CN103160776B - Titanium diboride-nickel coating or film and preparation method thereof - Google Patents

Abstract

The invention relates to a preparation method of a titanium diboride-nickel coating or film. By using the method, a metal Ni toughened TiB2 coating or film is prepared through in-situ synthesis; and the coating has hardness up to higher than 25GPa, good conductive properties, good toughness, corrosion resistance and erosion resistance, and excellent friction and wear performance, and can be widely applied to the fields of cutting tool, mold, electric contact and protection. The preparation process has advantages of simpleness, short production cycle and low cost, and is convenient for industrialized mass production.

Description

A kind of preparation method of titanium diboride-nickel coating or thin film

technical field

The invention belongs to the field of new materials, and relates to a TiB ₂ -Ni material, in particular to a preparation method of an in-situ synthesized metal Ni toughened TiB ₂ coating or film.

Background technique

TiB ₂ has the advantages of high hardness, high melting point, low density, high Young's modulus, good thermal conductivity, electrical conductivity, wear resistance and chemical stability, etc. It is an advanced ceramic material with excellent structural and functional properties. Therefore, it is widely used in many fields, especially as a coating material for hard, protective, and electrical contacts. However, the brittleness of TiB ₂ ceramic materials limits its single application to a certain extent. Therefore, based on the high hardness of TiB ₂ materials, TiB ₂ particle-reinforced metal matrix composites have been widely studied recently based on the research ideas of material composites. For example: titanium diboride dispersion strengthened copper-based composite material (Chinese patent, 200910095176.9), _TiB2 particle reinforced magnesium-based composite material (Chinese patent, 200710047943.X), etc., these materials maintain the toughness and electrical conductivity of the metal matrix very well It has excellent properties such as toughness and easy processing, and improves the strength and hardness of the metal to a certain extent, so it has a good application prospect. However, TiB ₂ in the material is only added in a small amount inside the metal matrix as a reinforcing phase, which is extremely limited in improving the strength and hardness of the material. On the contrary, there are few reports on composite materials with _TiB2 as the main crystal phase and a small amount of metal phase. Zhang Xinghong et al obtained a bulk composite material with a TiB ₂ content as high as 75% and a lower Cu-Ni content by sintering the previously obtained TiB ₂ phase and metal phase, and the obtained material was close to the equilibrium state. (Xinghong Zhang, Changqing Hong, Jiecai Hana and Hexin Zhang, Microstructure and mechanical properties of TiB ₂ /(Cu,Ni) interpenetrating phase composites, Scripta Materialia, 55, 2006, 565–568) and in-situ vapor phase synthesized metallic Ni toughened TiB ₂ coatings or thin films have not been reported.

Contents of the invention

The technical problem to be solved by the present invention is to provide a preparation method of TiB ₂ -Ni coating or thin film, which not only has low preparation cost, but also has simple operation, short preparation period, strong repeatability and can be used in large-scale industrial production.

The technical scheme adopted by the present invention to solve the above-mentioned technical problems is: a preparation method of TiB ₂ -Ni coating or film, which is characterized in that high-purity TiB ₂ ceramic target and metal Ni target are used as raw materials, and physical vapor deposition technology is adopted. , by in-situ deposition of coatings or films with different _TiB2 and Ni ratios, preferably, the specific steps for preparing the coating or films by magnetron sputtering technology are:

a) installing the target and substrate;

b) vacuuming and substrate heating;

c) Pass in inert gas, set power supply and substrate parameters, start glow, after pre-sputtering, sputter deposition;

d) After the deposition is over, turn off the electricity, gas and water circuits, and take samples.

As an improvement, the substrate in step a) is ultrasonically cleaned with absolute ethanol, acetone, and absolute ethanol for 10-20 minutes before installation, and then air-dried at 70-90° C. for 1-2 hours.

Preferably, the vacuuming in the step b) means that the background vacuum in the deposition chamber is lower than 9.5×10 ^-4 Pa, and the heating temperature of the substrate is from room temperature to 500° C. for 20 to 30 minutes.

The power supply and substrate parameters in the step c) are: TiB ₂ ceramic target power supply parameters are: intermediate frequency 50-200KHZ, power 100-500W, duty cycle 60-90%; Ni metal target power supply parameters are: DC power 0- 20W; the pre-sputtering time is 8-15 minutes, and the sputtering deposition time is 30-200 minutes. The parameters of the substrate are: bias voltage 0V, temperature room temperature to 500°C.

