CN103938198A - Phosphorus-free nano vitrification agent, and preparation method and application thereof - Google Patents
Phosphorus-free nano vitrification agent, and preparation method and application thereof Download PDFInfo
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- CN103938198A CN103938198A CN201410166953.5A CN201410166953A CN103938198A CN 103938198 A CN103938198 A CN 103938198A CN 201410166953 A CN201410166953 A CN 201410166953A CN 103938198 A CN103938198 A CN 103938198A
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Abstract
The invention relates to the field of metal surface treatment agents, and relates to a phosphorus-free nano vitrification agent, and a preparation method and application thereof. The phosphorus-free nano vitrification agent is prepared from the following raw materials in percentage by mass: 3-6% of fluorozirconic acid, 3-7% of zirconium oxychloride, 0.1-0.6% of ammonium fluozirconate, 0.8-2% of tartaric acid, 0.5-1% of sodium nitrate and the balance of water. The phosphorus-free nano vitrification agent provided by the invention can be operated at normal temperature, and is short in treatment time and simple in process; almost no deposit exists, and nozzle blocking is avoided; the waste treatment cost is reduced; and the adhesive force between paint and metal can be obviously improved, and the corrosion resistance time of the metal can be prolonged.
Description
Technical field
The present invention the present invention relates to metal conditioner field, is exactly a kind of phosphate-free metal surface treatment agent, preparation method and application thereof.
Background technology
Increasingly important along with environmental requirement, traditional phosphating process is phosphorous, nickel and sediment are processed problem, cannot meet gradually the demand of modern environmental protection, a new generation's Phosphateless environmentally friendly conversion process can form in metallic surface nano level film, have the application sticking power of enhancing and corrosion-resistant function, can process iron and steel, zinc, aluminium and alloy material thereof is the good selection that substitutes conventional phosphatizing treatment process.Current without phosphorus conversion film product, actual application in the industry such as automobile, household electrical appliances, the product of without phosphorus conversion film becomes the emphasis of the front metal finishing related industries development of following whole each application gradually, brings a new ripple development climax for substituting conventional phosphatizing technology.
Chinese patent CN 102586769A discloses a kind of phosphate-free metal surface treatment agent and using method thereof, component by following weight parts forms: 5～20 parts of the nano zirconium dioxide dispersion liquids that concentration is 28%, 6～30 parts, hydrofluoric acid, 3～15 parts of propylene glycol, eight 6～20 parts of vinyl cagelike silsesquioxanes, 3～20 parts of acetic acid, 0.03～0.5 part of cerium salt, 1～5 part, sodium hydroxide, 50～76 parts of deionized waters, described a kind of phosphate-free metal surface treatment agent, after being processed, metal can form in metallic surface the without phosphorus conversion composite membrane of nanometer silane.But there is following shortcoming in this patent: cerium salt is containing heavy metal element, thereby this formula do not meet national environmental protection policy, can not in the competition of future market, obtain one seat.
Chinese patent CN 102747355A discloses a kind of metallic surface vitrified agent and using method thereof, metallic surface vitrified agent contains zirconium titanium salt 2.0～38.0%, silane 0.1～8.0%, buffer reagent 0.5～18.0%, film coalescence aid 0.01～5.00%, rust-preventive agent 0.1～6.1%, complexing agent 0.2～7.0%, apparent is as clear as crystal liquid, and no suspended substance; PH value is 1～2; Proportion is 1.05 ± 0.02g/cm
3.Its useful technique effect is under normal temperature state, to generate a kind of embedded property heterozygosis indissoluble nanometer scale ceramics conversion film in metallic surface, has and good anti-impact force, can improve the sticking power of coating, strengthens the erosion resistance of metallic surface.But there is following shortcoming in this patent: in this formula, do not add stablizer, can cause in product use procedure quality often to occur unstable, while even occurring that all technical is in scope, can not form ceramic film in metallic surface.
Chinese patent CN101629286 discloses a kind of vitrified agent, and it becomes the starting material of umber to make by following quality group: titanium zirconium composite: 20～30 parts, and fluorochemical: 5～10 parts, complexing agent: 5～10 parts, water: 40～60 parts.The vitrified agent good stability of making by this patent, without sediment, not phosphate-containing, can on the surface of iron and steel, zinc and aluminium, form one deck vitrification layer, the coating bonding force of itself and each model is strong, be applicable to spray and the immersion treatment of normal temperature, need not heating installation, reach save energy, be easy to the object of producing.But there is following shortcoming in this patent: although this formula can film forming, flying power is limited, that is to say that the cycle of changing groove, again joining groove shortens greatly, so just increased client's use cost, reduced product competitive power in market.
