CN102899650A - Steel normal-temperature blackening solution composite film-forming accelerator, steel normal-temperature blackening solution and preparation method of steel normal-temperature blackening solution - Google Patents

Steel normal-temperature blackening solution composite film-forming accelerator, steel normal-temperature blackening solution and preparation method of steel normal-temperature blackening solution Download PDF

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CN102899650A
CN102899650A CN2012104059522A CN201210405952A CN102899650A CN 102899650 A CN102899650 A CN 102899650A CN 2012104059522 A CN2012104059522 A CN 2012104059522A CN 201210405952 A CN201210405952 A CN 201210405952A CN 102899650 A CN102899650 A CN 102899650A
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steel
room temperature
temperature liquid
composite membrane
blackening solution
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CN102899650B (en
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田康
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Tian Kang
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ZIGONG BOSHENG SURFACE TECHNOLOGY PROMOTION CO LTD
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Abstract

The invention discloses a steel normal-temperature blackening solution composite film-forming accelerator which comprises the following components in parts by weight: 1-3 parts of calcium nitrate, 4-8 parts of cobalt nitrate, 2.5-5 parts of sodium borate and 0.3-0.6 part of metanitrobenzene sulfonic acid. The adhesive force and corrosion resistance of a blackening film are obviously improved, and the film-forming speed is also increased. The invention also discloses a steel normal-temperature blackening solution. The steel normal-temperature blackening solution takes water as a solvent, has a pH value of 2-3 and comprises the main components of 2-8 g/L copper sulfate, 3-6.5 g/L selenium dioxide, 2-10 g/L potassium dihydrogen phosphate, 2-6 g/L zinc nitrate, 1-3 g/L nickel sulfate, 2-6 g/L composite film-forming accelerator, 3-8 g/L urea and 0.5-8 g/L complexing agent. The invention also discloses a preparation method of the steel normal-temperature blackening solution. The blackening film of the prepared blackening solution has firm adhesive force, high corrosion resistance and less sediment.

