CN101570860A - Removing liquid of titanium nitride film and method for removing titanium nitride film - Google Patents
Removing liquid of titanium nitride film and method for removing titanium nitride film Download PDFInfo
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- CN101570860A CN101570860A CNA2008100934805A CN200810093480A CN101570860A CN 101570860 A CN101570860 A CN 101570860A CN A2008100934805 A CNA2008100934805 A CN A2008100934805A CN 200810093480 A CN200810093480 A CN 200810093480A CN 101570860 A CN101570860 A CN 101570860A
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Abstract
The invention provides a removing liquid of a titanium nitride film. The removing liquid refers to a aqueous solution containing peroxido hidrogeno, hydroxid and stabilizer; wherein the stabilizer is one or more of water-solubility citrate, water-solubility pyrophosphate and water-solubility versenate. The invention also provides a method for removing the titanium nitride film. The removing liquid of the titanium nitride film and the method for removing the film ensure that no corrosion is formed on the surface of base materials after removing the titanium nitride film so as not to damage the surface of the base materials, and the titanium nitride film can be removed stably, evenly and completely.
Description
Technical field
The present invention relates to a kind of stripping liquid of titanium nitride film, also relate to the stripping method of this titanium nitride film.
Background technology
The plating hard film layer is the strengthening material surface, improves one of important means of material property, has a wide range of applications at industrial circle.Titanium nitride (TiN) rete has anticorrosive, antioxidant property, therefore the excellent properties of good chemical stability, abrasion resistance properties and high rigidity is extensively developed and uses in various fields such as jewelry jewelry, household electrical appliances, electronic product, hardware ﹠ tools, turning cutting tool, mould and medical facilities.
Yet needing to strip rete under following two kinds of situations usually: through behind the life-time service, the rete of workpiece surface has been damaged or serious aging (1); (2) aborning, the rete of institute's plating does not meet quality requirements and produces substandard products.Therefore in order reducing the loss, to save cost, to need the stripping rete, the plated film again of then workpiece being done over again.Therefore, how under the situation of not damaging base material, it is a major issue the industrial application that rete is stripped fully from substrate surface.
Disclose a kind of stable decoating liquid among the CN1896314A, this decoating liquid comprises sulfuric acid and hydrogen peroxide (H
2O
2), also comprising the stablizer that stops decomposing hydrogen dioxide solution and accelerate strip speed, described stablizer is n-C
4H
9NH
2And n-C
8H
17NH
2In two kinds of combination of agents or the two kinds of reagent any.
This patent application adopts sulfuric acid and hydrogen peroxide to strip rete, but this decoating liquid poor stability, and the corroding metal base material, be unfavorable for industrial production.
Summary of the invention
The objective of the invention is to overcome the defective of above-mentioned stripping corrosion base material of the prior art, a kind of stripping liquid to the free from corrosion titanium nitride film of base material is provided, a kind of stripping method of titanium nitride film also is provided.
The invention provides a kind of stripping liquid of titanium nitride film, described stripping liquid is the aqueous solution that contains hydrogen peroxide, oxyhydroxide and stablizer, and described stablizer is one or more in water-soluble citrate, water-soluble pyrophosphate salt and the water-soluble edetate.
The present invention also provides a kind of stripping method of titanium nitride film, and this method comprises that the titanium nitride film that substrate surface is adhered to contacts with stripping liquid, and wherein, described stripping liquid is stripping liquid provided by the invention.
The stripping liquid of titanium nitride film provided by the invention and the stripping method of this rete make the not corrosion of the substrate surface of stripping behind the titanium nitride film, do not damage substrate surface, and can stablize, remove evenly, up hill and dale titanium nitride film.
Embodiment
The stripping liquid of titanium nitride film provided by the invention is the aqueous solution that contains hydrogen peroxide, oxyhydroxide and stablizer, and described stablizer is one or more in water-soluble citrate, water-soluble pyrophosphate salt and the water-soluble edetate.
According to stripping liquid provided by the invention, described stablizer can play the effect of stable stripping liquid in the liquid in stripping, and the stripping that can accelerate rete can successfully be carried out the stripping reaction.The environment that described oxyhydroxide provides alkalescence can for stripping liquid can carry out the stripping reaction, thereby can protect substrate surface not corroded, thereby do not damage substrate surface under alkaline environment.
According to stripping liquid provided by the invention, in the preferred case, in described stripping liquid, the concentration of hydrogen peroxide is 10-28g/L, be preferably 15-20g/L, the concentration of described oxyhydroxide is 20-200g/L, be preferably 50-150g/L, and the concentration of described stablizer is 50-320g/L, be preferably 100-250g/L.
