CN110607544B - Aqueous electroplating solution for preparing titanium nitride coating film and preparation method and application thereof - Google Patents
Aqueous electroplating solution for preparing titanium nitride coating film and preparation method and application thereof Download PDFInfo
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Abstract
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.
Description
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.
Example 1
(1) Weighing 26g of sodium metasilicate pentahydrate and 200g of potassium acetate in a glove box;
(2) dissolving the potassium acetate weighed in the step (1) in 400ml of deionized water, and then placing the deionized water in a magnetic stirrer for stirring until the potassium acetate is completely dissolved; pouring the sodium metasilicate pentahydrate weighed in the step (1) into the solution, and simultaneously adding 5.9g of sodium citrate, 0.58g of sodium benzoate and 2.4g of sodium dodecyl sulfate to continue stirring until the sodium metasilicate pentahydrate is completely dissolved; standing for 3h to obtain an aqueous electroplating solution for preparing the titanium nitride coating;
(3) pouring 200ml of the aqueous electroplating solution for preparing the titanium nitride coating prepared in the step (2) into an electroplating bath, taking out two titanium sheets which are cleaned by clear water, alcohol, hydrochloric acid and ultrasound and are taken as a working electrode and a counter electrode, and putting the titanium sheets into the electroplating bath for electroplating, wherein the reference electrode used in the electroplating is an Ag/AgCl electrode, the reduction current is-0.5 mA, and the electroplating time is 6 hours, so as to obtain the titanium nitride coating.
Example 2
(1) Weighing 140g of sodium metasilicate pentahydrate and 590g of potassium acetate in a glove box;
(2) dissolving the potassium acetate weighed in the step (1) in 400ml of deionized water, and then placing the deionized water in a magnetic stirrer for stirring until the potassium acetate is completely dissolved; pouring the sodium metasilicate pentahydrate weighed in the step (1) into the solution, and adding 17.2g of calcium gluconate, 3.3g of naphthalenesulfonic acid and 4.2g of isooctanol at the same time, and continuing stirring until the calcium gluconate, the naphthalenesulfonic acid and the isooctanol are completely dissolved; standing for a period of time to obtain the aqueous electroplating solution for preparing the titanium nitride coating.
(3) Pouring 200ml of the aqueous electroplating solution for preparing the titanium nitride coating prepared in the step (2) into an electroplating bath, taking out two titanium sheets which are cleaned by clear water, alcohol, hydrochloric acid and ultrasound and are used as a working electrode and a counter electrode, putting the titanium sheets into the electroplating bath, introducing nitrogen, and then electroplating, wherein the reference electrode used in the electroplating is an Ag/AgCl electrode, the reduction current is-0.5 mA/cm2And the electroplating time is 6 hours, so that the titanium nitride coating is obtained.
Example 3
(1) Weighing 583g of potassium thiocyanate and 127g of sodium metasilicate pentahydrate in a glove box;
(2) dissolving the potassium thiocyanate weighed in the step (1) in 200ml of deionized water, and then placing the deionized water in a magnetic stirrer for stirring until the potassium thiocyanate is completely dissolved; pouring the sodium metasilicate pentahydrate weighed in the step (1) into the solution, and simultaneously adding 16.5g of dilauryl thiodipropionate, 1.2g of butynediol and 8g of lithium dodecyl sulfate, and continuously stirring until the materials are completely dissolved; standing for a period of time to obtain an aqueous electroplating solution for preparing the titanium nitride coating;
(3) mixing 100ml of the mixture(2) Pouring the prepared aqueous electroplating solution for preparing the titanium nitride coating into an electroplating bath, taking out two titanium sheets which are cleaned by clear water, alcohol, hydrochloric acid and ultrasonic wave as a working electrode and a counter electrode, and putting the titanium sheets into the electroplating bath for electroplating, wherein the reference electrode used in the electroplating is an Ag/AgCl electrode, and the reduction current is-0.5 mA/cm2And the electroplating time is 4 hours, so that the titanium nitride coating is obtained.
Example 4
(1) Weighing 520g of potassium thiocyanate, 60g of potassium acetate and 127g of sodium metasilicate pentahydrate in a glove box;
(2) dissolving the potassium thiocyanate weighed in the step (1) in 200ml of deionized water, and then placing the deionized water in a magnetic stirrer for stirring until the potassium thiocyanate is completely dissolved; then adding 60g of potassium acetate weighed in the step (1), and stirring until the potassium acetate is completely dissolved; then the sodium metasilicate pentahydrate weighed in the step (1) is poured into the solution, and 9.1g of trinitrophenol, 3.6g of saccharin and 9.6g of polyoxyethylene laurate are added at the same time, and stirring is continued until complete dissolution. Standing for a period of time to obtain an aqueous electroplating solution for preparing the titanium nitride coating;
(3) pouring 100ml of the aqueous electroplating solution for preparing the titanium nitride coating prepared in the step (2) into an electroplating bath. Taking out two titanium sheets which are cleaned by clear water, alcohol, hydrochloric acid and ultrasonic wave as a working electrode and a counter electrode, putting the titanium sheets into a plating bath for plating, wherein the reference electrode used in the plating is an Ag/AgCl electrode, and the reduction potential is-0.2 mA/cm2And the electroplating time is 6 hours, so that the titanium nitride coating is obtained.