Description

The preparation method of Chemical Colouring of Steel at Room Temperature liquid composite membrane-forming promotor and Chemical Colouring of Steel at Room Temperature liquid and Chemical Colouring of Steel at Room Temperature liquid
Technical field
The invention belongs to chemical treatment field, metallic surface, relate to concretely the preparation method of Chemical Colouring of Steel at Room Temperature liquid composite membrane-forming promotor and Chemical Colouring of Steel at Room Temperature liquid and this Chemical Colouring of Steel at Room Temperature liquid.
Background technology
The steel blackening technology is mainly used in the anticorrosion and decorative appearance of iron and steel parts.Blackening can be divided into two large classes, and a class is traditional high temperature blackening, and another kind of is New Process of Room Temperature Blackening.From the beginning of the eighties by American engineer invention Chemical Colouring of Steel at Room Temperature technology since because the room temperature blackening technology is compared the outstanding advantages such as have energy-saving and environmental protection, efficient with traditional high temperature blackening, be subject to social extensive concern.The development of technique experience many decades has had large increase qualitatively.The application of Chemical Colouring of Steel at Room Temperature technology increases also in continuous development.But in general, the application of room temperature blackening technology also is not very extensive.Most surface treatment producer still adopts traditional high temperature blackening in the reality.One of factor that it is important is exactly that is that all right is ripe for present room temperature blackening technology, also there is not good film forming accelerating, except only a few blackout prescription can be produced quality of forming film preferably the product, the blackout effect of the disclosed hair blackening liquid prescription of existing major part is all undesirable, and its common defective is:
1, the common fault of traditional normal temperature steel blackening liquid is that precipitation or postprecipitation phenomenon are serious, causes the unnecessary consumption of mass efficient composition, Efficiency Decreasing.This is because workpiece when blackout, the oxidized generation of steel substrate Fe 2+, Fe 2+Can be further oxided and be Fe 3+,
Fe 3+With the SeO in the solution 3 2-Chemical reaction occurs form precipitation:
Fe 3++SeO 3 2-=Fe 2(SeO 3) 3
The generation of precipitation must consume the effective constituent tin anhydride of adding, makes Efficiency Decreasing.
2, also to have a defective that is difficult to overcome be that operating time model restriction is tighter to existing room temperature blackening product, and the blackout time is slightly long, and black film will occur a large amount of floating black, even loose scrapping.This is because its black film enough fine and closely woven, poor adhesive force not, and hair blackening liquid can penetrate that the film that has formed continues and metallic matrix reacts, and causes rete to be destroyed.
3, anticorrosive power is poor, and the workpiece salt mist experiment that the current ambient temperature blackening is processed was difficult to above 5 hours.
4, black film sticking power is insecure: several similar blackout product of selling on the market, and back and forth wipe its wear resistance at the blackout workpiece surface with the equal power of experiment filter paper and be difficult to above 100 times.
Summary of the invention
The object of the present invention is to provide a kind of sticking power and erosion resistance that can significantly improve black film, the Chemical Colouring of Steel at Room Temperature liquid film forming accelerating that film forming speed is fast.
Second purpose of the present invention is to provide the Chemical Colouring of Steel at Room Temperature that a kind of erosion resistance is strong, sediment is few, efficient is high liquid.The present invention also provides the preparation method of this kind Chemical Colouring of Steel at Room Temperature liquid.
The first purpose of the present invention is achieved in that a kind of Chemical Colouring of Steel at Room Temperature liquid composite membrane-forming promotor, is comprised of the following component of parts by weight: nitrocalcite 1-3 part, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 4-8 part, Sodium Tetraborate 2.5-5 part, m-nitrobenzene sulfonic acid 0.3-0.6 part.
Adopt technique scheme, this film forming accelerating is fit to exist the Chemical Colouring of Steel at Room Temperature liquid of phosphate radical, owing to having a large amount of phosphate anions in the hair blackening liquid, adds calcium salt and the cobalt salt of suitable proportion, these materials itself can form the phosphatoptosis layer in the metallic surface, such as Ca 3(PO 4) 2, Co 3(PO 4) 2Deng, the film forming accelerating of having served as phosphatize phosphate coat.In addition, m-nitrobenzene sulfonic acid and Sodium Tetraborate also are effective phosphatize phosphate coat promotor, with the compound action of other composition in the solution, have accelerated phosphatic formation and composition ratio row in the black film, significantly improved sticking power and the erosion resistance of black film, film forming speed also increases.