More preferably, the inert gas injected in the step c) is argon, the flow rate of the inert gas is controlled at 20-40 sccm, and the pressure in the deposition chamber is adjusted in the range of 0.1-1 Pa.

The TiB ₂ -Ni coating or film prepared by the above method is composed of TiB ₂ as the main crystal phase and metal Ni as the secondary crystal phase by physical vapor deposition technology, wherein the TiB ₂ content is 65-95 at.%, The Ni content is 5-35 at.%.

The substrate material of the TiB ₂ -Ni coating or film is selected from single crystal silicon, glass, high-speed steel, alloy steel or titanium alloy.

The thickness of the film is 20nm-1um; the thickness of the coating is 1um-1mm.

Compared with the prior art, the present invention has the advantages of:

1) A new coating material system is designed, that is, in situ synthesized metallic Ni toughened TiB ₂ coating or film.

2) The coating has a hardness of over 25GPa, good electrical conductivity, good toughness, corrosion resistance, ablation resistance, and excellent friction and wear properties.

3) The process for preparing the TiB ₂ -Ni coating or thin film is simple, easy to operate, short in the preparation period, low in cost, and convenient for industrial production.

Description of drawings

Fig. 1 is the surface (XRD) pattern of the _TiB2 -Ni coating sample prepared by the present invention, wherein the abscissa is the diffraction angle 2θ, the unit is °, and the ordinate is the diffraction peak intensity, the unit is au;

Fig. 2 is a scanning electron microscope (SEM) photograph of a TiB ₂ -Ni coating sample prepared by the present invention, wherein a is a section, and b is a surface.

Detailed ways

The present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments.

Example 1:

1) A commercially available TiB ₂ ceramic target with a purity of 99.9% and a commercially available metallic Ni target with a purity of 99.99% are selected as raw materials; the substrate is a (100) oriented single crystal silicon substrate.

2) Firstly, the substrate is cleaned, and the substrate is ultrasonically cleaned with absolute ethanol, acetone, and absolute ethanol for 20 minutes in sequence, and then dried at 80° C. for 2 hours by blasting, and then set aside.

3) Using the magnetron sputtering system independently designed and produced by our research group, first open the cavity and install the substrate and target correctly, first check that the gas, electricity, and water circuits are normal, then turn on the main power supply and start the mechanical pump, when the deposition chamber and the sample After the air pressure in the chamber is below 10Pa, close the valve between the mechanical pump and the chamber, open the baffle valve, start the molecular pump, and unscrew the gate valve. When the vacuum in the sample chamber reaches 10 ^-3 Pa, stop the fine vacuuming. , to speed up the pumping speed of the vacuum in the deposition chamber.

4) When the background vacuum in the deposition chamber reaches 8.7×10 ^-5 Pa, turn on the sample substrate heating mode, set the temperature at 200°C, keep it warm for 20 minutes after reaching the specified temperature, and record the background when the vacuum reaches 9.1×10 ^-5 Pa. Bottom vacuum.

5) Open the argon gas cylinder, control the flow rate at 30 sccm, unscrew the corresponding valve, feed inert gas, properly close the gate valve between the deposition chamber and the molecular pump, and adjust the air pressure in the deposition chamber to 0.5Pa.

6) Set the TiB ₂ ceramic target power supply parameters as: intermediate frequency (MF) 100HKZ, power 400W, duty cycle 80%; Ni metal target power supply parameters: direct current (DC), power 4W; after about 10 minutes of pre-sputtering, open the sample Baffle, formal sputtering deposition, deposition time: 180min.

7) After the deposition is completed, close the sample baffle, target power supply, gas path, etc. in sequence; after the sample is cooled, take a sample to obtain the final product TiB ₂ -Ni coating sample.

