CN104059495A - Chromium-free passivation solution and preparation method and use thereof, and metal material - Google Patents
Chromium-free passivation solution and preparation method and use thereof, and metal material Download PDFInfo
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Abstract
The invention provides a preparation method of a chromium-free passivation solution. The method comprises successively mixing evenly water, silane coupling agents, water-soluble silicate, an accelerant, a silica filler and water-soluble film-forming resin. The invention also provides the chromium-free passivation solution prepared according to the preparation method and a use thereof in preparation of metal materials. The invention further provides a metal material which comprises a metal substrate and a coating layer adhering onto the metal substrate, wherein the coating layer is a cured product of the chromium-free passivation solution. A protective film formed by the chromium-free passivation solution provided by the invention is quite excellent in corrosion resistance. In addition, the chromium-free passivation solution provided by the invention is quite excellent in storage resistance, and can be stored for 180 days at room temperature after completion of preparation but does not generate obvious character changes and performance reduction.
Description
Technical field
The present invention relates to metal protection field, particularly, relate to purposes and the metallic substance of a kind of preparation method of chromium-free passivation liquid, the chromium-free passivation liquid being obtained by this preparation method, this chromium-free passivation liquid.
Background technology
Metallic substance, comprises hot-dip galvanized metal material and hot-dip aluminizing zinc metallic substance, in order to prevent corrosion, and all can be at the surface of metallic substance coating one deck chromium-free passivation liquid to form protective film.Thereby the performance of chromium-free passivation liquid is very important for the rust protection of metallic substance.
For example, CN101608306A discloses a kind of passivating solution, also belongs to a kind of chromium-free passivation liquid, it is characterized in that, this passivating solution is the aqueous solution that contains water-soluble molybdenum compound, boric acid, water soluble organic substance and silicon sol, and wherein, described water soluble organic substance is the mixture of alcohol and organic carboxyl acid.
But the solidity to corrosion that experiment showed, the protective film that this chromium-free passivation liquid forms is still poor.
Summary of the invention
The poor defect of solidity to corrosion that the object of the invention is to overcome the protective film that existing chromium-free passivation liquid forms, provides a kind of chromium-free passivation liquid that can form the good protective film of solidity to corrosion.
To achieve these goals, the invention provides a kind of preparation method of chromium-free passivation liquid, the method comprises water, silane coupling agent, water-soluble silicate, promotor, cilicon oxide filler and water-soluble film-forming resin is mixed successively; Described silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3, CH
2=C (CH
3) COO (CH
2)
3si (OC
2h
5)
3, CH
2=C (CH
3) COO (CH
2)
3siCH
3(OCH
3)
2and CH
2=C (CH
3) COO (CH
2)
3siCH
3(OC
2h
5)
2in at least one; Described promotor is thiocarbamide and/or urea.
The present invention also provides the chromium-free passivation liquid preparing according to preparation method as above.
The present invention also provides the purposes of above-mentioned chromium-free passivation liquid in preparing metallic substance.
The present invention also provides a kind of metallic substance, this metallic substance comprises metal base and is attached to the coating on this metal base, described metal base is at least one in pot galvanize metal base, hot-dip aluminizing zinc metal base and hot-dip aluminizing zinc magnesium metal base material, it is characterized in that the cured product that described coating is chromium-free passivation liquid as above.
By technique scheme, the solidity to corrosion of the protective film that chromium-free passivation liquid provided by the invention forms is very good.In addition, the storage endurance of chromium-free passivation liquid provided by the invention is very excellent, can at room temperature store 180 days and obvious proterties does not occur change and degradation after preparation completes.
Other features and advantages of the present invention partly in detail are described the embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of chromium-free passivation liquid, the method comprises water, silane coupling agent, water-soluble silicate, promotor, cilicon oxide filler and water-soluble film-forming resin is mixed successively; Described silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3, CH
2=C (CH
3) COO (CH
2)
3si (OC
2h
5)
3, CH
2=C (CH
3) COO (CH
2)
3siCH
3(OCH
3)
2and CH
2=C (CH
3) COO (CH
2)
3siCH
3(OC
2h
5)
2in at least one; Described promotor is thiocarbamide and/or urea.
Wherein, at length, the method comprises: (1) mixes water and described silane coupling agent, obtains uniform liquid A; (2) described uniform liquid A and water-soluble silicate are mixed, obtain uniform liquid B; (3) described uniform liquid B and promotor are mixed, obtain uniform liquid C; (4) described uniform liquid C and cilicon oxide filler are mixed, obtain uniform liquid D; (5) described uniform liquid D is mixed with water-soluble film-forming resin, obtain uniform liquid E.Wherein, there is no particular limitation for the method mixing, as long as can obtain uniform stable phase, preferably by stirring, makes to mix more even.
According to the preparation method of chromium-free passivation liquid provided by the invention, wherein, with respect to the described water-soluble silicate of 1 weight part, the consumption of described silane coupling agent can be 0.5-4.5 weight part, is preferably 1.4-1.8 weight part.