Summary of the invention
One of object of the present invention is to overcome the deficiencies in the prior art, a kind of without phosphorus nanometer vitrified agent is provided, the without phosphorus pre-treating technology of this without phosphorus nanometer vitrified agent, the waste water producing do not contain chromium, nickel and other toxic heavy metals, without nitrite, without phosphoric acid salt and volatility organic component, alleviate wastewater treatment and environmental pressure.
Two of object of the present invention is to provide the preparation method of above-mentioned without phosphorus nanometer vitrified agent.
Three of object of the present invention is to provide the using method of above-mentioned without phosphorus nanometer vitrified agent.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of without phosphorus nanometer vitrified agent, by percentage to the quality, made by following raw material:
Fluorine zirconic acid 3-6%, basic zirconium chloride 3-7%, ammonium fluozirconate 0.1-0.6%, tartrate 0.8-2%, SODIUMNITRATE 0.5-1%, surplus is water.
The wherein said preferred 4-5% of fluorine zirconic acid; The preferred 4-6% of described basic zirconium chloride, the preferred 0.3-0.6% of described ammonium fluozirconate.
The preferred technical scheme of the present invention is: a kind of without phosphorus nanometer vitrified agent, by percentage to the quality, made by following raw material:
Fluorine zirconic acid 5%, basic zirconium chloride 6%, ammonium fluozirconate 0.6%, tartrate 1.5%, SODIUMNITRATE 0.8%, water 86.1%.
The preparation method of the without phosphorus nanometer vitrified agent of the present invention, in turn includes the following steps:
(1) in reactor, add water;
(2) in reactor, add fluorine zirconic acid, then stir;
(3) in reactor, add basic zirconium chloride, then stir, until dissolve completely;
(4) in reactor, add ammonium fluozirconate, stir and make solution clarification;
(5) in reactor, add tartrate, stir and make solution clarification;
(6) in reactor, add SODIUMNITRATE, wait to stir and make solution clarification.
Wherein the churning time of step (2) is 0.5-1.5 hour; The churning time of step (3) is 1-3 hour; The churning time of step (4) is 0.5-1.5 hour; The churning time of step (5) is 0.5-1.5 hour; The churning time of step (6) is 20-40 minutes.
The using method of without phosphorus nanometer vitrified agent of the present invention, is characterized in that by following steps, metal being processed:
(1) degreasing;
(2) twice washing;
(3) without phosphorus nanometer vitrified agent is processed and is transformed, and working temperature is normal temperature, and processing mode is spray or immersion, and the treatment time is 3-5 minute;
(4) twice washing;
(5) dry.
Wherein in step (2) and step (4) washing for the second time of twice washing all preferably pure water wash;
In step (3), the collocation method of without phosphorus nanometer vitrified agent is: 30 kilograms of without phosphorus nanometer vitrified agents, then it is formulated to add 970 kg of water, stirs.
While adopting spray or soaking technology in step (3), processing condition are respectively in table 1.Adopt without phosphorus nanometer vitrified agent of the present invention to process metal, can form the without phosphorus conversion composite membrane of nanometer on its surface.
The without phosphorus nanometer vitrified agent of table 1 is processed smithcraft condition
The present invention has following beneficial effect:
(1) without phosphorus pre-treating technology, the waste water producing do not contain chromium, nickel and other toxic heavy metals, without nitrite, without phosphoric acid salt and volatility organic component, alleviates wastewater treatment and environmental pressure;
(2) have the function that increases coating bonding force, prevents corrosion, alternative conventional iron is phosphatization;
(3) be applicable to iron and steel, zinc, the pre-treatment of aluminium various metals;
(4) under normal temperature, operate, the short treatment time, adjust without surface, in the situation that does not need to change original production unit, use nanometer non-phosphate film agent can save the cost of 15%-30%, and technique is simpler, " table is adjusted " operation can be saved and do not used;
(5) almost there is no sediment, nonchoking nozzle, reduces offal treatment cost;
(6) do not need " Chi Shui " of frequent replacing " phosphorization agent ", when concentration is inadequate, add;
(7) can significantly improve the sticking power of coating and metal, extend the corrosion-resistant time of metal.