According to stripping liquid provided by the invention, described oxyhydroxide can be preferably alkali metal hydroxide, more preferably sodium hydroxide and/or potassium hydroxide for water miscible and do not produce sedimentary various oxyhydroxide with described stablizer.
According to stripping liquid provided by the invention, described Citrate trianion can be preferably alkali-metal Citrate trianion, more preferably Trisodium Citrate and/or Tripotassium Citrate for various water miscible Citrate trianions.
According to stripping liquid provided by the invention, described pyrophosphate salt can be preferably alkali-metal pyrophosphate salt, more preferably trisodium phosphate and/or potassium pyrophosphate for various water miscible pyrophosphate salts.
According to stripping liquid provided by the invention, edetate can be preferably alkali-metal edetate, more preferably disodium ethylene diamine tetraacetate for various water miscible edetates.
The stripping method of the titanium nitride film that the present invention also provides comprises that under the condition of stripping titanium nitride film, the titanium nitride film that substrate surface is adhered to contacts with stripping liquid, and wherein, described stripping liquid is stripping liquid provided by the invention.
According to stripping method provided by the invention, to the not restriction especially of condition of stripping titanium nitride film, as long as can strip titanium nitride film fully, for example Jie Chu temperature is 20-60 ℃, and the time of contact is 0.5-30 minute.
According to stripping method provided by the invention, the titanium nitride film that substrate surface is adhered to can be the various ways of contact with the mode that stripping liquid contacts, for example, the base material that is attached with titanium nitride film is immersed in the stripping liquid, perhaps will strip liquid and be sprayed on the base material that is attached with titanium nitride film, preferred mode of soaking.The consumption of stripping liquid is unrestricted, and in order to economize in raw materials, the consumption of preferred this stripping liquid is a 3-10 grams per cubic centimter rete.
According to stripping method provided by the invention, this method also comprises described stripping liquid with after titanium nitride film contacts, and described base material washed and dry.Base material washed to make water or conventional washing, preferably wash with water with for example washing such as dehydrated alcohol of organic solvent.Base material is carried out drying can use conventional various drying meanss, for example hot blast drying or dry naturally.
The stripping liquid of titanium nitride film provided by the invention and the stripping method of this rete can be used to strip the titanium nitride film of various substrate surfaces, and described base material is preferably alkaline-resisting base material.Described alkaline-resisting base material includes but not limited to steel, copper, steel alloy and nickel-base alloy.
Text described " alkaline-resisting base material " is meant can alkali resistance reagent corrosive base material, specifically refer to the condition of stripping titanium nitride film not with the base material of alkaline reagents generation chemical reaction.
Adopt the mode of embodiment that the present invention is described in further detail below.
Embodiment 1
1, plating chromium nitride film layer
Utilize vacuum ionic coating apparatus (the Shenzhen permanent Industrial Co., Ltd. of shaking, model ZHC-800) in stainless steel substrate (the good stainless steel starting material of the Dongguan City banyan company of 40mm * 80mm * 1mm, 304 types) coating surface one layer thickness is the titanium nitride film of 3 μ m, as sample.
2, preparation chromium nitride film layer stripping liquid
31 gram citric acids and 103 gram potassium hydroxide are dissolved in 500 ml deionized water, add 25 milliliters then and contain 30 weight %H
2O
2Hydrogen peroxide stir, obtain stripping liquid.Wherein, citric acid generates Tripotassium Citrate with the potassium hydroxide reaction, and therefore in this stripping liquid, the concentration of Tripotassium Citrate is 100g/L, and the concentration of potassium hydroxide is 150g/L, and the concentration of hydrogen peroxide is 15g/L.
3, stripping titanium nitride film
Above-mentioned sample is immersed in the resulting stripping liquid under 20 ℃ fully soaked the stripping titanium nitride film 30 minutes.Take out the sample after soaking then, wash totally hot blast drying with water.
Through visual observations, the titanium nitride film on the discovery sample strips totally, does not have residual fully, and stainless steel substrate is not subjected to the burn into damage.
Comparative Examples 1
According to the method steps stripping titanium nitride film of describing among the embodiment 1, different is to contain 98% sulfuric acid 150 grams per liters, 27.5% hydrogen peroxide 25 grams per liters, stablizer n-C in the stripping liquid
4H
9NH
28 grams per liters.