Wherein, with respect to the described water-soluble silicate of 1 weight part, the consumption of described promotor can be 0.2-1.8 weight part, is preferably 0.5-0.7 weight part.
Wherein, with respect to the described water-soluble silicate of 1 weight part, the consumption of described cilicon oxide filler can be 0.25-2.2 weight part, is preferably 0.6-0.85 weight part.
Wherein, with respect to the described water-soluble silicate of 1 weight part, in solid, the consumption of described water-soluble film-forming resin can be 0.8-6.8 weight part, is preferably 2.1-2.7 weight part.Herein solid with for calculating or representing that the solid implication of solid content is identical, be water-soluble film-forming resin except remaining composition after desolventizing.
Wherein, with respect to the described water-soluble silicate of 1 weight part, the consumption of water is 10-100 weight part, is preferably 25-40 weight part.It should be noted that, in the present invention, the consumption of said water refers to the amount of the water of other interpolation, do not comprise in above-mentioned other component of adding with solution or emulsion mode with the amount of water.
According to the preparation method of chromium-free passivation liquid provided by the invention, wherein, described silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3, CH
2=C (CH
3) COO (CH
2)
3si (OC
2h
5)
3, CH
2=C (CH
3) COO (CH
2)
3siCH
3(OCH
3)
2and CH
2=C (CH
3) COO (CH
2)
3siCH
3(OC
2h
5)
2in at least one.Wherein, CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3(being called γ-methacryloxypropyl trimethoxy silane), CH
2=C (CH
3) COO (CH
2)
3si (OC
2h
5)
3(being called γ-methacryloxypropyl triethoxyl silane), CH
2=C (CH
3) COO (CH
2)
3siCH
3(OCH
3)
2(being called γ-methacryloxypropyl methyl dimethoxysilane) and CH
2=C (CH
3) COO (CH
2)
3siCH
3(OC
2h
5)
2(being called γ-methacryloxypropyl methyldiethoxysilane) can be used as silane coupling agent, commodity shown in the commercially available various above-mentioned chemical formula that can be used as silane coupling agent may be used to the present invention, for example the trade mark purchased from Debang Chemical New Material Co., Ltd. is the commercially available product of DB-570, DB-571 and DB-572, and the commercially available product that is Luer-1512 purchased from the trade mark of Rule, Shanghai Chemical trade company limited.Wherein, preferred described silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3.
According to the preparation method of chromium-free passivation liquid provided by the invention, wherein, described water-soluble silicate can be water glass and/or potassium silicate.Described water glass can be at least one in anhydrous sodium metasilicate, SODIUM METASILICATE PENTAHYDRATE and nine water water glass.And the consumption of described water-soluble silicate is to calculate with the amount of anhydrous silicate.
According to the preparation method of chromium-free passivation liquid provided by the invention, wherein, described cilicon oxide filler does not have special requirement, can be for take the various fillers that silicon oxide is main body, for example, described cilicon oxide filler can be nano-silica powder and/or nano silicon dioxide sol; Under preferable case, the particle diameter of the silicon oxide in described cilicon oxide filler can be 5-90nm, 5-30nm more preferably, for example, can use the commercially available product that the trade mark purchased from Asahi Denka Co., Ltd. is AT-30, AT-30S, AT-40, AT-30A and AT-20, or be the commercially available product of SS-25 and SS-30 purchased from the trade mark of Shandong Bai Te novel material company limited.And, the consumption of cilicon oxide filler is to calculate with the weight of silicon oxide itself, for example the consumption of nano silicon dioxide sol is to calculate with the amount of the silicon-dioxide in colloidal sol, and the weight with nano silicon dioxide sol is multiplied by the numerical evaluation obtaining after its dioxide-containing silica percentage ratio (weight).
