CN102775833B - Nanometer oxide coated phosphate rust resisting pigment and preparation method thereof - Google Patents
Nanometer oxide coated phosphate rust resisting pigment and preparation method thereof Download PDFInfo
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- CN102775833B CN102775833B CN201210295743.7A CN201210295743A CN102775833B CN 102775833 B CN102775833 B CN 102775833B CN 201210295743 A CN201210295743 A CN 201210295743A CN 102775833 B CN102775833 B CN 102775833B
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Abstract
The invention discloses a nanometer oxide coated phosphate rust resisting pigment which is a composite rust resisting pigment formed by coating a nanometer-scale oxide on micron-scale phosphate, wherein the weight ratio of the nanometer-scale oxide to the micron-scale phosphate is (1-10):100. The preparation of the nanometer oxide coated phosphate rust resisting pigment comprises the following steps of: A, preparing calcium phosphate through carrying out liquid phase reaction on a calcium-containing compound and phosphoric acid; B, adding a titanyl sulfate or zinc sulfate solution into a calcium phosphate solution, mixing evenly, then stirring and slowly dripping calcium hydroxide emulsion into the mixture to generate nanometer titanium dioxide or nanometer zinc oxide which is coated on the surface of the calcium phosphate; and C, filtering the reaction solution and drying and roasting a filter cake to obtain the nanometer oxide coated phosphate rust resisting pigment. The rust resisting pigment provided by the invention has the advantages of excellent metal rust resisting property and very low cost.
Description
Technical field
The present invention relates to metal rust preventing technical field, especially a kind of rust-stabilising pigment.
Background technology
The financial loss that the whole world causes because of metallic corrosion every year up to 7,000 hundred million dollars, higher than the summation of the lose from natural calamity such as earthquake, fire, typhoon.In China, the loss caused due to metallic corrosion is also huge, accounts for 4% of gross national product.In order to prevent metal from corroding, diversified safeguard procedures can be adopted as biology measure, metallurgy, electrochemistry measure and coating protection measure.Be wherein one of method preventing metallic corrosion effective, the most the most frequently used at metallic surface coating erosion shield, this is because adopt coating protection suitability strong, both economical, in addition, the effects such as protection and decoration can be combined.
Selected resin system is not only depended in coating protection metallic corrosion, and also depend on selected rust-stabilising pigment to a great extent, therefore, the antiseptic property of coating is the mutual coefficient result of resin system and rust-stabilising pigment simultaneously.Rust-stabilising pigment is in the market of a great variety, substantially can be divided into inertia rust-stabilising pigment (shielding pigment), sacrificial pigment, active rust-stabilising pigment three major types:
What 1, inert pigment played is physical action, and it can strengthen the shielding effect of film, and in general, they are being chemically inertia;
2, sacrificial pigment is metallic pigment, belongs to the special class in reactive pigment, is sprayed on iron dust base material, plays rustless property by galvanic protection effect;
3, reactive pigment prevents metallic corrosion by chemistry and (or) electrochemical action, is the main flow of rust-stabilising pigment, the present invention just belongs to this type of.
Reactive pigment is directly or by intermediate and metal base generation interaction with slowing down corrosion, and they have the pH value maintaining coating, the effect that saponification reaction and passive metal occur.The kind of active rust-stabilising pigment has a lot, mainly comprises: lead pigment (as red lead), chromate pigments (as zinc-chrome yellow, lead-chrome yellow etc.), phosphoric acid salt, molybdate, metaborate etc.
For a long time, leaded, the chromium (VI) that coatings industry uses etc. the rust-stabilising pigment of toxic heavy metal although there is excellent rustless property, but its toxicity is large, color dark, and the rust-proofing primer of configuration needs the finish paint of high covering power supporting, brings very large difficulty to the deep processing of paint industry.In addition, poisonous paint film after the gas distributed during welding and cutting after the dust produced in the three wastes that leaded, chromium (VI) pigment produces in production process, painting process, metallized paint and coating damage etc. all can cause serious harm and pollution to human body and environment, therefore, the manufacture and usage of this kind of pigment is progressively restricted.Along with world community environmental legislation, legislation on labour protection and industrial hygiene standard increasingly strict and perfect, seek the ecological rust-stabilising pigment of nontoxic or low toxicity and progressively replace the common recognition that traditional poisonous rust-stabilising pigment has become people.