As preferably: described Chemical Colouring of Steel at Room Temperature liquid composite membrane-forming promotor is comprised of the following component of weight fraction: nitrocalcite 2-3 part, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 5-7 part, Sodium Tetraborate 3-4 part, m-nitrobenzene sulfonic acid 0.4-0.5 part.
Another object of the present invention is achieved in that a kind of Chemical Colouring of Steel at Room Temperature liquid, take water as solvent, pH value is 2-3, and main component is copper sulfate 2~8g/L, tin anhydride 3~6.5g/L, potassium primary phosphate 2~10g/L, zinc nitrate 2~6g/L, single nickel salt 1~3g/L, composite membrane-forming promotor 2~6g/L, urea 3~8g/L, complexing agent 0.5-8g/L;
Described composite membrane-forming promotor is comprised of the following component of parts by weight: nitrocalcite 1-3 part, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 4-8 part, Sodium Tetraborate 2.5-5 part, m-nitrobenzene sulfonic acid 0.3-0.6 part.
Adopt technique scheme, for significantly improving of sticking power and anticorrosive power, mainly be based on the following principles of chemistry:
It is generally acknowledged, contain CuSe in the room temperature blackening film, FeSe, Fe 2(SeO 3) 3Deng composition, when containing phosphate radical in the hair blackening liquid, also can contain part FeHPO in the black film 4, FePO 4Deng phosphate component, thereby further improve the corrosion-resistant energy of black film and the bonding force of rete and metallic matrix.
Not firm in order to overcome the existing ubiquitous sticking power of room temperature blackening liquid, the defective that erosion resistance is poor, this programme has adopted a kind of " composite membrane-forming promotor ", experiment is found, the adding of this NEW TYPE OF COMPOSITE material, significantly improved sticking power and the erosion resistance of black film, film forming speed also increases.
Adopt this composite membrane-forming material that black film is produced modified effect, may be interpreted as from principle: have a large amount of phosphate anions the hair blackening liquid, add calcium salt and the cobalt salt of suitable proportion, these materials itself can form the phosphatoptosis layer in the metallic surface, such as Ca 3(PO 4) 2, Co 3(PO 4) 2Deng, the film forming accelerating of having served as phosphatize phosphate coat.In addition, m-nitrobenzene sulfonic acid and Sodium Tetraborate also are effective phosphatize phosphate coat promotor, with the compound action of other composition in the solution, have increased phosphatic formation and composition ratio row in the black film, have improved quality of forming film.
This prescription has also added complexing agent and an amount of inhibiter-urea.
Complexing agent and Fe 3+Ion forms the very strong complex compound of stability, establishment Fe 2(SeO 3) 3The generation of precipitation has reduced sediment, thereby has reduced the consumption of this effective constituent of tin anhydride, has significantly improved the service efficiency of hair blackening liquid, and the treatment capacity of solution is improved, and has reduced production cost.
In order further to suppress matrix by excessive Quick Oxidation, produce rapidly a large amount of Fe 2+Ion, and be further converted to Fe 3+Ion, thus Fe easily formed 2(SeO 3) 3Precipitation, this prescription have added metal inhibitor urea reducing the oxidation rate of iron, thereby further suppress the generation that precipitates in the blackout process.
Blackout workpiece after this product treatment is not with any floating black.The black film firm adhesion, after tested, the blackout workpiece surface is back and forth wiped with the equal power of experiment filter paper and is loseed metallic matrix more than 200 times.And the similar experiment of traditional room temperature blackening liquid is difficult to above 100 times.Workpiece salt mist experiment through this technique blackout can reach 10 hours, and the workpiece of traditional high temperature and room temperature blackening art breading was difficult to above 5 hours.In the copper sulfate anti-corrosion test, can reach 80 to 150 seconds, be higher than ministerial standard far away 30 seconds.This hair blackening liquid black film is fine and closely woven, strong adhesion, even allow workpiece soak 2 hours, the loose phenomenon of rete still can not occur.Wide adaptability no matter to high carbon steel, soft steel, comprise and all can obtain color and luster such as silicon steel, cast iron, 40 chromium, chromium 12, powder metallurgy etc. pure by the very unmanageable steel of some high temperature blackenings, rete is fine and closely woven, without floating black high-quality rete.
As preferably: the pH value with sodium hydrate regulator solution is 2-3.
As preferably: the pH value with the potassium hydroxide regulator solution is 2-3.
As preferably: described complexing agent is cyclohexanediaminetetraacetic acid.
Cyclohexanediaminetetraacetic acid (CyDTA) and Fe 3+Ion forms the very strong aminoxatyl complex of stability:
CyDTA+Fe 3+→Fe(CyDTA) -+4H +