According to the preparation method of chromium-free passivation liquid provided by the invention, wherein, described water-soluble film-forming resin can be for various water miscible and can be used in modification or the unmodified resin of film forming, described resin can be used with suitable goods form, water-soluble emulsion for example, at least one in water-soluble solution and water-soluble solid, the present invention does not have special requirement, as long as the film forming of can be used in, for example, described water-soluble film-forming resin can be the water-soluble polyester film-forming resin (water-soluble film-forming resin being obtained by polyalcohols monomer and polynary acids monomer polymerization, for example, purchased from Guangzhou Lapo Fine Chemicals Co., Ltd., the vibrin of trade mark CB2200), water-soluble phenylpropyl alcohol film-forming resin (by styrene monomer and vinylformic acid (ester) class monomer polymerization and water-soluble film-forming resin, for example, purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is the benzene emulsion of xy-108b), soluble epoxide film-forming resin (the water-soluble film-forming resin being obtained by the monomer polymerization that contains epoxy group(ing), for example, purchased from Dongguan City Heima Chemical Co., Ltd., the trade mark is the epoxy resin of BH620), aqurous ployurethane film-forming resin (by multicomponent isocyanate class monomer and multi-hydroxy compounds monomer polymerization and water-soluble film-forming resin, for example, purchased from Jinjiang, Fujian Province Jian Hua company, the urethane resin of the trade mark 812), water-soluble silicon the third film-forming resin (by silicone based monomer and vinylformic acid (ester) class monomer polymerization and water-soluble film-forming resin, the Qingdao paint company TC-05 type organosilicon crylic acid latex of making the country prosperous for example, solid content is 48 % by weight), water-soluble acrylic film-forming resin (the water-soluble film-forming resin being obtained by vinylformic acid (ester) class monomer polymerization, the acrylic resin that is for example A-3418 purchased from the trade mark of Guangzhou Ou Peng chemical industry) and the water-soluble fluorine carbon film-forming resin (water-soluble film-forming resin being obtained by fluorinated monomer polymerization, for example, purchased from Beijing Shouchuang Nano Techn Co., Ltd., the trade mark is the water-base fluorocarbon emulsion of SKFT-I) at least one, under preferable case, described water-soluble film-forming resin is at least one in water-soluble phenylpropyl alcohol film-forming resin, soluble epoxide film-forming resin, water-soluble silicon the third film-forming resin, water-soluble acrylic film-forming resin, aqurous ployurethane film-forming resin and water-soluble polyester film-forming resin.More preferably, wherein, described water-soluble silicon the third film-forming resin is Silomer8861 emulsion (purchased from Richdale Special Chemicals Inc., Rui De special chemical company).
According to the preparation method of chromium-free passivation liquid provided by the invention, wherein, in order further to improve the lubricity of the protective film forming, under preferable case, this preparation method also comprises: the material after water and silane coupling agent are mixed mixes with lubricating auxiliary agent, one or more in the water-based emulsion that described lubricating auxiliary agent is dimethyl silicone oil, polyether-modified polysiloxane, the water-based emulsion of polyethylene wax and the water-based emulsion of oxidized polyethlene wax.
More preferably, with respect to the described water-soluble silicate of 1 weight part, the content of described lubricating auxiliary agent is 0.2-1.8 weight part, more preferably 0.5-0.7 weight part.
Wherein, the solid content of the water-based emulsion of described dimethyl silicone oil can be 10-90 % by weight, is preferably 30-80 % by weight.It should be noted that, the water-based emulsion of dimethyl silicone oil is when preparing chromium-free passivation liquid provided by the invention, and its consumption refers to that the gross weight of water-based emulsion is multiplied by the numerical value obtaining after its solid content.It should be noted that, the solid content of the water-based emulsion of described dimethyl silicone oil refers to the content of the dimethyl silicone oil that the water-based emulsion of the described dimethyl silicone oil of preparation is used.Described dimethyl silicone oil refers to water-insoluble unmodified dimethyl silicone oil.
Wherein, the dimethyl-silicon oil viscosity in the water-based emulsion of described dimethyl silicone oil can be 500-50000mPas, is preferably 1000-40000mPas, more preferably 1500-30000mPas.
Wherein, described polyether-modified polysiloxane is commonly called as water-soluble dimethyl silicone oil, and existing various water-soluble dimethyl silicone oil all can be used for realizing object of the present invention as described lubricating auxiliary agent in the present invention.Preferably described polyether-modified polysiloxane is that viscosity is 100-10000mPas, is preferably 500-8000mPas, and 1000-6000mPas more preferably is further preferably the water-soluble dimethyl silicone oil of 2000-5000mPas.
It should be noted that, in the present invention, do not do in the situation of contrary explanation, described viscosity refers to the apparent viscosity numerical value recording at 25 ℃.
Wherein, the water-based emulsion of described polyethylene wax can be according to ordinary method by the water-based emulsion obtaining after polyethylene wax emulsification, the solid content of the water-based emulsion of described polyethylene wax can be 30-60 % by weight, is preferably 40-50 % by weight.It should be noted that, the water-based emulsion of polyethylene wax is when preparing chromium-free passivation liquid provided by the invention, and its consumption refers to that the gross weight of water-based emulsion is multiplied by the numerical value obtaining after its solid content.
Wherein, the fusing point of the polyethylene wax in the water-based emulsion of described polyethylene wax can be 90-130 ℃, is preferably 100-120 ℃, more preferably 105-115 ℃.
Wherein, the water-based emulsion of described oxidized polyethlene wax can be according to ordinary method by the water-based emulsion obtaining after oxidized polyethlene wax emulsification, the solid content of the water-based emulsion of described oxidized polyethlene wax can be 30-60 % by weight, is preferably 40-50 % by weight.It should be noted that, the water-based emulsion of oxidized polyethlene wax is when preparing chromium-free passivation liquid provided by the invention, and its consumption refers to that the gross weight of water-based emulsion is multiplied by the numerical value obtaining after its solid content.
Wherein, the fusing point of the oxidized polyethlene wax in the water-based emulsion of described oxidized polyethlene wax can be 80-120 ℃, is preferably 90-115 ℃, more preferably 100-110 ℃.