Through visual observations, a large amount of bubbles of decoating liquid produce in the strip process, and decomposing hydrogen dioxide solution is serious, observe the titanium nitride film of finding on the sample behind the strip 1h and only partly come off, and the base material corrosion damage is serious.
Embodiment 2
1, preparation chromium nitride film layer stripping liquid
125 gram trisodium phosphates and 25 gram potassium hydroxide are dissolved in 500 ml deionized water, add 33 milliliters then and contain 30 weight %H
2O
2Hydrogen peroxide stir, obtain stripping liquid.In this stripping liquid, the concentration of trisodium phosphate is 250g/L, and the concentration of potassium hydroxide is 50g/L, and the concentration of hydrogen peroxide is 20g/L.
2, stripping titanium nitride film
The sample of making among the embodiment 1 is immersed in the above-mentioned stripping liquid under 25 ℃ that obtains fully soaked the stripping titanium nitride film 30 minutes.Take out the sample after soaking then, wash totally hot blast drying with water.
Through visual observations, the titanium nitride film on the discovery sample strips totally, does not have residual fully, and the stainless steel substrate surface is not subjected to the burn into damage.
Embodiment 3
1, preparation chromium nitride film layer stripping liquid
50 gram Trisodium Citrates, 25 gram trisodium phosphates, 25 gram disodium ethylene diamine tetraacetate and 50 gram sodium hydroxide are dissolved in 500 ml deionized water, add 30 milliliters then and contain 30 weight %H
2O
2Hydrogen peroxide stir, obtain stripping liquid.In this stripping liquid, the concentration of Trisodium Citrate is 100g/L, and the concentration of trisodium phosphate is 50g/L, and the concentration of disodium ethylene diamine tetraacetate is 50g/L, and concentration sodium hydroxide is 100g/L, and the concentration of hydrogen peroxide is 18g/L.
2, stripping titanium nitride film
The sample of making among the embodiment 1 is immersed in the above-mentioned stripping liquid under 30 ℃ that obtains fully soaked the stripping titanium nitride film 15 minutes.Take out the sample after soaking then, wash totally hot blast drying with water.
Through visual observations, the titanium nitride film on the discovery sample strips totally, does not have residual fully, and the stainless steel substrate surface is not subjected to the burn into damage.
Embodiment 4
1, preparation chromium nitride film layer stripping liquid
100 gram disodium ethylene diamine tetraacetate, 20 gram potassium hydroxide and 20 gram sodium hydroxide are dissolved in 500 ml deionized water, add 30 milliliters then and contain 30 weight %H
2O
2Hydrogen peroxide stir, obtain stripping liquid.In this stripping liquid, the concentration of disodium ethylene diamine tetraacetate is 250g/L, and the concentration of potassium hydroxide is 40g/L, and concentration sodium hydroxide is 40g/L, and the concentration of hydrogen peroxide is 18g/L.
2, stripping titanium nitride film
The sample of making among the embodiment 1 is immersed in the above-mentioned stripping solution under 40 ℃ that obtains fully soaked the stripping titanium nitride film 10 minutes.Take out the sample after soaking then, wash totally hot blast drying with water.
Through visual observations, the titanium nitride film on the discovery sample strips totally, does not have residual fully, and the nickel-base alloy substrate surface is not subjected to the burn into damage.
Embodiment 5
1, preparation chromium nitride film layer stripping liquid
100 gram disodium ethylene diamine tetraacetate and 70 gram potassium hydroxide are dissolved in 500 ml deionized water, add 27 milliliters then and contain 30 weight %H
2O
2Hydrogen peroxide stir, obtain stripping liquid.In this stripping liquid, the concentration of disodium ethylene diamine tetraacetate is 200g/L, and the concentration of potassium hydroxide is 140g/L, and the concentration of hydrogen peroxide is 16g/L.
2, stripping titanium nitride film
Sample made among the embodiment 1 is immersed in the above-mentioned stripping liquid under 50 ℃ that obtains fully soaked the stripping titanium nitride film 5 minutes.Take out the sample after soaking then, wash totally hot blast drying with water.
Through visual observations, the titanium nitride film on the discovery sample strips totally, does not have residual fully, and the stainless steel substrate surface is not subjected to the burn into damage.
