阅读说明：本技术 一种制备氮化钛镀膜的水性电镀液及其制备方法与应用 (Aqueous electroplating solution for preparing titanium nitride coating film and preparation method and application thereof ) 是由 罗锴 刘军 施志聪 陈镕枫 邹祖良 欧阳远 刘恒 黄蔼琪 于 2019-08-27 设计创作，主要内容包括：本发明涉及一种水性电镀液,具体涉及一种制备氮化钛镀膜的水性电镀液及其制备方法与应用。所述的制备氮化钛镀膜的水性电镀液包含钾盐、偏硅酸钠、润湿剂、稳定剂、光亮剂等。该制备氮化钛镀膜的水性电镀液廉价高效,原料易得成本低,制备条件要求低,无需使用价格高昂的设备；且应用范围广泛,可满足于任意形状表面。同时所制备薄膜的厚度更优,可显著提升其保护性能。(The invention relates to an aqueous electroplating solution, in particular to an aqueous electroplating solution for preparing a titanium nitride coating, and a preparation method and application thereof. The aqueous electroplating solution for preparing the titanium nitride coating comprises potassium salt, sodium metasilicate, a wetting agent, a stabilizer, a brightener and the like. The aqueous electroplating solution for preparing the titanium nitride coating is cheap and efficient, the raw materials are easy to obtain, the cost is low, the preparation condition requirement is low, and expensive equipment is not required; and the application range is wide, and the surface with any shape can be met. Meanwhile, the prepared film has better thickness and can obviously improve the protective performance.)

1. An aqueous plating solution for preparing a titanium nitride coating film, characterized by comprising the following components:

5-30 mol/Kg of potassium salt in water;

0.3-3 mol/Kg of water of sodium metasilicate;

the potassium salt is at least one of potassium acetate and potassium thiocyanate.

2. The aqueous plating solution for titanium nitride coating film formation according to claim 1, characterized by comprising:

10-23 mol/Kg of potassium salt in water;

0.6 to 2.3mol/Kg of water of sodium metasilicate.

3. The aqueous plating solution for titanium nitride coating film formation according to claim 1 or 2, further comprising:

0.05-0.2 mol/Kg of water as a stabilizer;

0.01-0.1 mol/Kg of water as brightener;

0.02-0.2 mol/Kg of water as a wetting agent.

4. The aqueous plating solution for titanium nitride coating film formation according to claim 3, further comprising:

0.08-0.18 mol/Kg of water as a stabilizer;

0.01-0.1 mol/Kg of water as brightener;

0.03 to 0.15mol/Kg of water as a wetting agent.

5. The aqueous plating solution for titanium nitride coating film formation according to claim 3, wherein:

the stabilizer is sodium citrate, calcium gluconate, 2, 6-di-tert-butyl-4-methylphenol, dilauryl thiodipropionate, distearyl thiodipropionate or trinitrophenol.

6. The aqueous plating solution for titanium nitride coating film formation according to claim 3, wherein:

the brightener is protein, sodium benzoate, naphthalenesulfonic acid, saccharin, butynediol, sulfimide or sulfobenzaldehyde.

7. The aqueous plating solution for titanium nitride coating film formation according to claim 3, wherein:

the wetting agent is sodium dodecyl sulfate, lithium dodecyl sulfate, isooctanol, epoxy acrylate, dicyclopentadiene dioxide epoxy resin or polyoxyethylene laurate.

8. Use of the aqueous plating solution for titanium nitride plating film according to any one of claims 1 to 7 for preparing a titanium nitride plating film.

9. A titanium nitride coating film produced from the aqueous plating solution for producing a titanium nitride coating film according to any one of claims 1 to 7.

10. The method of preparing a titanium nitride coating film according to claim 9, characterized by comprising the steps of:

pouring the aqueous plating solution for titanium nitride coating film preparation described in any one of claims 1 to 7 into a plating bath, placing a titanium plate as a working electrode and a counter electrode into the plating bath, and plating to obtain a titanium nitride coating film.