It should be noted that, in the present invention, do not do in the situation of contrary explanation, the fusing point of polyethylene wax and oxidized polyethlene wax refers to the numerical value of measuring according to mensuration-cooling curve method of GB/T2539-2008 petroleum wax fusing point.
Wherein, the acid number of the oxidized polyethlene wax in the water-based emulsion of described oxidized polyethlene wax can be 5-60mgKOH/g, is preferably 10-50mgKOH/g.Wherein, described acid number is the numerical value of measuring according to GB/T264-83 petroleum product acid value measuring method.
The present invention also provides the chromium-free passivation liquid preparing according to preparation method as above.Wherein, in preparation method as above, obtain added water-soluble film-forming resin and mix after material (that is the uniform liquid E, obtaining) can be used as chromium-free passivation liquid of the present invention and use.
In addition, chromium-free passivation liquid of the present invention can also contain other various components that do not affect chromium-free passivation liquid character, as one or more in dyestuff, pigment, dispersion agent and defoamer.The gross weight of this chromium-free passivation liquid of take is benchmark, and the content of other component is no more than 20 % by weight, is preferably no more than 10 % by weight.Described defoamer can be various defoamer well known in the art, such as one or more in polyethers defoamer, higher alcohols defoamer and silicon defoamer etc.More particularly, described defoamer can be for being purchased one or more in the SD-401 of limited liability company of the large Creative Science and Technology Co. Ltd of Dongying dan for example series defoamer.Under preferable case, the total amount of described chromium-free passivation liquid of take is benchmark, and the content of described defoamer is 0.01-0.05 % by weight.
Correspondingly, the preparation method of chromium-free passivation liquid provided by the invention can also comprise and adds other the various component of chromium-free passivation liquid character steps that mix of not affecting.These other various components that do not affect chromium-free passivation liquid character can add after adding water-soluble film-forming resin again.
Chromium-free passivation liquid of the present invention can directly be used without dilution.
The present invention also provides the purposes of above-mentioned chromium-free passivation liquid in preparing metallic substance.Above-mentioned chromium-free passivation liquid can be in the mode of this area routine for the preparation of various metallic substance.
According to metallic substance provided by the invention, this metallic substance comprises pot galvanize metal base and is attached to the coating on this metal base, described metal base is at least one in pot galvanize metal base, hot-dip aluminizing zinc metal base and hot-dip aluminizing zinc magnesium metal base material, it is characterized in that the cured product that described coating is chromium-free passivation liquid as above.
Wherein, described pot galvanize metal base can be for containing the metal base of zinc coating, and in described zinc coating, the content of zinc can be 92.5-95.5 % by weight.Described zinc coating also can contain other conventional ingredient, as silicon.
Wherein, described hot-dip aluminizing zinc metal base can be for containing the metal base of zinc-aluminium coating, and in described zinc-aluminium coating, the content of zinc can be 41.5-43.5 % by weight, and the content of aluminium can be 51.5-55.0 % by weight.Described zinc-aluminium coating also can contain other conventional ingredient, as silicon.
Wherein, hot-dip aluminizing zinc magnesium metal base material can be for containing the metal base of aluminium zinc-magnesium coating, and in described aluminium zinc-magnesium coating, the content of zinc can be 85.5-99.2 % by weight, and the content of aluminium can be 0.2-11 % by weight, and the content of magnesium can be 0.5-3 % by weight.Described aluminium zinc-magnesium coating also can contain other conventional ingredient, as silicon.
According to metallic substance provided by the invention, wherein, the thickness of described coating can be the conventional thickness of the erosion shield on metal base, in order to improve the performance of described coating, under preferable case, the thickness of described coating is 0.05-2 micron, can be preferably 0.1-1 micron.Wherein, the thickness of coating is to use XRF(fluorescence spectrophotometer) numerical value measured of survey meter.
According to metallic substance provided by the invention, wherein, the method for adhering to described coating on metal base can comprise described chromium-free passivation liquid is attached on the surface of metal base, then dry, dry temperature can be 60-120 ℃, is preferably 90-110 ℃, and the time can be 0.5-3 second.The consumption of described chromium-free passivation liquid can be determined according to the thickness of coating.
Wherein, described dry method, can be one or more in warm air drying, induction heating and infrared radiation heating.
In the present invention, do not do in the situation of contrary explanation, the volume of all liquid and solid all refers to 20 ℃, the volume that 1 standard atmosphere is depressed.
Below will to the present invention, be explained in further detail by embodiment.
Embodiment 1
By the silane coupling agent (CH of the water of 28 weight parts and 1.6 weight parts
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-570) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid A.
The water-soluble silicate of whole uniform liquid A and 1 weight part (metasilicate pentahydrate sodium, purchased from Qingdao great Run Chemical Co., Ltd.) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid B.
The promotor (thiocarbamide) of whole uniform liquid B and 0.6 weight part is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid C.
By the cilicon oxide filler (nano silicon dioxide sol of whole uniform liquid C and 0.72 weight part, purchased from Shandong Bai Te novel material company limited, the trade mark is SS-30, and weight is in silicon-dioxide) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid D.