British scholar Coslett T W. in 1906 is to prevent from for the purpose of iron and steel from getting rusty, having invented the treating method using phosphoric acid salt as rust-preventive agent.Nineteen fifty-nine Britain Harrison J B. etc. has carried out industrial performance test to zinc phosphate rust-preventive pigment first.Japan in 1972 is that opportunity brings into use poly aluminium phosphate series non-poisonous antirust pigment to substitute containing poisonous pigment such as chromium, plumbous chromic salt and red leads with pollution problem, promotes the use of gradually in countries such as China, West Europe, the U.S. later.Up to now, the multiple pigment such as phosphate-based, molybdate series, the borate series of development, wherein all occupy larger advantage with series of phosphate pigment with regard to the research in its kind, performance and use range, thus become the maximum non-poisonous antirust pigment of consumption.
Several the relevant enterprises that the pigment company of such as Germany, the U.S., Japan and China take as the leading factor with University Of Hebei have released one after another from the later stage eighties in last century the series of new rust-stabilising pigments such as zinc phosphate, modified zinc phosphate, polymer phosphate aluminium, and its rustless property quite or be better than traditional lead system, the poisonous rust-stabilising pigment of chromium system.But the subject matter existed at present is, these phosphoric acid salt rust-stabilising pigment costs are quite high, and (such as zinc phosphate market price is 1.5 ten thousand yuan/ton at present, polymer phosphate aluminium is 1.3 ten thousand yuan/ton), make these non-poisonous antirust pigments widely use and popularization is restricted.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of nano-oxide coated phosphate rust-stabilising pigment, and it not only has excellent metal rust preventing performance, and price is very cheap simultaneously; For this reason, the present invention provides the preparation method of this rust-stabilising pigment simultaneously.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows.
Nano-oxide coated phosphate rust-stabilising pigment, this rust-stabilising pigment is that nano-scale oxide is coated on the Composite Anticorrosive Pigment Using that micron order phosphoric acid salt is formed; Nano-scale oxide and the phosphatic weight ratio of micron order are (1-10): 100.
As a preferred technical solution of the present invention, described oxide compound is titanium dioxide or zinc oxide, and its particle diameter is 2-30nm; Described phosphoric acid salt is calcium phosphate, and its particle diameter is 0.3-5 μm.
The preparation method of above-mentioned nano-oxide coated phosphate rust-stabilising pigment, its step comprises:
A, calcium containing compound and phosphoric acid prepare calcium phosphate by liquid phase reaction;
B, titanyl sulfate or solution of zinc sulfate are joined calcium phosphate emulsion in and stir, then slowly instilled wherein by calcium hydroxide emulsion while stirring, namely the nano titanium oxide of generation or nano zine oxide are coated on calcium phosphate surface;
C, filtering reacting solution, filter cake drying, roasting, to obtain final product.
As a kind of optimal technical scheme of above-mentioned preparation method, the concrete operation method of steps A is:
A-1, take calcium carbonate, calcium hydroxide or calcium oxide, adding water to stir forms homogeneous latex emulsion;
A-2, to measure according to the ratio of mol ratio P:Ca=2:3 85% strong phosphoric acid, add the dilution of double water, stir;
A-3, be slowly added dropwise in the calcium containing compound emulsion of steps A-1 by the phosphoric acid solution of steps A-2, stirring reaction 1-3h, obtains calcium phosphate emulsion.
As a kind of optimal technical scheme of above-mentioned preparation method, the concrete operation method of step B is:
B-1, take titanyl sulfate or zinc sulfate, be dissolved in water for subsequent use; Wherein, the weight ratio of titanyl sulfate or zinc sulfate and steps A gained calcium phosphate is (2-20): 100;
B-2, take calcium hydroxide, adding water, it is for subsequent use to be mixed with emulsion; Wherein, the weight ratio of calcium hydroxide and steps A gained calcium phosphate is (0.1-0.9): 1;
B-3, the titanyl sulfate of step B-1 or solution of zinc sulfate are joined steps A calcium phosphate emulsion in and stir, then slowly instilled wherein by the calcium hydroxide emulsion of step B-2 while stirring, namely the nano titanium oxide of generation or nano zine oxide are coated on calcium phosphate surface.
As a kind of optimal technical scheme of above-mentioned preparation method, in step C, bake out temperature is 100 DEG C, and maturing temperature is 300 DEG C, and roasting time is 0.5-2h.
