阅读说明：本技术 一种含锆膜层的褪除液及使用方法 (Zirconium-containing film layer removing liquid and use method thereof ) 是由 赵力民 谢伟娜 黄思琪 邬钰娴 吴秋琴 于 2019-08-26 设计创作，主要内容包括：本发明提供了一种含锆膜层的褪除液及使用方法,属于真空镀膜技术领域。该褪除液由氧化剂、耦合剂和缓蚀剂溶于水配制而成。氧化剂的质量体积浓度为200g/L-500g/L；耦合剂的质量体积浓度为40g/L-120g/L；缓蚀剂的质量体积浓度为20g/L-100g/L；本发明还提供上述褪除液的使用方法,包括以下步骤：将基件完全浸入含锆膜层的褪除液；将基件清洗干燥。本发明提供的褪除液可褪除含锆膜层,成本低、简单有效且不伤害基件,具有广阔的应用前景。(The invention provides a zirconium-containing film layer removing liquid and a using method thereof, belonging to the technical field of vacuum coating. The fading liquid is prepared by dissolving an oxidant, a coupling agent and a corrosion inhibitor in water. The mass volume concentration of the oxidant is 200g/L-500 g/L; the mass volume concentration of the coupling agent is 40g/L-120 g/L; the mass volume concentration of the corrosion inhibitor is 20g/L-100 g/L; the invention also provides a use method of the fading liquid, which comprises the following steps: completely immersing the base piece into a removing liquid of a zirconium-containing film layer; the substrate is washed and dried. The removing liquid provided by the invention can remove the zirconium-containing film, is low in cost, simple and effective, does not damage the base piece, and has wide application prospect.)

1. The zirconium-containing film layer removing liquid is characterized by comprising an oxidant, a corrosion inhibitor, a coupling agent and water.

2. The removing liquid for the zirconium-containing film layer as claimed in claim 1, which comprises an oxidizing agent with a mass volume concentration of 200g/L-500g/L, a coupling agent with a mass volume concentration of 40g/L-120g/L, a corrosion inhibitor with a mass volume concentration of 20g/L-100g/L, and the balance of water.

3. The removing liquid for the zirconium-containing film layer as claimed in any one of claims 1 to 2, wherein the oxidizing agent is one or more of ammonium bifluoride, sodium bifluoride and potassium bifluoride.

4. The liquid for removing a zirconium-containing film according to any one of claims 1 to 2, wherein the corrosion inhibitor is one or both of urea and thiourea.

5. The removing liquid for the zirconium-containing film layer as claimed in any one of claims 1 to 2, wherein the coupling agent is one or more of triethanolamine, diethanolamine and dimethylethanolamine.

6. The method for removing the zirconium-containing film layer on the surface of the base member by applying the removing liquid for the zirconium-containing film layer according to any one of claims 1 to 2, comprising the steps of:

(1) completely immersing the base material with the zirconium-containing film layer on the surface into the removing liquid of the zirconium-containing film layer;

(2) the sample was removed, washed and dried.

7. The method of claim 6, wherein in step (1), the substrate of the zirconium-containing film layer is a stainless steel substrate.

8. The method of claim 6, wherein in step (1), the zirconium-containing film layer comprises a zirconium nitride film, a zirconium carbonitride film, a zirconium carbide film, a zirconium oxide film.

9. The method according to claim 6, wherein in step (1), the soaking time is 15 minutes to 30 minutes; the soaking temperature is 23-52 ℃.

10. The method of claim 6, wherein in step (2), the drying method comprises airing, drying and blow-drying.

Technical Field

The invention belongs to the technical field of vacuum coating, and particularly relates to a zirconium-containing film layer removing liquid and a using method thereof.

Background

Zirconium and its alloys have excellent properties such as extremely high melting point, hardness, strength, corrosion resistance, etc., and have a wide application value in the fields of nuclear industry and chemical industry, and more corrosion-resistant devices begin to use zirconium materials as raw materials. Meanwhile, in order to widen the application of the metal material, the zirconium alloy film layer is plated on the stainless steel through vacuum electroplating, so that the corrosion resistance of the stainless steel material can be improved, and the color and luster can be increased. During vacuum plating, different reaction gases are introduced, and zirconium-containing films with different colors can be presented, for example, the zirconium nitride film is light gold, the zirconium carbonitride film is rose gold, and the zirconium carbide film is black, so that the films are widely applied in hardware and bathroom industries. However, some substrates are damaged by corrosion and aging after long-term use, and industrial production needs to remove the original film on the surface of the substrate and then re-coat the substrate for cost saving. In addition, the required quality standards may not be met during coating, and the original surface film layer of the base member may be removed again to reduce the loss.