By the water-soluble film-forming resin of whole uniform liquid D and 2.4 weight parts (in solid), ((Silomer8861 emulsion is (purchased from Richdale Special Chemicals Inc. for water-soluble silicon the third film-forming resin, Rui De special chemical company, solid content is 43 % by weight))) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid E.Uniform liquid E is the chromium-free passivation liquid of the present embodiment.
Comparative example 1
Method according to embodiment 1 is prepared chromium-free passivation liquid, different is, in mixing container used, first add water, silane coupling agent, water-soluble silicate, promotor, cilicon oxide filler and water-soluble film-forming resin simultaneously, under the stirring velocity of 1500 revs/min, be mixed to again evenly, obtain the chromium-free passivation liquid of this comparative example.
Comparative example 2
Method according to embodiment 1 is prepared chromium-free passivation liquid, different, and water, water-soluble film-forming resin, water-soluble silicate, promotor, cilicon oxide filler and silane coupling agent are mixed successively, obtains the chromium-free passivation liquid of this comparative example.That is, the application of sample order of silane coupling agent and water-soluble film-forming resin is exchanged.
Comparative example 3
Method according to embodiment 1 is prepared chromium-free passivation liquid, different, and water, silane coupling agent, cilicon oxide filler, promotor, water-soluble silicate and water-soluble film-forming resin are mixed successively, obtains the chromium-free passivation liquid of this comparative example.That is, the application of sample order of water-soluble silicate and cilicon oxide filler is exchanged.
Embodiment 2
By the silane coupling agent (CH of the water of 25 weight parts and 1.4 weight parts
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-570) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid A.
The water-soluble silicate of whole uniform liquid A and 1 weight part (potassium silicate, purchased from Baoding Run Feng Industrial Co., Ltd.) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid B.
The promotor of whole uniform liquid B and 0.5 weight part (thiocarbamide and urea etc. weight mixture) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid C.
The cilicon oxide filler of whole uniform liquid C and 0.6 weight part (nano silicon dioxide sol, purchased from Asahi Denka Co., Ltd., the trade mark is AT-30, weight is in silicon-dioxide) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid D.
By the water-soluble film-forming resin of whole uniform liquid D and 2.1 weight parts (in solid), ((Silomer8861 emulsion is (purchased from Richdale Special Chemicals Inc. for water-soluble silicon the third film-forming resin, Rui De special chemical company, solid content is 43 % by weight))) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid E.Uniform liquid E is the chromium-free passivation liquid of the present embodiment.
Embodiment 3
By the silane coupling agent (CH of the water of 40 weight parts and 1.8 weight parts
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-570) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid A.
The water-soluble silicate of whole uniform liquid A and 1 weight part (metasilicate pentahydrate sodium, purchased from Qingdao great Run Chemical Co., Ltd.) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid B.
The promotor (urea) of whole uniform liquid B and 0.7 weight part is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid C.
The cilicon oxide filler of whole uniform liquid C and 0.85 weight part (nano silicon dioxide sol, purchased from Asahi Denka Co., Ltd., the trade mark is AT-30, weight is in silicon-dioxide) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid D.
By the water-soluble film-forming resin of whole uniform liquid D and 2.7 weight parts (in solid), ((Silomer8861 emulsion is (purchased from Richdale Special Chemicals Inc. for water-soluble silicon the third film-forming resin, Rui De special chemical company, solid content is 43 % by weight))) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid E.Uniform liquid E is the chromium-free passivation liquid of the present embodiment.
Embodiment 4
By the silane coupling agent (CH of the water of 90 weight parts and 0.6 weight part
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-570) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid A.
The water-soluble silicate of whole uniform liquid A and 1 weight part (metasilicate pentahydrate sodium, purchased from Qingdao great Run Chemical Co., Ltd.) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid B.
The promotor (thiocarbamide) of whole uniform liquid B and 0.3 weight part is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid C.
By the cilicon oxide filler (nano silicon dioxide sol of whole uniform liquid C and 2.1 weight parts, purchased from Shandong Bai Te novel material company limited, the trade mark is SS-30, and weight is in silicon-dioxide) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid D.
By the water-soluble film-forming resin of whole uniform liquid D and 6.5 weight parts (in solid), ((Silomer8861 emulsion is (purchased from Richdale Special Chemicals Inc. for water-soluble silicon the third film-forming resin, Rui De special chemical company, solid content is 43 % by weight))) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid E.Uniform liquid E is the chromium-free passivation liquid of the present embodiment.
Embodiment 5
By the silane coupling agent (CH of the water of 15 weight parts and 4.5 weight parts
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3, purchased from Debang Chemical New Material Co., Ltd., trade mark DB-570) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid A.
The water-soluble silicate of whole uniform liquid A and 1 weight part (metasilicate pentahydrate sodium, purchased from Qingdao great Run Chemical Co., Ltd.) is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid B.