The beneficial effect adopting technique scheme to produce is:
1. the analysis summary of beneficial effect of the present invention: analyze theoretically and find in the process preparing rust proof paint, " compound " of rust-stabilising pigment and " collocation " impact on film performance of pigment particle size are very important.If select 2 kinds or material of more than two kinds, wherein a kind of can select particle diameter more greatly and more cheap pigment as major ingredient, another kind of or severally material that particle diameter is relatively little can be selected as disperse phase auxiliary material, so both can reach material " compound ", the object of particle diameter " collocation " can have been reached again.In metal rust preventing system, mainly stop oxygen, water and chlorion to the oxidation corrosion of metal with coating, blocks current flow is to the galvanic corrosion of metal.If by nano material as disperse phase, be distributed in coating with rational proportioning, the performance of this coating is bound to exceed the performance of conventional coating.Obviously, use nanotechnology, by composite modified development nontoxic, rust-stabilising pigment that the ratio of performance to price is high is feasible.Because nano material has unique performance, nano material is used in coating, it can be made to obtain multiple special performance, as improved ageing resistance, erosion resistance, the radioresistance of coating, the sticking power, intensity, hardness, wear resistance etc. of coating can also be improved further, thus substantially increase the performance of traditional coating.The present invention, first by the series of calcium phosphate non-poisonous antirust pigment intermediate that chemical precipitation method preparation is cheap, then adopts chemical coprecipitation technique at surface of pigments clad nano TiO
2or nano-ZnO coating, make Composite Anticorrosive Pigment Using.
2. the checking of beneficial effect of the present invention: painting experiment proves, nano combined series of phosphate rust-stabilising pigment prepared by the present invention is cost low (about 3,000 yuan/ton) not only, and be all up to state standards with the indices that it prepares rust proof paint, especially salt spray resistance one (rustless property key index), not only be better than the zinc phosphate pigment that existing market is sold, and be better than the ZPA rust-stabilising pigment of Germany; Concrete test data sees the following form;
The rustless property test result of table 1. rust-stabilising pigment of the present invention
In addition, referring to accompanying drawing 1, for the embodiment of the present invention prepares the stereoscan photograph of sample, can see from photo, the particle diameter of main body calcium phosphate pigment is about 1-3 micron (nano-oxide is coated to be attached on calcium phosphate).
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of sample prepared by the embodiment of the present invention 1.
Embodiment
Following examples describe the present invention in detail.Various raw material used in the present invention and items of equipment are conventional commercial product, all can be bought by market and directly obtain.
Embodiment 1
The preparation method of rust-stabilising pigment of the present invention:
1: take 22.3g calcium hydroxide ［ Ca (OH)
2, slowly add 200ml water, fully stir, until emulsification is even.
2: measure the strong phosphoric acid 14ml that concentration is 85%, slowly add 28ml water, stir.
3: in stirring, the phosphoric acid after dilution is slowly added drop-wise in calcium hydroxide emulsion.After dropping terminates, continue stirring reaction under normal temperature and stop for 2 hours, obtain calcium phosphate intermediate emulsion.
4: by titanyl sulfate (TiOSO
4) 3.2g adds in 100ml water, for subsequent use after dissolving.
5: take calcium hydroxide 2.86g, adding 50ml water, to stir into emulsion for subsequent use.
6: the titanyl sulfate solution prepared in step 4 is added in the obtained calcium phosphate intermediate emulsion of step 3, instill while stirring after mixing system in step 5 calcium hydroxide emulsion, make the coated by titanium dioxide of generation on calcium phosphate surface.
7: filter, filter cake is dried at 100 DEG C.Put into retort furnace again and carry out roasting 1h in 300 DEG C, both obtain nano-TiO
2coated calcium phosphate Composite Anticorrosive Pigment Using.
Embodiment 2
The preparation method of rust-stabilising pigment of the present invention:
1: take 30g calcium carbonate ［ CaCO
3, slowly add 200ml water, fully stir, until emulsification is even.
2: measure the strong phosphoric acid 14ml that concentration is 85%, slowly add 28ml water, stir.
3: in stirring, the phosphoric acid after dilution is slowly added drop-wise in calcium hydroxide emulsion.After dropping terminates, continue stirring reaction under normal temperature and stop for 2 hours, obtain calcium phosphate intermediate emulsion.