Technical Field

The invention relates to an aqueous electroplating solution, in particular to an aqueous electroplating solution for preparing a titanium nitride coating, and a preparation method and application thereof.

Background

Conventional thin film fabrication methods have focused primarily on CVD and PVD. The disadvantages of both types of processes are the excessively thin film thickness (of the order of a few microns), the considerable reduction in the protective properties of the coating, in particular its corrosion protection, and the high cost, the need for expensive equipment and the relatively severe preparation conditions. Meanwhile, it is difficult to coat a material having a complicated surface shape.

The titanium nitride film is widely used, the most mature preparation technology, and has various excellent performances: including extremely high hardness, corrosion resistance, abrasion resistance, high melting point, and excellent electrical conductivity. TiN belongs to a gap phase, the melting point is as high as 2955 ℃, atoms are combined into a covalent bond, a metal bond and a mixed bond of ionic bonds, and the metal bond exists among the metal atoms. Therefore, the TiN coating (thin film) has high hardness (theoretical hardness 21GPa), excellent heat resistance, wear resistance, corrosion resistance, and the like, and has remarkable metal characteristics: metallic luster, excellent conductivity and superconductivity. Based on the advantages, the titanium nitride film has important applications in many fields, such as friction-resistant and corrosion-resistant coatings for cutting tools, mechanical parts and high-temperature structural materials, diffusion barrier layers and conductive films in the microelectronic industry, and can also be used for preparing high-efficiency energy-saving coated glass due to high reflectivity in the infrared band. In addition, its color comparable to gold makes it also useful for decorative coatings.

At present, the titanium nitride film is prepared by vapor deposition, magnetron sputtering, ion plating and other processes. However, the above process has inherent limitations due to its process characteristics, that is, the size and shape of the coated substrate are greatly limited due to the process characteristics, and high vacuum conditions are mostly required.

Therefore, it is desirable to provide a method for preparing a titanium nitride coating film with a suitable size and shape at a low cost and without strict requirements on production conditions.

Disclosure of Invention

In order to overcome the disadvantages and shortcomings of the prior art, the invention provides an aqueous electroplating solution for preparing a titanium nitride coating.

Another object of the present invention is to provide a method for preparing the above aqueous plating solution for titanium nitride plating film.

The invention also aims to provide application of the aqueous electroplating solution for preparing the titanium nitride coating.

The purpose of the invention is realized by the following technical scheme:

an aqueous plating solution for preparing a titanium nitride coating film, comprising the following components:

5-30 mol/Kg of potassium salt in water;

0.3-3 mol/Kg of water of sodium metasilicate;

the potassium salt is at least one of potassium acetate and potassium thiocyanate;

when the potassium salt is potassium acetate, the using amount of the potassium salt is 5-25 mol/Kg of water; when the potassium salt is potassium thiocyanate, the using amount of the potassium thiocyanate is 5-30 mol/Kg of water;

the aqueous electroplating solution for preparing the titanium nitride coating preferably comprises the following components:

10-23 mol/Kg of potassium salt in water;

0.6-2.3 mol/Kg of water of sodium metasilicate;

when the potassium salt is potassium acetate, the dosage is preferably 10-21 mol/Kg of water; when the potassium salt is potassium thiocyanate, the preferred dosage is 12-23 mol/Kg of water;

the aqueous plating solution for preparing the titanium nitride coating preferably further comprises the following components:

0.05-0.2 mol/Kg of water as a stabilizer;

0.01-0.1 mol/Kg of water as brightener;

0.02-0.2 mol/Kg of water as a wetting agent;

the aqueous plating solution for preparing a titanium nitride coating film further preferably further comprises the following components:

0.08-0.18 mol/Kg of water as a stabilizer;

0.01-0.1 mol/Kg of water as brightener;