Also, due to the excellent physical properties and corrosion resistance of zirconium alloys, there is a need for a solution and method that can effectively remove zirconium-containing films without damaging the base member.

Among other methods for deplating alloy film layers, chinese patent 201410331058.4 discloses a deplating solution for deplating a nickel-tungsten-phosphorus electroplated layer on the surface of a sintered neodymium-iron-boron magnet, and an application and a deplating process of the deplating solution. In the deplating solution, the neodymium iron boron magnet with the surface plated with the nickel-tungsten-phosphorus electroplated layer is used as an anode, and the inert electrode is used as a cathode to carry out anode electrolysis deplating. The stripping solution is used for electrolytic stripping, the traditional electrolytic process is used, additional operation is not needed, the process is simple and mature, safety and environmental protection are realized, and the nickel-tungsten-phosphorus electroplated layer can be rapidly and effectively stripped. However, in the process of removing the nickel-plated layer by using the electrochemical method, the low current density region is difficult to remove cleanly and the plating removal speed is slow, so that the method is limited to a certain extent.

Chinese patent 201610822788.3 discloses a chemical deplating solution for deplating a palladium-nickel alloy plating layer and a deplating method, which are characterized by comprising an oxidant, an accelerator, a complexing agent and a corrosion inhibitor. The plating removing process sequentially comprises the steps of alkali washing, water washing, drying, plating removing, water washing and drying. Can effectively reduce the adverse effect on the corrosion of the brass (or stainless steel) matrix, and has the advantages of clean removal and relatively high removal speed of the low current density region in the nickel layer removal process. The method uses the composite acid of the sulfuric acid and the nitric acid, finds out the optimal proportion, improves the current situation that the dissolution rate of the nitric acid to the palladium-nickel plating layer is not high, introduces the sulfuric acid, plays a role in accelerating the dissolution and greatly improves the working efficiency. The technology adds an alkali washing step before deplating, thereby improving the complexity of the process; compared with a simple electrochemical method, the cost is increased. Therefore, there is still much room for improvement in terms of cost and process.

Chinese patent 201010150010.5 discloses a liquid and a method for removing titanium carbide and/or titanium nitride film. The removing liquid is an aqueous solution containing acid, an accelerator and a corrosion inhibitor, wherein the acid is organic acid or inorganic acid, and the concentration of the acid is 90g/L-1000 g/L; the accelerator is acid or salt containing fluoride ions, and the concentration of the accelerator is 70g/L-500 g/L; the accelerator is an alcamines organic compound, and the concentration of the accelerator is 15g/L-200 g/L; the corrosion inhibitor is one or a combination of more of thiourea, thiourea derivatives and urea, and the concentration of the corrosion inhibitor is 2g/L-8 g/L. The temperature of the stripping liquid during the contact is 20-30 ℃, and the contact time is 0.5-2 h. The method can simply and effectively remove the titanium-containing film layer, but the higher acid content in the formula greatly increases the cost, and meanwhile, the contact time of the removing solution is longer, so that the method is not beneficial to quickly and efficiently removing the titanium-containing film layer.

Because a method for removing the zirconium-containing film layer, which can efficiently remove the zirconium-containing film layer without damaging the base piece, is lacked at present, the invention provides the removing liquid for the zirconium-containing film layer so as to achieve the aim of simply and effectively removing the zirconium-containing film layer.

Disclosure of Invention

In view of the above, the invention provides a removing liquid which can effectively remove a zirconium-containing film layer without damaging a base member and a using method thereof.

The water involved in the implementation process of the invention can be distilled water, pure water, deionized water, drinking water, tap water and other various water.

The technical scheme of the invention is as follows:

the invention provides a removing liquid capable of removing a zirconium-containing film layer on the surface of a base piece, which comprises an oxidant, a coupling agent, a corrosion inhibitor and water.

Wherein the mass volume concentration of the oxidant is 200g/L-500 g/L.

