resisting can be improved
Performance, change boron, boric acid or antifungin in coating can significantly improve the corrosion resistance and tension effect of coating.
It should be noted that prior art part is not limited to given by present specification in protection scope of the present invention
Embodiment, all prior arts not contradicted with the solution of the present invention, including but not limited to first patent document, formerly
Public publication, formerly openly use etc., it can all be included in protection scope of the present invention.
In addition, in this case in the combination of each technical characteristic and unlimited this case claim documented combination or
It is combination documented by specific embodiment, all technical characteristics that this case is recorded can be freely combined in any way
Or combine, unless generating contradiction between each other.
It is also to be noted that embodiment enumerated above is only specific embodiments of the present invention.The obvious present invention is not
Above embodiments are confined to, the similar variation or deformation made therewith are that those skilled in the art can be from present disclosure
It immediately arrives at or is easy to just to associate, be within the scope of protection of the invention.
Claims (5)
1. a kind of not chromyl environment-friendly type coating of steel plate, it is characterised in that: include:
Based on 100g phosphate radical in the coating phosphate,
The colloidal silicon dioxide of 60 ~ 120g,
The Fe of 1 ~ 10g3O4、V2O3、Cr2O3And Mo2O3At least one of,
At least one of boron oxide, boric acid and antifungin of 2 ~ 40g.
2. the not chromyl environment-friendly type coating of a kind of steel plate according to claim 1, it is characterised in that above-mentioned phosphoric acid
Salt is at least one of the phosphate of Mg, Ca, Zn, Al and Mn.
3. the not chromyl environment-friendly type coating of a kind of steel plate according to claim 1, it is characterised in that above-mentioned colloid
The size of silica is 5-50nm.
4. the not chromyl environment-friendly type coating of a kind of steel plate according to claim 1, the Fe3O4、V2O3、
Cr2O3And Mo2O3For powder, powder predecessor size is less than 100nm.
5. based on a kind of preparation method of the steel plate without hexavalent chromium environment friendly type coating described in claim 1, feature includes
Following steps: one of boron oxide, boric acid and antifungin or it is a variety of be dispersed in silica solution, add Fe3O4、V2O3、Cr2O3
And Mo2O3One of powder is a variety of, and stable mixed liquor is formed by way of mechanical dispersion or ultrasonic disperse；Mixing
Liquid and phosphate are mixed and stirred for forming coating.
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