0.03-0.15 mol/Kg of water as a wetting agent;

the stabilizer is preferably sodium citrate, calcium gluconate, 2, 6-di-tert-butyl-4-methylphenol, dilauryl thiodipropionate, distearyl thiodipropionate or trinitrophenol;

the brightener is preferably protein, sodium benzoate, naphthalenesulfonic acid, saccharin, butynediol, sulfimide or sulfobenzaldehyde;

the composition unit of the protein is preferably glycine, glutamic acid and lysine, and the molecular weight is less than 8000;

the wetting agent is preferably sodium dodecyl sulfate, lithium dodecyl sulfate, isooctyl alcohol, epoxy acrylate, dicyclopentadiene dioxide epoxy resin or polyoxyethylene laurate;

the preparation method of the aqueous electroplating solution for preparing the titanium nitride coating comprises the following steps:

dissolving potassium salt of the aqueous electroplating solution for preparing the titanium nitride coating in water, adding the rest components, and uniformly mixing to obtain the aqueous electroplating solution for preparing the titanium nitride coating;

the application of the aqueous electroplating solution for preparing the titanium nitride coating in preparing the titanium nitride coating;

a titanium nitride coating film, which is prepared from the aqueous electroplating solution for preparing the titanium nitride coating film;

the preparation method of the titanium nitride coating film comprises the following steps:

pouring the aqueous electroplating solution for preparing the titanium nitride coating into an electroplating bath, taking a titanium sheet as a working electrode and a counter electrode, and putting the titanium sheet into the electroplating bath for electroplating to obtain the titanium nitride coating;

the titanium sheet is pretreated as follows: cleaning with clear water, alcohol, hydrochloric acid and ultrasound;

the electroplating conditions are preferably as follows:

the reduction current is-0.5 to-0.2 mA/cm²The electroplating time is 4-6 h;

the principle of the invention is as follows:

the electrochemical window of water is narrow, many materials (such as titanium nitride) with standard reduction electrode potential lower than hydrogen cannot be prepared by an electroplating method, and water is electrolyzed to generate hydrogen during electroplating, so that a coating cannot be obtained. In conventional electroplating baths, potassium acetate or potassium thiocyanate is generally used as the supporting electrolyte, at very low concentrations. The invention utilizes the ultrahigh solubility of the titanium nitride and the titanium nitride, so that the addition amount of water in the plating solution is far less than that of salt, the activity of water molecules is reduced, the electrochemical window of the aqueous solution is enlarged, the reaction of hydrogen gas precipitation is more difficult to occur, and the electroplating of the titanium nitride is realized. While sodium metasilicate is added to stabilize the high concentration of potassium salt.

Compared with the prior art, the invention has the following advantages and effects:

(1) the electroplating solution provided by the invention contains potassium acetate and/or potassium thiocyanate, sodium metasilicate and other components, can expand the electrochemical window of the aqueous solution, restrain water molecules, make the reaction of hydrogen precipitation more difficult to occur, inhibit the generation of hydrogen, and enable the material with the standard reduction electrode potential lower than that of hydrogen to realize electroplating preparation.

(2) The titanium nitride coating prepared by the method is cheap and efficient, the raw materials are easy to obtain, the cost is low, expensive equipment is not required, and the preparation condition requirement is low; the application range is wide, and the material can meet the requirements of materials with surfaces of any shapes.

(3) The titanium nitride coating film is prepared in an electroplating mode, the surface with any shape can be met, the thickness of the film can be controlled through electroplating parameters, the thickness of the prepared coating film is more suitable, and the problem of poor coating protection performance, particularly poor corrosion resistance, caused by excessively thin coating thickness can be solved.

Drawings

FIG. 1 is a scanning electron micrograph of titanium nitride in example 1.

FIG. 2 is an energy dispersive X-ray spectroscopy chart of the titanium nitride composition of example 1.

FIG. 3 is a scanning electron micrograph of titanium nitride in example 2.

FIG. 4 is an energy dispersive X-ray spectroscopy plot of titanium nitride in example 2.

FIG. 5 is a scanning electron micrograph of titanium nitride in example 3.

FIG. 6 is an energy dispersive X-ray spectroscopy plot of titanium nitride in example 3.

FIG. 7 is a scanning electron micrograph of titanium nitride in example 4.

FIG. 8 is an energy dispersive X-ray spectroscopy plot of titanium nitride in example 4.

Detailed Description

The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.

The reagents used in the following examples are either commercially available or self-made.