Wherein the mass volume concentration of the coupling agent is 40g/L-120 g/L.

Wherein the mass volume concentration of the corrosion inhibitor is 20g/L-100 g/L.

Except the three components, the rest is water.

Wherein the oxidant is one or more of ammonium bifluoride, sodium bifluoride and potassium bifluoride, and ammonium bifluoride is preferred.

Wherein, the corrosion inhibitor is one or two of urea and thiourea.

Wherein the coupling agent is one or more of triethanolamine, diethanolamine and dimethylethanolamine, and preferably triethanolamine.

The invention also provides a using method of the zirconium-containing film layer removing liquid, which comprises the following steps:

(1) immersing the base material with the zirconium-containing film layer on the surface into the removing liquid;

(2) the sample was removed, washed and dried.

Wherein, the base material selected in the step (1) is a stainless steel base material.

In step (1), the zirconium-containing film layer on the selected substrate includes, but is not limited to, zirconium-containing film layers such as zirconium nitride film, zirconium carbide film, zirconium carbonitride film, zirconium oxide film, etc.

Wherein, in the step (1), the soaking time of the base material in the zirconium-containing film layer removing solution is 15 minutes to 30 minutes.

Wherein, in the step (1), the soaking temperature of the base material in the zirconium-containing film layer removing solution is 23-52 ℃.

In the step (1), the base material is soaked in the zirconium-containing film layer removing solution completely.

In the step (1), the method for controlling the temperature of the removed liquid comprises constant-temperature water bath treatment and Teflon heating pipe temperature control treatment.

In the step (2), the sample is dried by a method including but not limited to wiping, airing, drying in a dryer, and blow-drying, preferably drying and blow-drying.

Compared with the prior art, the invention has the following beneficial effects:

the stripping liquid of the present invention consists of oxidant, coupling agent and corrosion inhibitor.

(1) Zirconium has excellent corrosion resistance to various acids (such as hydrochloric acid, nitric acid, sulfuric acid and acetic acid), alkalis and salts, but can be dissolved in hydrofluoric acid, and the removing liquid selects acid salt containing fluorine ions, so that the defects of strong corrosion, easy volatilization, high toxicity and high cost of hydrofluoric acid can be avoided.

(2) Because the ammonium bifluoride can corrode stainless steel and dissolve in water to volatilize toxic substances, the base piece can be protected by adding the corrosion inhibitor, and meanwhile, a good fog inhibiting effect is achieved.

(3) Addition of coupling agent can accelerate H⁺And (5) permeating to promote the dissolution of the film layer.

(4) Compared with the prior art, the liquid phase for removing the zirconium-containing film layer has the advantages that the effect of completely removing the zirconium-containing film layer can be obtained by using less components, the base piece is not damaged, the method is low in cost, simple and effective, the electrochemical operation is omitted, and the application prospect is good.

Drawings

FIG. 1 is a graph showing the effect of example 1 on removing a zirconium-containing film layer from the surface of a wafer-shaped sample, wherein the sample in FIG. 1(a) is brass and the sample in FIG. 1(b) is silver black;

FIG. 2 is a graph showing the effect of example 2 on the removal of a zirconium-containing film layer from the surface of a cylindrical sample, wherein the sample in FIG. 2(a) is silver and the sample in FIG. 2(b) is brass;

fig. 3 is a graph showing the removing effect of example 3 on the zirconium-containing film layer on the surface of the irregular sample, wherein the color of the sample in fig. 3(a) is golden yellow, and the color of the sample in fig. 3(b) is silvery white.

Detailed Description

The present invention will be further explained with reference to specific embodiments in order to make the technical means, the original characteristics, the achieved objects and the effects of the present invention easy to understand, but the following embodiments are only preferred embodiments of the present invention, and not all embodiments are possible. Based on the embodiments in the implementation, other embodiments obtained by those skilled in the art without any creative efforts belong to the protection scope of the present invention.

The experimental methods in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used in the following examples are commercially available unless otherwise specified.

Ammonium bifluoride was purchased from Fuchen chemical reagent GmbH with a product number of 13-011-;

the urea is purchased from national medicine group chemical reagent limited company, and the product number is 57-13-6;

triethanolamine is purchased from Yongda chemical reagents, Inc. of Tianjin, with a product number of 102-71-6.