Groundwork principle of the present invention is as follows:
Burning is without phosphorus conversion film, that the electrochemical reaction of metal in acidic solution and indifferent oxide colloid are on metal (iron, zinc, aluminium and alloy thereof) surface, cohesion deposition changes into has nano level complex metal oxides rete, and has ZrO
2conversion film processing be at acid H
2zrF
6in solution, carry out, principal reaction is as follows:
Acid etching reaction H
2zrF
6+ Me+2H
2o → ZrO
2+ Me
2++ 4H
++ 6F
++ H
2me:Fe, Zn, Al metal base
The reaction 1. hydrolysis reaction ZrOCl of indifferent oxide
2+ H
2o → ZrO (OH)
2+ 2HCl zirconium hydroxide is a kind of white gels, may be dissolved in diluted acid, and generates colloidal sol
2. polycondensation Me ≡ Zr-OH+HO-Zr ≡ Me → Me ≡ Zr-O-Zr ≡ Me+H
2o
Above-mentioned reaction, according to sol gel processing, forms a kind of ZrO
2-Me-ZrO
2sol particles structure, sol particles has very strong cohesion function.Along with the carrying out of reaction, form gradually three-dimensional netted ZrO
2-Me-ZrO
2collosol structure, cohesion deposition produces has nano level ZrO
2conversion film.
Bath maintenance: at ordinary times by adding, guarantee that tank liquor concentration is normal.Suggestion tank liquor, through circulating filtration equipment mistake, is avoided impurity accumulation.In the time accumulating more impurity in groove, recommended replacement tank liquor.
Embodiment
Embodiment 1
The without phosphorus nanometer vitrified agent of every 1000Kg, made by following raw material:
Fluorine zirconic acid 30 Kg, basic zirconium chloride 30 Kg, ammonium fluozirconate 1 Kg, tartrate 8 Kg, SODIUMNITRATE 5 Kg, water 926 Kg.
Its preparation method in turn includes the following steps:
(in 1 reactor, add water;
(2) in reactor, add fluorine zirconic acid, then stir churning time 1-1.5 hour;
(3) in reactor, add basic zirconium chloride, then stir, until dissolve completely, the time is 1-3 hour;
(4) in reactor, add ammonium fluozirconate, stir and make solution clarification, the time is 0.5-1.5 hour;
(5) in reactor, add tartrate, stir and make solution clarification, the time is 0.5-1.5 hour;
(6) in reactor, add SODIUMNITRATE, wait to stir and make solution clarification, the time is 20-40 minutes;
(7) product is carried out to physical and chemical index detection, packaging warehouse-in.
Without phosphorus nanometer vitrified agent of the present invention is processed metal by following steps:
(1) degreasing;
(2) twice washing;
(3) without phosphorus nanometer vitrified agent is processed and is transformed, and working temperature is normal temperature, and processing mode is for soaking, and the treatment time is 3-5 minute;
(4) twice washing;
(5) dry.
Wherein in step (2) and step (4), the washing for the second time of twice washing all adopts pure water to wash; In step (3), the collocation method of without phosphorus nanometer vitrified agent is: 30 kilograms of without phosphorus nanometer vitrified agents, then it is formulated to add 970 kg of water, stirs.
Embodiment 2
The without phosphorus nanometer vitrified agent of every 1000Kg, made by following raw material:
Fluorine zirconic acid 40 Kg, basic zirconium chloride 40 Kg, ammonium fluozirconate 3 Kg, tartrate 9 Kg, SODIUMNITRATE 6 Kg, water 902 Kg.
Preparation method and metal is carried out to treatment step with embodiment 1.
Embodiment 3
The without phosphorus nanometer vitrified agent of every 1000Kg, made by following raw material:
Fluorine zirconic acid 50 Kg, basic zirconium chloride 50 Kg, ammonium fluozirconate 4 Kg, tartrate 9 Kg, SODIUMNITRATE 7 Kg, water 880 Kg.
Preparation method and metal is carried out to treatment step with embodiment 1.