Effects of the embodiment
(1) Scanning Electron Microscope (SEM) analysis of each of the titanium nitride coatings obtained in examples 1 to 4 showed that the titanium nitride coatings were as shown in FIGS. 1, 3, 5 and 7.
As can be seen from fig. 1, the titanium nitride coating film prepared in example 1 was wrinkled; as can be seen from FIG. 3, in example 2, after nitrogen gas was introduced during the process of preparing the coating film, the morphology of the prepared titanium nitride coating film was similar to that of example 1, but the nitrogen content was increased from 8.681% to 13.957% (tables 1 and 2).
TABLE 1 energy dispersive X-ray spectroscopy analysis of the titanium nitride coating composition obtained in example 1
TABLE 2 energy dispersive X-ray spectroscopy analysis of the titanium nitride coating composition obtained in example 2
| Element(s) | Crest line | Strength (c/s) | Atomic percent (%) | Concentration (wt.%) | |
| C | Ka | 0.00 | 0.000 | 0.000 | |
| N | Ka | 44.54 | 13.957 | 4.547 | |
| O | Ka | 0.00 | 0.000 | 0.000 | |
| K | Ka | 0.44 | 0.018 | 0.016 | |
| Ti | Ka | 1,196.73 | 86.025 | 95.437 | |
| 100.000 | 100.000 | Sum of |
FIGS. 5 and 7 are scanning electron micrographs of the titanium nitride coating films obtained in examples 3 and 4, respectively. Among them, examples 3 and 4 in which potassium thiocyanate was used as a potassium salt were significantly changed in morphology, as compared with example 1 in which potassium acetate was used as a potassium salt, the titanium nitride coating film obtained in example 3 was composed of fine particles, and the titanium nitride coating film obtained in example 4 was large in titanium nitride particles.
FIGS. 2, 4, 6 and 8 are graphs of energy dispersive X-ray spectroscopy of the titanium nitride coating films prepared in examples 1 to 4, respectively.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. A preparation method of a titanium nitride coating film is characterized by comprising 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 placing the titanium sheet into the electroplating bath for electroplating to obtain the titanium nitride coating; the electroplating conditions are as follows: the reduction current is-0.5 to-0.2 mA/cm2The electroplating time is 4-6 h;
the aqueous electroplating solution for preparing the titanium nitride coating comprises the following components:
5-30 mol/Kg of water of potassium salt and 0.3-3 mol/Kg of water of sodium metasilicate;
the potassium salt is potassium acetate and potassium thiocyanate.
2. The method of preparing a titanium nitride coating film according to claim 1, characterized in that:
the aqueous electroplating solution for preparing the titanium nitride coating comprises the following components:
10 to 23mol/Kg of water of potassium salt and 0.6 to 2.3mol/Kg of water of sodium metasilicate.
3. The method for producing a titanium nitride coating film according to claim 1 or 2, characterized in that:
the aqueous electroplating solution for preparing the titanium nitride coating also comprises the following components:
0.05 to 0.2mol/Kg of water as a stabilizer, 0.01 to 0.1mol/Kg of water as a brightener, and 0.02 to 0.2mol/Kg of water as a wetting agent.
4. The method of preparing a titanium nitride coating film according to claim 3, characterized in that:
the aqueous electroplating solution for preparing the titanium nitride coating also comprises the following components:
0.08-0.18 mol/Kg of water as stabilizer, 0.01-0.1 mol/Kg of water as brightener, and 0.03-0.15 mol/Kg of water as wetting agent.
5. The method of preparing a titanium nitride coating film according to claim 3, characterized in that:
the stabilizer is sodium citrate, calcium gluconate, 2, 6-di-tert-butyl-4-methylphenol, dilauryl thiodipropionate, distearyl thiodipropionate or trinitrophenol.
6. The method of preparing a titanium nitride coating film according to claim 3, characterized in that: the brightener is protein, sodium benzoate, naphthalenesulfonic acid, saccharin, butynediol, sulfimide or sulfobenzaldehyde.
7. The method of preparing a titanium nitride coating film according to claim 3, characterized in that:
the wetting agent is sodium dodecyl sulfate, lithium dodecyl sulfate, isooctanol, epoxy acrylate, dicyclopentadiene dioxide epoxy resin or polyoxyethylene laurate.
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