Embodiment 6
1, preparation chromium nitride film layer stripping liquid
40 gram Trisodium Citrates, 35 gram disodium ethylene diamine tetraacetate and 40 gram potassium hydroxide, 20 gram sodium hydroxide are dissolved in 500 ml deionized water, add 27 milliliters then and contain 30 weight %H
2O
2Hydrogen peroxide stir, obtain stripping liquid.In this stripping liquid, the concentration of Trisodium Citrate is 80g/L, and the concentration of disodium ethylene diamine tetraacetate is 70g/L, and the concentration of potassium hydroxide is 80g/L, and concentration sodium hydroxide is 40g/L, and the concentration of hydrogen peroxide is 16g/L.
2, stripping titanium nitride film
Sample made among the embodiment 1 is immersed in the above-mentioned stripping liquid under 60 ℃ that obtains fully soaked the stripping titanium nitride film 1 minute.Take out the sample after soaking then, wash totally hot blast drying with water.
Through visual observations, the titanium nitride film on the discovery sample strips totally, does not have residual fully, and the stainless steel substrate surface is not subjected to the burn into damage.
Embodiment 7-12
According to the stripping of the method steps described in embodiment 1-6 titanium nitride film, different is that each replaces with rapid steel (40mm * 80mm * 1mm, the permanent grand die steel company limited in Shenzhen, M2 type) with the stainless steel substrate among the embodiment 1-6 respectively.
Through visual observations, the titanium nitride film on the discovery sample strips totally, does not have residual fully, and rapid steel base material surface is not corroded.
Embodiment 13-18
According to the stripping of the method steps described in embodiment 1-6 titanium nitride film, different is that each replaces with nickel-base alloy (40mm * 80mm * 1mm, Shanghai hawk despot metallic substance company limited, 800H type) with the stainless steel substrate among the embodiment 1-6 respectively.
Through visual observations, the titanium nitride film on the discovery sample strips totally, does not have residual fully, and the nickel-base alloy substrate surface is not subjected to the burn into damage.
From the foregoing description 1-18 and Comparative Examples 1 as can be seen, adopt the stripping method of stripping liquid He this rete of titanium nitride film provided by the invention, can stablize, up hill and dale that the stripping of the titanium nitride film of substrate surface is clean, and substrate surface is not received any corrosion and damage.
Claims (9)
1, a kind of stripping liquid of titanium nitride film, it is characterized in that, described stripping liquid is the aqueous solution that contains hydrogen peroxide, oxyhydroxide and stablizer, and described stablizer is one or more in water-soluble citrate, water-soluble pyrophosphate salt and the water-soluble edetate.
2, stripping liquid according to claim 1, wherein, in described stripping liquid, the concentration of hydrogen peroxide is 10-28g/L, and the concentration of oxyhydroxide is 20-200g/L, and the concentration of stablizer is 50-320g/L.
3, stripping liquid according to claim 2, wherein, the concentration 15-20g/L of hydrogen peroxide, the concentration of oxyhydroxide is 50-150g/L, the concentration of stablizer is 100-250g/L.
4, stripping liquid according to claim 1, wherein, described oxyhydroxide is alkali metal hydroxide; Described Citrate trianion is alkali-metal Citrate trianion; Described pyrophosphate salt is alkali-metal pyrophosphate salt, and edetate is the basic metal edetate.
5, stripping liquid according to claim 4, wherein, described oxyhydroxide is sodium hydroxide and/or potassium hydroxide; Described Citrate trianion is Tripotassium Citrate and/or Trisodium Citrate; Described pyrophosphate salt is potassium pyrophosphate and/or trisodium phosphate, and edetate is a disodium ethylene diamine tetraacetate.
6, a kind of stripping method of titanium nitride film, this method comprise that the titanium nitride film that substrate surface is adhered to contacts with stripping liquid, it is characterized in that described stripping liquid is any described stripping liquid among the claim 1-5.
7, method according to claim 6, wherein, the condition that the titanium nitride film that substrate surface is adhered to contacts with stripping liquid comprises that the contact temperature is 20-60 ℃, the time of contact is 0.5-30 minute.
8, according to claim 6 or 7 described methods, wherein, described base material is alkaline-resisting base material.