4: by titanyl sulfate (TiOSO
4) 3.2g adds in 100ml water, for subsequent use after dissolving.
5: take calcium hydroxide 2.86g, adding 50ml water, to stir into emulsion for subsequent use.
6: the titanyl sulfate solution prepared in step 4 is added in the obtained calcium phosphate intermediate emulsion of step 3, instill while stirring after mixing system in step 5 calcium hydroxide emulsion, make the coated by titanium dioxide of generation on calcium phosphate surface.
7: filter, filter cake is dried at 100 DEG C.Put into retort furnace again and carry out roasting 1h in 300 DEG C, both obtain nano-TiO
2coated calcium phosphate Composite Anticorrosive Pigment Using.
Embodiment 3
The preparation method of rust-stabilising pigment of the present invention:
1: take 16.8g calcium oxide ［ CaO ］, slowly add 200ml water, fully stir, until emulsification is even.
2: measure the strong phosphoric acid 14ml that concentration is 85%, slowly add 28ml water, stir.
3: in stirring, the phosphoric acid after dilution is slowly added drop-wise in calcium hydroxide emulsion.After dropping terminates, continue stirring reaction under normal temperature and stop for 2 hours, obtain calcium phosphate intermediate emulsion.
4: by titanyl sulfate (TiOSO
4) 3.2g adds in 100ml water, for subsequent use after dissolving.
5: take calcium hydroxide 2.86g, adding 50ml water, to stir into emulsion for subsequent use.
6: the titanyl sulfate solution prepared in step 4 is added in the obtained calcium phosphate intermediate emulsion of step 3, instill while stirring after mixing system in step 5 calcium hydroxide emulsion, make the coated by titanium dioxide of generation on calcium phosphate surface.
7: filter, filter cake is dried at 100 DEG C.Put into retort furnace again and carry out roasting 1h in 300 DEG C, both obtain nano-TiO
2coated calcium phosphate Composite Anticorrosive Pigment Using.
Embodiment 4
The preparation method of rust-stabilising pigment of the present invention:
1: take 22.3g calcium hydroxide ［ Ca (OH)
2, slowly add 200ml water, fully stir, until emulsification is even.
2: measure the strong phosphoric acid 14ml that concentration is 85%, slowly add 28ml water, stir.
3: in stirring, the phosphoric acid after dilution is slowly added drop-wise in calcium hydroxide emulsion.After dropping terminates, continue stirring reaction under normal temperature and stop for 2 hours, obtain calcium phosphate intermediate emulsion.
4: by zinc sulfate (ZnSO
4) 3.2g adds in 100ml water, for subsequent use after dissolving.
5: take calcium hydroxide 2.86g, adding 50ml water, to stir into emulsion for subsequent use.
6: the titanyl sulfate solution prepared in step 4 is added in the obtained calcium phosphate intermediate emulsion of step 3, instill while stirring after mixing system in step 5 calcium hydroxide emulsion, make the coated by titanium dioxide of generation on calcium phosphate surface.
7: filter, filter cake is dried at 100 DEG C.Put into retort furnace again and carry out roasting 1h in 300 DEG C, both obtain nano-TiO
2coated calcium phosphate Composite Anticorrosive Pigment Using.
Foregoing description only proposes, not as the single restricted condition to its technical scheme itself as the enforceable technical scheme of the present invention.Except clad nano titanium dioxide, nano zine oxide, this technology can also be utilized at phosphate pigment Surface coating nano-sized iron oxide, nano silicon oxide, a series of nano material of rare-earth nano oxide etc.
Claims (5)
1. nano-oxide coated phosphate rust-stabilising pigment, is characterized in that: this rust-stabilising pigment is that nano-scale oxide is coated on the Composite Anticorrosive Pigment Using that micron order phosphoric acid salt is formed; Nano-scale oxide and the phosphatic weight ratio of micron order are (1-10): 100;
Described oxide compound is titanium dioxide or zinc oxide, and its particle diameter is 2-30nm; Described phosphoric acid salt is calcium phosphate, and its particle diameter is 0.3-5 μm.
2. the preparation method of nano-oxide coated phosphate rust-stabilising pigment according to claim 1, its characterization step comprises:
A, calcium containing compound and phosphoric acid prepare calcium phosphate by liquid phase reaction;
B, titanyl sulfate or solution of zinc sulfate are joined calcium phosphate emulsion in and stir, then slowly instilled wherein by calcium hydroxide emulsion while stirring, namely the nano titanium oxide of generation or nano zine oxide are coated on calcium phosphate surface;
C, filtering reacting solution, filter cake drying, roasting, to obtain final product.