The prepared typical sample of TiB ₂ -Ni coating was analyzed and tested, and the following results and data were obtained. The obtained TiB ₂ -Ni coating sample was tested with an Alpha-Step IQ surface profiler produced by Xinyun Technology Engineering Co., Ltd. of the United States, and the coating thickness was about 1.3 μm. The resulting TiB ₂ -Ni coating sample was analyzed by a D8Advance X-ray diffractometer produced by German Bruker Company to analyze the crystal phase composition of the sample surface. It can be seen that the diffraction peak of TiB ₂ in the prepared TiB ₂ -Ni coating is stronger ( 150a.u.), while the diffraction peak of Ni is not obvious (Figure 1). The S-4800 scanning electron microscope produced by Hitachi, Japan was used to analyze the surface and cross-section microstructure of the prepared TiB ₂ -Ni coating sample. It can be seen from the micrograph of the coating surface (Fig. 2) The surface of the coating is relatively flat, dense and without microcracks; it can be clearly seen from the cross-sectional micrographs of the coating that the thickness of the coating is uniform, and the crystals grow in a columnar shape and are closely arranged. The obtained TiB ₂ -Ni coating sample was analyzed by AXIS UTLTRADLD type XPS produced by Shimadzu Corporation, showing that the Ni content inside the coating was about 20.50%. The prepared TiB ₂ -Ni coating sample was tested under 5N force on a multifunctional friction and wear testing machine (UMT-3), and the friction coefficient of the coating was measured to be about 0.68. After the sample was worn for 1 hour, no failure was observed. , it can be seen that the TiB ₂ -Ni coating has good anti-friction and wear properties. Finally, the prepared TiB ₂ -Ni coating sample was subjected to acid and alkali corrosion resistance at room temperature, and the results showed that the coating had good stability.

Example 2:

1) A commercially available TiB ₂ ceramic target with a purity of 99.9% and a commercially available metal Ni target with a purity of 99.99% are selected as raw materials; the substrate is an ordinary flat glass substrate.

2) Firstly, the substrate is cleaned, and the substrate is ultrasonically cleaned with absolute ethanol, acetone, and absolute ethanol for 20 minutes in sequence, and then dried at 80° C. for 2 hours by blasting, and then set aside.

3) Using the magnetron sputtering system independently designed and produced by our research group, first open the cavity and install the substrate and target correctly, first check that the gas, electricity, and water circuits are normal, then turn on the main power supply and start the mechanical pump, when the deposition chamber and the sample After the air pressure in the chamber is below 10Pa, close the valve between the mechanical pump and the chamber, open the baffle valve, start the molecular pump, and unscrew the gate valve. When the vacuum in the sample chamber reaches 10 ^-3 Pa, stop the fine vacuuming. , to speed up the pumping speed of the vacuum in the deposition chamber.

4) When the background vacuum in the deposition chamber reaches 7×10 ^-5 Pa, turn on the heating mode of the sample substrate, set the temperature at 300°C, keep it warm for 20 minutes after reaching the specified temperature, and record the background when the vacuum reaches 7.8×10 ^-5 Pa. Bottom vacuum.

5) Open the argon gas bottle, control the flow rate at 26 sccm, unscrew the corresponding valve, feed inert gas, properly close the gate valve between the deposition chamber and the molecular pump, and adjust the air pressure in the deposition chamber to 0.3Pa.

6) Set the TiB ₂ ceramic target power supply parameters as: intermediate frequency (MF) 150HKZ, power 300W, duty cycle 90%; Ni metal target power supply parameters: direct current (DC), power 8W; after about 10 minutes of pre-sputtering, open the sample Baffle, formal sputtering deposition, deposition time: 30min.

7) After the deposition is completed, turn off the sample baffle, target power supply, gas path, etc. in turn; after the sample is cooled, take a sample to obtain the final product TiB ₂ -Ni thin film sample.

Example 3:

1) A commercially available TiB ₂ ceramic target with a purity of 99.9% and a commercially available metal Ni target with a purity of 99.99% are selected as raw materials; the substrate is a high-speed steel substrate.

2) Firstly, the substrate is cleaned, and the substrate is ultrasonically cleaned with absolute ethanol, acetone, and absolute ethanol for 20 minutes in sequence, and then dried at 80° C. for 2 hours by blasting, and then set aside.

3) Using the magnetron sputtering system independently designed and produced by our research group, first open the cavity and install the substrate and target correctly, first check that the gas, electricity, and water circuits are normal, then turn on the main power supply and start the mechanical pump, when the deposition chamber and the sample After the air pressure in the chamber is below 10Pa, close the valve between the mechanical pump and the chamber, open the baffle valve, start the molecular pump, and unscrew the gate valve. When the vacuum in the sample chamber reaches 10 ^-3 Pa, stop the fine vacuuming. , to speed up the pumping speed of the vacuum in the deposition chamber.