9, method according to claim 8, wherein, described base material is steel, copper, steel alloy or nickel-base alloy.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100934805A CN101570860A (en) | 2008-04-28 | 2008-04-28 | Removing liquid of titanium nitride film and method for removing titanium nitride film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100934805A CN101570860A (en) | 2008-04-28 | 2008-04-28 | Removing liquid of titanium nitride film and method for removing titanium nitride film |
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|---|---|
| CN101570860A true CN101570860A (en) | 2009-11-04 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102234513A (en) * | 2010-04-20 | 2011-11-09 | 深圳富泰宏精密工业有限公司 | Stripping solution for titanium-containing film and using method for stripping solution |
| CN102260872A (en) * | 2011-07-29 | 2011-11-30 | 沈阳大学 | Method for removing hard nitride reaction film |
| CN102634808A (en) * | 2012-03-19 | 2012-08-15 | 南昌大学 | Method for stripping Al2O3-contained multi-element composite coating from surface of waste coated hard alloy |
| CN103046052A (en) * | 2012-12-27 | 2013-04-17 | 广东山之风环保科技有限公司 | Environment-friendly decoating liquid for titanium-containing coatings and use method of environment-friendly decoating liquid |
| CN105018934A (en) * | 2015-07-15 | 2015-11-04 | 安徽多晶涂层科技有限公司 | Coating stripping powder for hard coating, prepared coating stripping liquid and coating stripping method |
| CN107759109A (en) * | 2017-09-22 | 2018-03-06 | 深圳市永安精细化工有限公司 | Glass is removed under a kind of normal temperature, coating takes off plating solution on ceramics |
| CN107988610A (en) * | 2017-11-27 | 2018-05-04 | 成都工具研究所有限公司 | Carbide chip TiAlN, TiN coating strip method |
| CN108588720A (en) * | 2015-10-19 | 2018-09-28 | 江苏理工学院 | Method for deplating copper-based palladium-nickel alloy coating |
| CN110180861A (en) * | 2019-04-28 | 2019-08-30 | 周丹丹 | A kind of clean preparation method of the useless packaging metal bucket of recycling |
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2008
- 2008-04-28 CN CNA2008100934805A patent/CN101570860A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102234513A (en) * | 2010-04-20 | 2011-11-09 | 深圳富泰宏精密工业有限公司 | Stripping solution for titanium-containing film and using method for stripping solution |
| CN102260872A (en) * | 2011-07-29 | 2011-11-30 | 沈阳大学 | Method for removing hard nitride reaction film |
| CN102260872B (en) * | 2011-07-29 | 2012-11-14 | 沈阳大学 | Method for removing hard nitride reaction film |
| CN102634808A (en) * | 2012-03-19 | 2012-08-15 | 南昌大学 | Method for stripping Al2O3-contained multi-element composite coating from surface of waste coated hard alloy |
| CN102634808B (en) * | 2012-03-19 | 2014-07-16 | 南昌大学 | Method for stripping Al2O3-contained multi-element composite coating from surface of waste coated hard alloy |
| CN103046052A (en) * | 2012-12-27 | 2013-04-17 | 广东山之风环保科技有限公司 | Environment-friendly decoating liquid for titanium-containing coatings and use method of environment-friendly decoating liquid |
| CN103046052B (en) * | 2012-12-27 | 2016-01-20 | 广东山之风环保科技有限公司 | The stripping liquid of environment-friendly type titanium-containing film and using method thereof |
| CN105018934A (en) * | 2015-07-15 | 2015-11-04 | 安徽多晶涂层科技有限公司 | Coating stripping powder for hard coating, prepared coating stripping liquid and coating stripping method |
| CN108588720A (en) * | 2015-10-19 | 2018-09-28 | 江苏理工学院 | Method for deplating copper-based palladium-nickel alloy coating |
| CN107759109A (en) * | 2017-09-22 | 2018-03-06 | 深圳市永安精细化工有限公司 | Glass is removed under a kind of normal temperature, coating takes off plating solution on ceramics |
| CN107988610A (en) * | 2017-11-27 | 2018-05-04 | 成都工具研究所有限公司 | Carbide chip TiAlN, TiN coating strip method |
| CN110180861A (en) * | 2019-04-28 | 2019-08-30 | 周丹丹 | A kind of clean preparation method of the useless packaging metal bucket of recycling |
| CN110180861B (en) * | 2019-04-28 | 2021-07-09 | 周丹丹 | Clean production method for recycling waste packaging iron drum |
| CN111850564A (en) * | 2020-07-16 | 2020-10-30 | 桂林理工大学 | Titanium compound film deplating solution and deplating method |
| CN115449796A (en) * | 2022-09-23 | 2022-12-09 | 易安爱富(武汉)科技有限公司 | Alkaline etching solution for titanium-aluminum-titanium composite film and preparation method thereof |
| CN115449796B (en) * | 2022-09-23 | 2023-11-28 | 易安爱富(武汉)科技有限公司 | Alkaline etching solution for titanium-aluminum-titanium composite film and preparation method thereof |
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