The Fe that produces in the blackout process 3+Ion conversion is stable water-soluble complexing ion Fe (CyDTA) -, CyDTA and Fe 3+The complex compound that forms forms constant up to logK=30.1, and its complex ability is strong, and complex compound forms constant and exceeds at least 5 orders of magnitude than the analog value of ethylenediamine tetraacetic acid (EDTA) (EDTA) and citric acid, establishment Fe 2(SeO 3) 3The generation of precipitation has reduced sediment, thereby has reduced the consumption of this effective constituent of tin anhydride, has significantly improved the service efficiency of hair blackening liquid, and the treatment capacity of solution is improved, and has reduced production cost.
As preferably: described complexing agent is sodium tartrate.
The preparation method of described Chemical Colouring of Steel at Room Temperature liquid is: finish in accordance with the following steps:
(1) copper sulfate in the claim 3, tin anhydride, potassium primary phosphate, zinc nitrate, single nickel salt, urea, composite membrane-forming promotor, complexing agent are added water to respectively dissolving, then with each solution mixing and stirring;
(2) regulator solution PH to 2-3, then add water mixing solutions is diluted to scale, so that the content of each component is copper sulfate 2~8g/L, tin anhydride 3~6.5g/L, potassium primary phosphate 2~10g/L, zinc nitrate 2~6g/L, single nickel salt 1~3g/L, composite membrane-forming promotor 2~6g/L, urea 3~8g/L, complexing agent 0.5-8g/L.This preparation technology is simple, low cost of manufacture.
Beneficial effect: compare with currently available products, the blackout workpiece after this product treatment is not with any floating black.The black film firm adhesion, erosion resistance is strong, even sediment is few, the fine and closely woven workpiece that allows of black film soaked 2 hours, the loose phenomenon of rete still can not occur.Wide adaptability no matter to high carbon steel, soft steel, comprise the very unmanageable steel of some high temperature blackenings, all can obtain color and luster such as silicon steel, cast iron, 40 chromium, chromium 12, powder metallurgy etc. pure, rete is fine and closely woven, without floating black high-quality rete.
Embodiment
The present invention is described further below in conjunction with specific embodiment:
Embodiment 1
With copper sulfate 2g, tin anhydride 3g, potassium primary phosphate 2g, zinc nitrate 2g, single nickel salt 1g, composite membrane-forming promotor 2g, urea 8g/L, sodium tartrate 2.5g add respectively a small amount of water and get final product to dissolving fully, then with each solution mixing and stirring; In above-mentioned mixing solutions, add an amount of sodium hydroxide and regulate PH to 2-3, then add water mixing solutions is diluted 1L, obtain hair blackening liquid.
Described composite membrane-forming promotor is by 1 part in nitrocalcite, 8 parts of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs, 2.5 parts of Sodium Tetraboratees, 0.3 part of composition of m-nitrobenzene sulfonic acid.
Embodiment 2
With copper sulfate 8g, tin anhydride 6.5g, potassium primary phosphate 8g, zinc nitrate 4g, single nickel salt 2g, composite membrane-forming promotor 4g, urea 3g, cyclohexanediaminetetraacetic acid 8g add respectively a small amount of water and get final product to dissolving fully, then with each solution mixing and stirring; In above-mentioned mixing solutions, add potassium hydroxide and regulate PH to 2-3, then add water mixing solutions is diluted 1L, obtain hair blackening liquid.
Described composite membrane-forming promotor is by 3 parts in the nitrocalcite of weight fraction, 4 parts of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs, 5 parts of Sodium Tetraboratees, 0.6 part of composition of m-nitrobenzene sulfonic acid.
Embodiment 3
With copper sulfate 6g, tin anhydride 4.5g, potassium primary phosphate 10g, zinc nitrate 6g, single nickel salt 3g, composite membrane-forming promotor 6g, urea 5g, cyclohexanediaminetetraacetic acid 6g add respectively a small amount of water and get final product to dissolving fully, then with each solution mixing and stirring; In above-mentioned mixing solutions, add sodium hydroxide and regulate PH to 2-3, then add water mixing solutions is diluted 1L, obtain hair blackening liquid.
Described composite membrane-forming promotor is by weight fraction: 2 parts in nitrocalcite, 5 parts of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs, 3 parts of Sodium Tetraboratees, 0.4 part of m-nitrobenzene sulfonic acid.
Embodiment 4
With copper sulfate 4g, tin anhydride 5g, potassium primary phosphate 6g, zinc nitrate 3g, single nickel salt 1.5g, composite membrane-forming promotor 5g, urea 6g, cyclohexanediaminetetraacetic acid 4g add respectively a small amount of water and get final product to dissolving fully, then with each solution mixing and stirring; In above-mentioned mixing solutions, add potassium hydroxide and regulate PH to 2-3, then add water mixing solutions is diluted 1L, obtain hair blackening liquid.
Described composite membrane-forming promotor is by weight fraction: 3 parts in nitrocalcite, 7 parts of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs, 4 parts of Sodium Tetraboratees, 0.5 part of m-nitrobenzene sulfonic acid.