Embodiment 4
The without phosphorus nanometer vitrified agent of every 1000Kg, made by following raw material:
Fluorine zirconic acid 60 Kg, basic zirconium chloride 50 Kg, ammonium fluozirconate 4 Kg, tartrate 9 Kg, SODIUMNITRATE 7 Kg, water 870 Kg.
Preparation method and metal is carried out to treatment step with embodiment 1.
Embodiment 5
The without phosphorus nanometer vitrified agent of every 1000Kg, made by following raw material:
Fluorine zirconic acid 40 Kg, basic zirconium chloride 60 Kg, ammonium fluozirconate 5 Kg, tartrate 10 Kg, SODIUMNITRATE 7 Kg, water 878 Kg.
Preparation method and metal is carried out to treatment step with embodiment 1.
Preparation method is with embodiment 1.
Embodiment 6
The without phosphorus nanometer vitrified agent of every 1000Kg, made by following raw material:
Fluorine zirconic acid 50 Kg, basic zirconium chloride 60 Kg, ammonium fluozirconate 6 Kg, tartrate 15 Kg, SODIUMNITRATE 8 Kg, water 861 Kg.
Preparation method and metal is carried out to treatment step with embodiment 1.
Embodiment 7
The without phosphorus nanometer vitrified agent of every 1000Kg, made by following raw material:
Fluorine zirconic acid 50 Kg, basic zirconium chloride 60 Kg, ammonium fluozirconate 5 Kg, tartrate 17 Kg, SODIUMNITRATE 9 Kg, water 859 Kg.
Preparation method and metal is carried out to treatment step with embodiment 1.
Embodiment 8
The without phosphorus nanometer vitrified agent of every 1000Kg, made by following raw material:
Fluorine zirconic acid 50 Kg, basic zirconium chloride 40 Kg, ammonium fluozirconate 6 Kg, tartrate 20 Kg, SODIUMNITRATE 10 Kg, water 874 Kg.
Preparation method and metal is carried out to treatment step with embodiment 1.
Embodiment 9
The without phosphorus nanometer vitrified agent of every 1000Kg, made by following raw material:
Fluorine zirconic acid 50 Kg, basic zirconium chloride 40 Kg, ammonium fluozirconate 4 Kg, tartrate 16 Kg, SODIUMNITRATE 6 Kg, water 884 Kg.
Preparation method and metal is carried out to treatment step with embodiment 1.
Embodiment 10
The without phosphorus nanometer vitrified agent of every 1000Kg, made by following raw material:
Fluorine zirconic acid 40 Kg, basic zirconium chloride 50 Kg, ammonium fluozirconate 5 Kg, tartrate 10 Kg, SODIUMNITRATE 9 Kg, water 886 Kg.
Preparation method and metal is carried out to treatment step with embodiment 1.
Embodiment 11
The without phosphorus nanometer vitrified agent of every 1000Kg, made by following raw material:
Fluorine zirconic acid 40 Kg, basic zirconium chloride 70 Kg, ammonium fluozirconate 3 Kg, tartrate 12 Kg, SODIUMNITRATE 8 Kg, water 867 Kg.
Preparation method and metal is carried out to treatment step with embodiment 1.
The formula of embodiment of the present invention 1-6 in Table 2(with the without phosphorus nanometer vitrified agent of 1000Kg), the formula of embodiment 7-11 is in table 3.
The formula of table 2 embodiment 1-6
| Raw material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Fluorine zirconic acid | 30 | 40 | 50 | 60 | 40 | 50 |
| Five nitric hydrate zirconiums | 30 | 40 | 50 | 50 | 60 | 60 |
| Ammonium fluozirconate | 1 | 3 | 4 | 4 | 5 | 6 |
| Tartrate | 8 | 9 | 9 | 9 | 10 | 15 |
| SODIUMNITRATE | 5 | 6 | 7 | 7 | 7 | 8 |
| Water | 926 | 902 | 880 | 870 | 878 | 861 |
The formula of table 3 embodiment 7-11
| Raw material | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 |
| Fluorine zirconic acid | 50 | 50 | 50 | 40 | 40 |
| Five nitric hydrate zirconiums | 60 | 40 | 40 | 50 | 70 |
| Ammonium fluozirconate | 5 | 6 | 4 | 5 | 3 |
| Tartrate | 17 | 20 | 16 | 10 | 12 |
| SODIUMNITRATE | 9 | 10 | 6 | 9 | 8 |
| Water | 859 | 874 | 884 | 886 | 867 |
Embodiment of the present invention 1-6 to the treatment effect of metal in table 4, embodiment 7-11 to the treatment effect of metal in table 5.