The promotor (thiocarbamide) of whole uniform liquid B and 1.7 weight parts is mixed to evenly under the stirring velocity of 1500 revs/min, obtains uniform liquid C.
By the cilicon oxide filler (nano silicon dioxide sol of whole uniform liquid C and 0.3 weight part, purchased from Shandong Bai Te novel material company limited, the trade mark is SS-30, and weight is in silicon-dioxide) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid D.
By the water-soluble film-forming resin of whole uniform liquid D and 1.0 weight parts (in solid), ((Silomer8861 emulsion is (purchased from Richdale Special Chemicals Inc. for water-soluble silicon the third film-forming resin, Rui De special chemical company, solid content is 43 % by weight))) under the stirring velocity of 1500 revs/min, be mixed to evenly, obtain uniform liquid E.Uniform liquid E is the chromium-free passivation liquid of the present embodiment.
Embodiment 6
Method according to embodiment 1 is prepared chromium-free passivation liquid, different, and silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OC
2h
5)
3(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-572).
Embodiment 7
Method according to embodiment 1 is prepared chromium-free passivation liquid, different, and silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3siCH
3(OCH
3)
2(purchased from Debang Chemical New Material Co., Ltd., trade mark DB-571).
Embodiment 8
Method according to embodiment 1 is prepared chromium-free passivation liquid, different, and silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3siCH
3(OC
2h
5)
2(purchased from Rule, Shanghai Chemical trade company limited, trade mark Luer-1512).
Embodiment 9
Method according to embodiment 1 is prepared chromium-free passivation liquid, different is, use water-soluble silicon the third film-forming resin (Qingdao paint company TC-05 type organosilicon crylic acid latex of making the country prosperous, solid content is 48 % by weight) as water-soluble film-forming resin, and (water-based emulsion of dimethyl silicone oil and polyether-modified polysiloxane obtain after 1:1 mixes in the material after water and silane coupling agent are mixed, to add lubricating auxiliary agent, the water-based emulsion of dimethyl silicone oil is purchased from Nanjing Hua Tuo Chemical Co., Ltd., the trade mark is HTR-1, solid content is 30 % by weight, to obtain after the dimethyl silicone oil emulsification that is 25000mPaS by the apparent viscosity at 25 ℃, polyether-modified polysiloxane is purchased from Dongguan Acer dyeing and finishing auxiliaries for textile Co., Ltd., Factory, and the apparent viscosity at 25 ℃ is 3000mPaS) and mix, wherein, with respect to the water-soluble silicate of 1 weight part, the consumption of lubricating auxiliary agent is 0.6 weight part.
Embodiment 10
Method according to embodiment 9 is prepared chromium-free passivation liquid, different, does not add lubricating auxiliary agent.
Embodiment 11
Method according to embodiment 1 is prepared chromium-free passivation liquid, different is, use water-soluble phenylpropyl alcohol film-forming resin (purchased from Guangzhou Chao Long Chemical Industry Science Co., Ltd, the trade mark is the benzene emulsion of xy-108b) as water-soluble film-forming resin, and (water-based emulsion of polyethylene wax and the water-based emulsion of oxidized polyethlene wax obtain after 1:1 mixes in the material after water and silane coupling agent are mixed, to add lubricating auxiliary agent, the water-based emulsion of polyethylene wax is purchased from Dongguan City Hong Guang plastic material business department, solid content is 48 % by weight, the fusing point of polyethylene wax is 110-115 ℃, the water-based emulsion of oxidized polyethlene wax is purchased from Beijing Zhong Guan special wax company limited, solid content is 48 % by weight, the fusing point of oxidized polyethlene wax is 105-110 ℃, acid number is 14-21mgKOH/g) and mix, wherein, with respect to the water-soluble silicate of 1 weight part, the consumption of lubricating auxiliary agent is 0.5 weight part.
Embodiment 12
Method according to embodiment 1 is prepared chromium-free passivation liquid, different is, use soluble epoxide film-forming resin (purchased from Dongguan City Heima Chemical Co., Ltd., the trade mark is the aqueous epoxy resin emulsion of BH620) as water-soluble film-forming resin, and add the lubricating auxiliary agent (water-based emulsion of dimethyl silicone oil in the material after water and silane coupling agent are mixed, purchased from Guangzhou Si Luoke Chemical Co., Ltd., solid content is 80 % by weight, to obtain after the dimethyl silicone oil emulsification that is 1500mPaS by the apparent viscosity at 25 ℃) and mix, wherein, water-soluble silicate with respect to 1 weight part, the consumption of lubricating auxiliary agent is 0.7 weight part.
Embodiment 13
Method according to embodiment 1 is prepared chromium-free passivation liquid, different is, use water-soluble polyester film-forming resin (purchased from Yancheng, Jiangsu Province Ju Ke Chemical Co., Ltd., the trade mark is the waterborne polyester of PE-10030-P) as water-soluble film-forming resin, and add the lubricating auxiliary agent (water-based emulsion of dimethyl silicone oil in the material after water and silane coupling agent are mixed, purchased from Guangzhou Si Luoke Chemical Co., Ltd., solid content is 80 % by weight, to obtain after the dimethyl silicone oil emulsification that is 1500mPaS by the apparent viscosity at 25 ℃) and mix, wherein, water-soluble silicate with respect to 1 weight part, the consumption of lubricating auxiliary agent is 0.7 weight part.
