CN107937914B - Method for preparing diamond film on transition layer on surface of stainless steel - Google Patents
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- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/271—Diamond only using hot filaments
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/343—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one DLC or an amorphous carbon based layer, the layer being doped or not
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Abstract
The invention provides a method for preparing a continuous diamond film with good adhesive force on the surface of stainless steel, which comprises the following steps: the method comprises the steps of respectively ultrasonically cleaning and drying a stainless steel sheet by using acetone and absolute ethyl alcohol to be used as a substrate for growing a diamond film, before depositing the diamond film, putting the stainless steel substrate into vacuum ion plating equipment, preparing a new-structure film on the surface of the stainless steel substrate to be used as a transition layer, then carrying out ultrasonic seed crystal in an acetone solution of diamond powder, and finally putting the diamond film into hot filament chemical vapor deposition equipment to grow the diamond film. The invention can produce continuous diamond film with good adhesive force. Has wide application prospect in the product field taking stainless steel as a base material.
Description
(I) technical field
The invention discloses a method for preparing a diamond film with high hardness and good adhesive force on a transition layer on the surface of stainless steel.
(II) background of the invention
The diamond film has a plurality of excellent performances such as high hardness, small friction coefficient, excellent corrosion resistance, good heat conductivity and the like. The stainless steel is the most widely used material in the current market, and the preparation of the diamond film on the surface of the stainless steel can greatly improve the service life of the stainless steel product. However, the diamond film cannot be directly prepared on the surface of the stainless steel due to a series of reasons such as catalytic graphitization of Fe and difference in thermal matching and structural matching between the stainless steel substrate and the diamond film. The traditional method is to prepare one or more transition layers between stainless steel and a diamond film, and although the method can play a role in hindering the diffusion of Fe and C, so that the diamond film can grow on the surface of the stainless steel and can play a role in buffering stress to a certain extent, the difference of the thermal expansion coefficients of the stainless steel substrate and the diamond film is very large, and the adhesion force of the diamond film is not ideal enough. Moreover, the transition layer used at present is mostly a heavy metal harmful substance such as chromium, nickel and the like, so that the diamond film prepared on the surface of the stainless steel is difficult to be applied to the aspects of food, medical instruments and the like. In the previous work, we received the patent "a method for preparing diamond films on metastable austenitic stainless steel surfaces, patent No. 201610789664. X". The invention adopts sand blasting and a Cr/CrN transition layer to improve the adhesive force of the diamond film, wherein the sand blasting method can convert metastable austenite in the surface of austenitic stainless steel into martensite with smaller thermal expansion coefficient, can effectively reduce the thermal expansion coefficient difference between the substrate and the diamond film, and improves the adhesive force between the diamond film and the substrate. We have also developed a new CVD process accepting the patent "a method of making diamond films on stainless steel using Cr/CrN/CrTiAlN as the transition layer, patent No. 201710532082.8". Taking Cr/CrN/CrTiAlN as a transition layer, depositing for a period of time under a higher power when preparing the diamond film, and then reducing the deposition power to continue growing. On one hand, the performances of the adhesion force and the like of the diamond film are improved by utilizing the high hardness of the Cr/CrN/CrTiAlN transition layer and the good bonding force between the Cr/CrN/CrTiAlN transition layer and the stainless steel base and the diamond film. On the other hand, the residual thermal stress is reduced by a double deposition method of the CVD process.
The Al-Si-N film is made of amorphous Si3N4And crystalline AlN, which is distinct from the Cr/CrN and Cr/CrN/CrTiAlN transition layers of our accepted patents 201610789664.X and 201710532082.8. The composite film not only meets the characteristics of a common transition layer, namely the thermal expansion coefficient of the composite film is between that of stainless steel and a diamond film, and can relieve the thermal stress caused by the difference of the thermal expansion coefficients, but also is expected to relieve the stress generated in the growth process of the diamond film by the special structure formed by the crystal and the amorphous of the Al-Si-N nano composite film. Compared with the common transition layer, the diamond film prepared on the Al-Si-N nano composite film transition layer has better adhesive force. Secondly, the self hardness of the Al-Si-N nano composite film is very high and can reach 30-50GPa, which is greatly helpful for improving the comprehensive hardness of the product. Thirdly, the aluminum element in the Al-Si-N nano composite film can promote the nucleation of the diamond film, inhibit the generation of graphite phase, improve the growth rate of the diamond film and reduce the content of the graphite phase in the film. Fourthly, the surface appearance of the Al-Si-N nano composite film can be regulated and controlled by changing the thickness of the Al layer between the Al-Si-N nano composite transition layer and the stainless steel, and further the nucleation and growth of the diamond are influenced. Fifthly, the Al-Si-N nano composite film does not contain heavy metal elements, is harmless to human bodies and is beneficial to the application of the stainless steel base diamond film in the aspects of food processing and medical appliances; and the Al-Si-N nano composite film transition layer has good corrosion resistance, and when the diamond film is not very compact in growth, the transition layer can also play a role in protecting the stainless steel substrate from being corroded to a certain extent. Meanwhile, in order to obtain an Al-Si-N film with a rough surface, firstly an Al layer is prepared on a stainless steel substrate, then an Al-Si-N nano composite film is prepared on the Al layer, and then a diamond film is grown on the Al layer, so that the diamond film with good adhesive force is obtained on the stainless steel substrate.