3. the preparation method of nano-oxide coated phosphate rust-stabilising pigment according to claim 2, is characterized in that: the concrete operation method of steps A is:
A-1, take calcium carbonate, calcium hydroxide or calcium oxide, adding water to stir forms homogeneous latex emulsion;
A-2, to measure according to the ratio of mol ratio P:Ca=2:3 85% strong phosphoric acid, add the dilution of double water, stir;
A-3, be slowly added dropwise in the calcium containing compound emulsion of steps A-1 by the phosphoric acid solution of steps A-2, stirring reaction 1-3h, obtains calcium phosphate emulsion.
4. the preparation method of nano-oxide coated phosphate rust-stabilising pigment according to claim 2, is characterized in that: the concrete operation method of step B is:
B-1, take titanyl sulfate or zinc sulfate, be dissolved in water for subsequent use; Wherein, the weight ratio of titanyl sulfate or zinc sulfate and steps A gained calcium phosphate is (2-20): 100;
B-2, take calcium hydroxide, adding water, it is for subsequent use to be mixed with emulsion; Wherein, the weight ratio of calcium hydroxide and steps A gained calcium phosphate is (0.1-0.9): 1;
B-3, the titanyl sulfate of step B-1 or solution of zinc sulfate are joined steps A calcium phosphate emulsion in and stir, then slowly instilled wherein by the calcium hydroxide emulsion of step B-2 while stirring, namely the nano titanium oxide of generation or nano zine oxide are coated on calcium phosphate surface.
5. the preparation method of nano-oxide coated phosphate rust-stabilising pigment according to claim 2, it is characterized in that: in step C, bake out temperature is 100 DEG C, and maturing temperature is 300 DEG C, and roasting time is 0.5-2h.
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| CN105440740A (en) * | 2015-12-15 | 2016-03-30 | 上海纳旭实业有限公司 | Preparation method of nanometer aluminum triphosphate-titanium dioxide composite dispersion liquid for anticorrosion paint |
| CN105400266A (en) * | 2015-12-15 | 2016-03-16 | 上海纳旭实业有限公司 | Preparation method for nano zinc phosphate-titanium dioxide composite dispersion liquid for anticorrosive paint |
| CN106590034B (en) * | 2016-12-13 | 2019-01-01 | 广西壮族自治区化工研究院 | A kind of phosphite powder of nano-oxide inorganic coating and water paint containing the powder |
| CN108986950B (en) * | 2018-06-28 | 2019-11-12 | 浙江加州国际纳米技术研究院台州分院 | A kind of preparation method of phosphate/nano silver composite conductive powder |
| CN110066528A (en) * | 2019-06-08 | 2019-07-30 | 华东理工大学 | A kind of weather-proof inhibition integration composite pigment |
| CN111154291A (en) * | 2019-12-22 | 2020-05-15 | 贵州师范学院 | Surface modifier modified zinc phosphate antirust pigment |
| CN111484775A (en) * | 2020-06-17 | 2020-08-04 | 福建佳辉塑粉有限公司 | Epoxy anticorrosive antibacterial powder coating special for valve fire protection and preparation method thereof |
| CN112175432A (en) * | 2020-10-16 | 2021-01-05 | 北京航天赛德科技发展有限公司 | Composite anticorrosive pigment and preparation method and application thereof |
| CN112251106B (en) * | 2020-10-16 | 2022-04-08 | 北京航天赛德科技发展有限公司 | Composite anticorrosive paint and application thereof |
| CN112251063B (en) * | 2020-10-16 | 2022-04-08 | 北京航天赛德科技发展有限公司 | Preparation method and application of composite anticorrosive paint |
| CN112391101A (en) * | 2020-11-13 | 2021-02-23 | 阜南县大自然工艺品股份有限公司 | Antirust spray paint for protecting iron braided product and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101045828A (en) * | 2006-07-03 | 2007-10-03 | 张义纲 | Phosphate film-coated powder and preparation method thereof |
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| JP2986962B2 (en) * | 1991-05-20 | 1999-12-06 | テイカ株式会社 | Rust preventive pigment composition and paint containing the same |
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