Preparation Example 1
Get the chromium-free passivation liquid that embodiment 1-13 and comparative example 1-3 obtain and be coated on respectively steel plate galvanized (purchased from Pangang Group Panzhihua Steel Vanadium Co., Ltd., model DX54D, in zinc coating containing zinc 95 % by weight) surface, warm air drying is 2 seconds at 90-110 ℃, the steel plate galvanized after being processed respectively.Wherein, coating amount makes the thickness of the coating on the steel plate galvanized after processing be 0.8 micron.The thickness of coating is to use XRF(fluorescence spectrophotometer) numerical value measured of survey meter.Wherein, the chromium-free passivation liquid using in this Preparation Example is all to have stored the chromium-free passivation liquid of 1 day after having prepared (obtaining uniform liquid E).
Preparation Example 2-4
Steel plate galvanized after processing according to the method preparation of Preparation Example 1, different, the chromium-free passivation liquid of use is all to have stored the chromium-free passivation liquid of 60,120 and 180 days after having prepared (obtaining uniform liquid E).
Test implementation example 1
By the requirement of stipulating in GB/T101251997, carry out neutral salt spray test, measure respectively the corrosion resisting property of the steel plate galvanized after the processing of Preparation Example 1-4.It is qualified by " salt-fog test 120h, corrosion area < 3% ", to be considered as.
On M-2000 ring block type friction and wear tester, the kinetic friction coefficient of the coating of the steel plate galvanized after the processing obtaining according to its specification sheets mensuration Preparation Example 1.
Test result as above is as shown in table 1.Number of days in bracket represents the storage time of chromium-free passivation liquid.
Table 1
Visible according to the data of table 1, the solidity to corrosion of the protective film that chromium-free passivation liquid provided by the invention forms is very good, and the storage endurance of chromium-free passivation liquid provided by the invention is also very good.And, visible according to the data of table 1, at the preferred described water-soluble silicate with respect to 1 weight part, the content of described promotor is 0.5-0.7 weight part, and the consumption of described silane coupling agent is 1.4-1.8 weight part, and the consumption of described cilicon oxide filler is 0.6-0.85 weight part, in solid, the consumption of described water-soluble film-forming resin is 2.1-2.7 weight part, and the consumption of water is in the situation of 25-40 weight part, can further improve the solidity to corrosion of the protective film of described chromium-free passivation liquid formation.And, visible according to the data of table 1, in the situation that preferred described water-soluble silicon the third film-forming resin is Silomer8861 emulsion, or preferred described raw mixture also contains in the situation of lubricating auxiliary agent, can further improve the oilness of the protective film that described chromium-free passivation liquid forms.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a preparation method for chromium-free passivation liquid, the method comprises water, silane coupling agent, water-soluble silicate, promotor, cilicon oxide filler and water-soluble film-forming resin is mixed successively; Described silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3, CH
2=C (CH
3) COO (CH
2)
3si (OC
2h
5)
3, CH
2=C (CH
3) COO (CH
2)
3siCH
3(OCH
3)
2and CH
2=C (CH
3) COO (CH
2)
3siCH
3(OC
2h
5)
2in at least one; Described promotor is thiocarbamide and/or urea.
2. preparation method according to claim 1, wherein, described water-soluble silicate with respect to 1 weight part, the consumption of described promotor is 0.2-1.8 weight part, the consumption of described silane coupling agent is 0.5-4.5 weight part, the consumption of described cilicon oxide filler is 0.25-2.2 weight part, in solid, the consumption of described water-soluble film-forming resin is 0.8-6.8 weight part, the consumption of water is 10-100 weight part, preferably, described water-soluble silicate with respect to 1 weight part, the consumption of described promotor is 0.5-0.7 weight part, the consumption of described silane coupling agent is 1.4-1.8 weight part, the consumption of described cilicon oxide filler is 0.6-0.85 weight part, in solid, the consumption of described water-soluble film-forming resin is 2.1-2.7 weight part, the consumption of water is 25-40 weight part.
3. preparation method according to claim 1 and 2, wherein, described silane coupling agent is CH
2=C (CH
3) COO (CH
2)
3si (OCH
3)
3.
4. preparation method according to claim 1 and 2, wherein, described cilicon oxide filler is nano-silica powder and/or nano silicon dioxide sol.
5. according to the described preparation method of claim 1 or 2, wherein, described water-soluble film-forming resin is at least one in water-soluble polyester film-forming resin, water-soluble phenylpropyl alcohol film-forming resin, soluble epoxide film-forming resin, aqurous ployurethane film-forming resin, water-soluble silicon the third film-forming resin, water-soluble acrylic film-forming resin and water-soluble fluorine carbon film-forming resin, wherein, described water-soluble silicon the third film-forming resin is preferably Silomer8861 emulsion.