4) When the background vacuum in the deposition chamber reaches 5×10 ^-5 Pa, turn on the heating mode of the sample substrate, set the temperature at 500°C, keep it warm for 30 minutes after reaching the specified temperature, and record the background when the vacuum reaches 5.8×10 ^-5 Pa. Bottom vacuum.

5) Open the argon gas bottle, control the flow rate at 20 sccm, unscrew the corresponding valve, feed inert gas, properly close the gate valve between the deposition chamber and the molecular pump, and adjust the air pressure in the deposition chamber to 0.2Pa.

6) Set the TiB ₂ ceramic target power supply parameters as: intermediate frequency (MF) 50HKZ, power 400W, duty cycle 70%; Ni metal target power supply parameters: direct current (DC), power 18W; after about 10 minutes of pre-sputtering, open the sample Baffle, formal sputtering deposition, deposition time: 40min.

7) After the deposition is completed, close the sample baffle, target power supply, gas path, etc. in sequence; after the sample is cooled, take a sample to obtain the final product TiB ₂ -Ni coating sample.

Example 4:

1) A commercially available TiB ₂ ceramic target with a purity of 99.9% and a commercially available metallic Ni target with a purity of 99.99% are selected as raw materials; the substrate is a titanium alloy substrate.

2) Firstly, the substrate was cleaned, and the substrate was ultrasonically cleaned with absolute ethanol, acetone, and absolute ethanol for 15 minutes, and then dried at 80° C. for 1 hour, and then used for later use.

3) Using the magnetron sputtering system independently designed and produced by our research group, first open the cavity and install the plate and target correctly, first check that the gas, electricity, and water circuits are normal, then turn on the main power supply and start the mechanical pump, when the deposition chamber and the sample After the air pressure in the chamber is below 10Pa, close the valve between the mechanical pump and the chamber, open the baffle valve, start the molecular pump, and unscrew the gate valve. When the vacuum in the sample chamber reaches 10 ^-3 Pa, stop the fine vacuuming. , to speed up the pumping speed of the vacuum in the deposition chamber.

4) When the background vacuum in the deposition chamber reaches 8×10 ^-5 Pa, record the background vacuum.

5) Open the argon gas bottle, control the flow rate at 35 sccm, unscrew the corresponding valve, feed inert gas, properly close the gate valve between the deposition chamber and the molecular pump, and adjust the air pressure in the deposition chamber to 0.8Pa.

6) Set the TiB ₂ ceramic target power supply parameters as: intermediate frequency (MF) 100HKZ, power 200W, duty cycle 80%; Ni metal target power supply parameters: direct current (DC), power 15W; after about 10 minutes of pre-sputtering, open the sample Baffle, formal sputtering deposition, deposition time: 180min.

7) After the deposition is completed, close the sample baffle, target power supply, gas path, etc. in sequence; after the sample is cooled, take a sample to obtain the final product TiB ₂ -Ni coating sample.

Claims (2)

1. a kind of preparation method of titanium diboride-nickel coating or thin film, it is characterized in that with TiB ₂ ceramic target and metal Ni target are raw material, adopt physical vapor deposition technology, in-situ deposition different TiB ₂ and Ni proportioning Coating or film, the specific steps are: a) installing the target and substrate; b) vacuuming and substrate heating; vacuuming means that the vacuum of the back and bottom of the deposition chamber is lower than 9.5×10 ^-4 Pa, and the heating temperature of the substrate is from room temperature to 500°C and kept for 20 to 30 minutes; c) Feed an inert gas, set the power supply and substrate parameters, start, pre-sputter, and sputter deposition; the inert gas fed is argon, the flow of the inert gas is controlled at 20-40 sccm, and the pressure in the deposition chamber is adjusted to 0.1 The range of -1Pa; power supply and substrate parameters: TiB ₂ ceramic target power supply parameters: intermediate frequency 50-200KHZ, power 100-500W, duty cycle 60-90%; Ni metal target power supply parameters: DC power 0-20W; The pre-sputtering time is 8-15 minutes, and the sputtering deposition time is 30-200 minutes; the substrate parameters are bias voltage 0V, temperature room temperature-500°C; d) After the deposition is over, turn off the electricity, gas and water circuits, and take samples. 2. The preparation method according to claim 1, wherein the substrate in step a) is ultrasonically cleaned for 10 to 20 minutes with dehydrated alcohol, acetone and dehydrated alcohol respectively before installation, and then heated at 70 to 90° C. Dry under blast for 1-2 hours.