Claims (8)

1. Chemical Colouring of Steel at Room Temperature liquid composite membrane-forming promotor, it is characterized in that: the following component by parts by weight forms:
Nitrocalcite 1-3 part, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 4-8 part, Sodium Tetraborate 2.5-5 part, m-nitrobenzene sulfonic acid 0.3-0.6 part.
2. described Chemical Colouring of Steel at Room Temperature liquid composite membrane-forming promotor according to claim 1, it is characterized in that: the following component by weight fraction forms: nitrocalcite 2-3 part, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 5-7 part, Sodium Tetraborate 3-4 part, m-nitrobenzene sulfonic acid 0.4-0.5 part.
3. Chemical Colouring of Steel at Room Temperature liquid, it is characterized in that: take water as solvent, pH value is 2-3, and main component is copper sulfate 2~8g/L, tin anhydride 3~6.5g/L, potassium primary phosphate 2~10g/L, zinc nitrate 2~6g/L, single nickel salt 1~3g/L, composite membrane-forming promotor 2~6g/L, urea 3~8g/L, complexing agent 0.5-8g/L;
Described composite membrane-forming promotor is comprised of the following component of parts by weight: nitrocalcite 1-3 part, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 4-8 part, Sodium Tetraborate 2.5-5 part, m-nitrobenzene sulfonic acid 0.3-0.6 part.
4. described Chemical Colouring of Steel at Room Temperature liquid according to claim 3, it is characterized in that: the pH value with sodium hydrate regulator solution is 2-3.
5. described Chemical Colouring of Steel at Room Temperature liquid according to claim 3, it is characterized in that: the pH value with the potassium hydroxide regulator solution is 2-3.
6. described Chemical Colouring of Steel at Room Temperature liquid according to claim 3, it is characterized in that: described complexing agent is cyclohexanediaminetetraacetic acid.
7. described Chemical Colouring of Steel at Room Temperature liquid according to claim 3, it is characterized in that: described complexing agent is sodium tartrate.
8. the preparation method of a Chemical Colouring of Steel at Room Temperature liquid is characterized in that: finish in accordance with the following steps:
(1) copper sulfate in the claim 3, tin anhydride, potassium primary phosphate, zinc nitrate, single nickel salt, urea, composite membrane-forming promotor, complexing agent are added water to respectively dissolving, then with each solution mixing and stirring;
(2) regulator solution PH to 2-3, then add water mixing solutions is diluted to scale, so that the content of each component is copper sulfate 2~8g/L, tin anhydride 3~6.5g/L, potassium primary phosphate 2~10g/L, zinc nitrate 2~6g/L, single nickel salt 1~3g/L, composite membrane-forming promotor 2~6g/L, urea 3~8g/L, complexing agent 0.5-8g/L.
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CN105270782A (en) * 2014-07-19 2016-01-27 湖北吉奥特安全科技有限公司 Installation process for special alloy insulating explosion-proof oil storage tank
CN105525315A (en) * 2016-01-18 2016-04-27 苏州市华婷特种电镀有限公司 Electroplating solution for obtaining ancient bronze plating
CN106086680A (en) * 2016-08-16 2016-11-09 宁波瑞国精机工业有限公司 A kind of high strength nut and processing method thereof
CN106282819A (en) * 2016-08-16 2017-01-04 宁波瑞国精机工业有限公司 A kind of high-strength pin and processing method thereof
CN106967970A (en) * 2017-04-10 2017-07-21 武汉迪赛新材料有限公司 Normal-temperature blackening passivating agent for steel surface
CN103834942B (en) * 2013-11-30 2017-08-01 湖北侨光石化装备股份有限公司 Multifunction surface processing pond and its hair blackening liquid
CN109606001A (en) * 2018-12-28 2019-04-12 云南乌铜走银文化产业有限公司 Old dose and its application method are done for what black copper walked silver-colored manufacturing process
CN113621954A (en) * 2021-07-05 2021-11-09 重庆信人科技发展有限公司 High-corrosion-resistance rust removal pre-blackening agent and preparation method and application thereof

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CN103834942B (en) * 2013-11-30 2017-08-01 湖北侨光石化装备股份有限公司 Multifunction surface processing pond and its hair blackening liquid
CN105270782A (en) * 2014-07-19 2016-01-27 湖北吉奥特安全科技有限公司 Installation process for special alloy insulating explosion-proof oil storage tank
CN105525315A (en) * 2016-01-18 2016-04-27 苏州市华婷特种电镀有限公司 Electroplating solution for obtaining ancient bronze plating
CN106086680A (en) * 2016-08-16 2016-11-09 宁波瑞国精机工业有限公司 A kind of high strength nut and processing method thereof
CN106282819A (en) * 2016-08-16 2017-01-04 宁波瑞国精机工业有限公司 A kind of high-strength pin and processing method thereof
CN106086680B (en) * 2016-08-16 2018-02-09 宁波瑞国精机工业有限公司 A kind of high strength nut and its processing method
CN106282819B (en) * 2016-08-16 2018-02-09 宁波瑞国精机工业有限公司 A kind of high-strength pin and its processing method
CN106967970A (en) * 2017-04-10 2017-07-21 武汉迪赛新材料有限公司 Normal-temperature blackening passivating agent for steel surface
CN109606001A (en) * 2018-12-28 2019-04-12 云南乌铜走银文化产业有限公司 Old dose and its application method are done for what black copper walked silver-colored manufacturing process
CN113621954A (en) * 2021-07-05 2021-11-09 重庆信人科技发展有限公司 High-corrosion-resistance rust removal pre-blackening agent and preparation method and application thereof
CN113621954B (en) * 2021-07-05 2023-12-29 重庆信人科技发展有限公司 High corrosion-resistant rust-removing pre-blackening agent and preparation method and application thereof

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Patentee after: Tian Kang

Address before: The big 643000 Anquma Sichuan city of Zigong province development zone draft

Patentee before: Zigong Bosheng Surface Technology Promotion Co.,Ltd.

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Granted publication date: 20140604

Termination date: 20201023

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