6. preparation method according to claim 1 and 2, wherein, this preparation method also comprises: the material after water and silane coupling agent are mixed mixes with lubricating auxiliary agent, described lubricating auxiliary agent is the water-based emulsion of dimethyl silicone oil, one or more in polyether-modified polysiloxane, the water-based emulsion of polyethylene wax and the water-based emulsion of oxidized polyethlene wax, with respect to the described water-soluble silicate of 1 weight part, the consumption of described lubricating auxiliary agent is 0.2-1.8 weight part.
7. the chromium-free passivation liquid that in claim 1-6, the preparation method described in any one prepares.
8. the purposes of chromium-free passivation liquid claimed in claim 7 in preparing metallic substance.
9. a metallic substance, this metallic substance comprises metal base and is attached to the coating on this metal base, described metal base is at least one in pot galvanize metal base, hot-dip aluminizing zinc metal base and hot-dip aluminizing zinc magnesium metal base material, it is characterized in that the cured product that described coating is chromium-free passivation liquid claimed in claim 7.
10. metallic substance according to claim 9, wherein, the thickness of described coating is 0.1-1 micron.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105803435A (en) * | 2016-05-03 | 2016-07-27 | 太仓市武锋金属制品有限公司 | Chromate-free passivation process of environment-friendly steel flywheel |
| EP3059277A1 (en) * | 2015-02-23 | 2016-08-24 | Enthone, Incorporated | Inhibitor composition for racks when using chrome free etches in a plating on plastics process |
| CN106086392A (en) * | 2016-07-13 | 2016-11-09 | 湘潭大学 | A kind of for suppressing the passivator of oxidation of pyrite and processing pyritous method based on passivator |
| CN106480443A (en) * | 2016-12-02 | 2017-03-08 | 兰州理工大学 | A kind of processing method enabling aluminum alloy to the golden yellow passivating film of surface acquisition |
| CN108004536A (en) * | 2017-11-22 | 2018-05-08 | 无锡伊佩克科技有限公司 | A kind of chrome-free tanning agent and preparation method thereof |
| CN109136896A (en) * | 2017-06-19 | 2019-01-04 | 镇江瑞德新材料科技研发有限公司 | A kind of preparation method of chromium-free passivation liquid |
| CN109763121A (en) * | 2019-03-15 | 2019-05-17 | 武汉迪赛环保新材料股份有限公司 | A kind of effective aqueous chromium-free passivator of hot-galvanized steel and preparation method thereof |
| CN109763086A (en) * | 2019-03-15 | 2019-05-17 | 武汉迪赛环保新材料股份有限公司 | A kind of manufacturing method of environment-friendly type hot galvanized steel pipe |
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| CN1730570A (en) * | 2005-08-02 | 2006-02-08 | 陈国军 | High temperature energy-saving corrosion-resisting paint , preparation and usage |
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2013
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1730570A (en) * | 2005-08-02 | 2006-02-08 | 陈国军 | High temperature energy-saving corrosion-resisting paint , preparation and usage |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3059277A1 (en) * | 2015-02-23 | 2016-08-24 | Enthone, Incorporated | Inhibitor composition for racks when using chrome free etches in a plating on plastics process |
| CN105803435A (en) * | 2016-05-03 | 2016-07-27 | 太仓市武锋金属制品有限公司 | Chromate-free passivation process of environment-friendly steel flywheel |
| CN106086392A (en) * | 2016-07-13 | 2016-11-09 | 湘潭大学 | A kind of for suppressing the passivator of oxidation of pyrite and processing pyritous method based on passivator |
| CN106086392B (en) * | 2016-07-13 | 2017-10-31 | 湘潭大学 | A kind of passivator for being used to suppress oxidation of pyrite and the method that pyrite is handled based on passivator |
| CN106480443A (en) * | 2016-12-02 | 2017-03-08 | 兰州理工大学 | A kind of processing method enabling aluminum alloy to the golden yellow passivating film of surface acquisition |
| CN106480443B (en) * | 2016-12-02 | 2018-10-12 | 兰州理工大学 | A kind of processing method for enabling aluminum alloy to surface and obtaining golden yellow passivating film |
| CN109136896A (en) * | 2017-06-19 | 2019-01-04 | 镇江瑞德新材料科技研发有限公司 | A kind of preparation method of chromium-free passivation liquid |
| CN108004536A (en) * | 2017-11-22 | 2018-05-08 | 无锡伊佩克科技有限公司 | A kind of chrome-free tanning agent and preparation method thereof |
| CN109763121A (en) * | 2019-03-15 | 2019-05-17 | 武汉迪赛环保新材料股份有限公司 | A kind of effective aqueous chromium-free passivator of hot-galvanized steel and preparation method thereof |
| CN109763086A (en) * | 2019-03-15 | 2019-05-17 | 武汉迪赛环保新材料股份有限公司 | A kind of manufacturing method of environment-friendly type hot galvanized steel pipe |
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