The metal treatment effect of table 4 embodiment 1-6
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Treatment time | 4min | 4min | 4min | 4min | 4min | 4min |
| Use temperature | Normal temperature | Normal temperature | Normal temperature | Normal temperature | Normal temperature | Normal temperature |
| Sediment weight after processing | 164mg/㎡ | 158mg/㎡ | 125mg/㎡ | 79mg/㎡ | 101mg/㎡ | 62mg/㎡ |
| Vitrification film thickness | 26nm | 31nm | 29nm | 35nm | 28nm | 42nm |
| Paint film adhesion grade | 0 grade | 0 grade | 0 grade | 0 grade | 0 grade | 0 grade |
| Paint film neutral salt spray test | 500h | 500h | 500h | 500h | 500h | 800h |
The treatment effect of table 5 embodiment 7-11 to metal
| Project | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 |
| Treatment time | 4min | 4min | 4min | 4min | 4min |
| Use temperature | Normal temperature | Normal temperature | Normal temperature | Normal temperature | Normal temperature |
| Sediment weight after processing | 87mg/㎡ | 115mg/㎡ | 126mg/㎡ | 95mg/㎡ | 88mg/㎡ |
| Vitrification film thickness | 25nm | 37nm | 33nm | 31nm | 30nm |
| Paint film adhesion grade | 0 grade | 0 grade | 0 grade | 0 grade | 0 grade |
| Paint film neutral salt spray test | 500h | 500h | 500h | 500h | 500h |
From table 4, table 5 can find out that the without phosphorus nanometer vitrified agent of the present invention is at same treatment time and temperature, and the effect after embodiment 6 uses is the best.Wherein vitrification thicknesses of layers reaches 42nm, and it applies rear enamelled coating sticking power grade is 0 grade, and neutral salt spray test reaches more than 800 hours, all more has superiority than other embodiment effects.The effect of embodiment 6 is best in sum.
In table 4, table 5, comparative run object testing method is as follows:
Sediment weight calculates: after sediment is dried, after weighing, show that sediment quality is divided by processing area with analytical balance.
Paint film neutral salt spray test: test according to GB 10125-1997 artificial atmosphere corrosion test salt-fog test standard;
Paint film adhesion grade: test according to the cross cut test standard of GB 9286-1998 paint and varnish paint film;
Above content description ultimate principle of the present invention and principal character; the present invention is not restricted to the described embodiments; without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (8)
1. a without phosphorus nanometer vitrified agent, is characterized in that by percentage to the quality, is made up of following raw material:
Fluorine zirconic acid 3-6%, basic zirconium chloride 3-7%, ammonium fluozirconate 0.1-0.6%, tartrate 0.8-2%, SODIUMNITRATE 0.5-1%, surplus is water.
2. without phosphorus nanometer vitrified agent according to claim 1, is characterized in that described fluorine zirconic acid consumption is 4-5%.
3. without phosphorus nanometer vitrified agent according to claim 1, is characterized in that described basic zirconium chloride consumption is 4-6%.
4. without phosphorus nanometer vitrified agent according to claim 1, is characterized in that described ammonium fluozirconate consumption is 0.3-0.6%.
5. without phosphorus nanometer vitrified agent according to claim 1, is characterized in that by percentage to the quality, is made up of following raw material: fluorine zirconic acid 5%, basic zirconium chloride 6%, ammonium fluozirconate 0.6%, tartrate 1.5%, SODIUMNITRATE 0.8%, water 86.1%.
6. the preparation method of without phosphorus nanometer vitrified agent according to claim 1, in turn includes the following steps:
(1) in reactor, add water;
(2) in reactor, add fluorine zirconic acid, then stir;
(3) in reactor, add basic zirconium chloride, then stir, until dissolve completely;
(4) in reactor, add ammonium fluozirconate, stir and make solution clarification;
(5) in reactor, add tartrate, stir and make solution clarification;
(6) in reactor, add SODIUMNITRATE, wait to stir and make solution clarification.
7. the preparation method of without phosphorus nanometer vitrified agent according to claim 6, the churning time that it is characterized in that step (2) is 0.5-1.5 hour; The churning time of step (3) is 1-3 hour; The churning time of step (4) is 0.5-1.5 hour; The churning time of step (5) is 0.5-1.5 hour; The churning time of step (6) is 20-40 minutes.
8. the application of without phosphorus nanometer vitrified agent in metal finishing according to claim 1.
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| CN104233252A (en) * | 2014-09-16 | 2014-12-24 | 南京华锐化工有限公司 | Novel room-temperature non-phosphorus coating agent |
| CN104726859A (en) * | 2014-12-31 | 2015-06-24 | 重庆建设摩托车股份有限公司 | Method for treating surface of oil tank under continuous production condition |
| CN106702361A (en) * | 2016-04-18 | 2017-05-24 | 佛山瑞箭体育器材有限公司 | Nanometer ceramic conversion agent and preparation method thereof |
| CN106702362A (en) * | 2016-11-27 | 2017-05-24 | 湖南金裕化工有限公司 | Fingerprint-resistant treating agent, preparing method and application thereof |
| CN107937903A (en) * | 2017-12-07 | 2018-04-20 | 佛山市高明高盛铝业有限公司 | A kind of preparation method of corrosive protection of aluminium alloy layer |
| CN107988604A (en) * | 2017-12-07 | 2018-05-04 | 佛山市高明高盛铝业有限公司 | A kind of preparation method of aluminum alloy surface protective layer |
| CN108047939A (en) * | 2017-12-25 | 2018-05-18 | 湖南德莱恩新材料科技有限公司 | Vitrified agent and preparation method thereof and application method |
| CN109868466A (en) * | 2019-01-31 | 2019-06-11 | 中锆纳米材料股份有限公司 | A kind of nano zircite metal rust preventing vitrification liquid |
| CN113215558A (en) * | 2021-05-18 | 2021-08-06 | 中山市壹桥环保科技有限公司 | Washing-free vitrification agent and use method thereof |
| CN113235078A (en) * | 2021-05-18 | 2021-08-10 | 中山市壹桥环保科技有限公司 | Washing-free silane agent and using method thereof |
| CN114016013A (en) * | 2021-09-23 | 2022-02-08 | 东莞市岩奥新材料有限公司 | Metal vitrification agent and preparation method and use method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104233252A (en) * | 2014-09-16 | 2014-12-24 | 南京华锐化工有限公司 | Novel room-temperature non-phosphorus coating agent |
| CN104233252B (en) * | 2014-09-16 | 2016-08-24 | 南京华锐化工有限公司 | A kind of room temperature non-phosphate film agent |
| CN104726859A (en) * | 2014-12-31 | 2015-06-24 | 重庆建设摩托车股份有限公司 | Method for treating surface of oil tank under continuous production condition |
| CN106702361A (en) * | 2016-04-18 | 2017-05-24 | 佛山瑞箭体育器材有限公司 | Nanometer ceramic conversion agent and preparation method thereof |
| CN106702362A (en) * | 2016-11-27 | 2017-05-24 | 湖南金裕化工有限公司 | Fingerprint-resistant treating agent, preparing method and application thereof |
| CN107937903A (en) * | 2017-12-07 | 2018-04-20 | 佛山市高明高盛铝业有限公司 | A kind of preparation method of corrosive protection of aluminium alloy layer |
| CN107988604A (en) * | 2017-12-07 | 2018-05-04 | 佛山市高明高盛铝业有限公司 | A kind of preparation method of aluminum alloy surface protective layer |
| CN108047939A (en) * | 2017-12-25 | 2018-05-18 | 湖南德莱恩新材料科技有限公司 | Vitrified agent and preparation method thereof and application method |
| CN109868466A (en) * | 2019-01-31 | 2019-06-11 | 中锆纳米材料股份有限公司 | A kind of nano zircite metal rust preventing vitrification liquid |
| CN113215558A (en) * | 2021-05-18 | 2021-08-06 | 中山市壹桥环保科技有限公司 | Washing-free vitrification agent and use method thereof |
| CN113235078A (en) * | 2021-05-18 | 2021-08-10 | 中山市壹桥环保科技有限公司 | Washing-free silane agent and using method thereof |
| CN114016013A (en) * | 2021-09-23 | 2022-02-08 | 东莞市岩奥新材料有限公司 | Metal vitrification agent and preparation method and use method thereof |
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