Disclosure of the invention
The invention aims to provide a diamond film with higher adhesive force and high hardness grown on a transition layer on the surface of stainless steel and a preparation method thereof.
The technical scheme of the invention is as follows: (1) preparing an Al layer with the thickness of 100-1000nm on the surface of the stainless steel by adopting a magnetron sputtering method; (2) preparing an Al-Si-N nano composite film on the Al layer of the stainless steel obtained in the step (1) by adopting a reactive sputtering method, wherein the thickness of the Al-Si-N nano composite film is 500-700 nm; (3) and (3) depositing a diamond film on the A1-Si-N nano composite film obtained in the step (2) by using a hot wire chemical vapor deposition device.
The stainless steel is preferably 3Cr13 stainless steel after pretreatment, wherein the pretreatment comprises the steps of sequentially polishing the 3Cr13 stainless steel by using sand paper of 400-.
Further, in the present invention,the specific steps in the step (1) are as follows: putting stainless steel into physical vapor deposition equipment, respectively putting (purity is 99.999%) Si and Al target materials on two independent target supports, wherein the target base distance is 70-75mm, and the vacuum degree is less than 1.0 multiplied by 10-3Pa, introducing high-purity Ar gas, wherein the flow rate of the Ar gas is 15-20mL/min (abbreviated as sccm in the text), the working pressure is 0.3-1Pa, the power of the Al target is 100-200W, the power of the Si target is 0W, the deposition time is 5-30 minutes, and preparing an Al layer with the thickness of 100-1000nm on the surface of the stainless steel.
Further, the specific steps in the step (2) are as follows: after the step (1) is finished, adjusting the power of the Al target to be 100-200W and the power of the Si target to be 5-200W; by Ar gas and N2The flow rate of Ar gas is 15-20sccm, N2The gas flow is 2-10sccm, the working gas pressure is controlled to be-0.3-1 Pa, the deposition time is 30-60min, the substrate temperature is 200-.
Further, the specific steps in the step (3) are as follows: ultrasonically oscillating the stainless steel of the Al/Al-Si-N nano composite film obtained in the step (2) in an acetone solution of diamond powder for 20-60 minutes, and carrying out seed crystal treatment; then placing the film into a cavity of hot wire chemical vapor deposition equipment to deposit a diamond film on the Al/Al-Si-N nano composite film, taking acetone as a carbon source, and carrying the acetone into a reaction chamber by adopting a hydrogen bubbling mode, wherein the flow ratio of hydrogen to acetone is 200: 80, the power is 1800-plus-2000W, the air pressure is 1-3Pa, the deposition time is 10-30min, the bias flow is 4A, then reducing the power to 1500-plus-1600W to continue to grow for 10-30min, and slowly cooling the film in a hydrogen atmosphere after the growth is finished to obtain the diamond film.
The physical vapor deposition equipment (PVD equipment) is purchased from Shenyang scientific instruments, Inc. of China academy of sciences, and is a JGP-450 type fast ion plating instrument.
The hot wire chemical vapor deposition equipment is purchased from Shanghai friend-making Diamond coatings Co., Ltd, and is of the type JUHF CVD 001.
The invention has the following beneficial effects: (1) the increase of the thickness of the Al layer can increase the roughness of the surface of the Al-Si-N nano composite film, thereby increasing the nucleation rate of the diamond. (2) The Al-Si-N nano composite film can relieve thermal stress through a special crystal and amorphous composite structure of the Al-Si-N nano composite film, so that the diamond film has better adhesive force; and the higher hardness is beneficial to improving the integral hardness of the system. (3) The aluminum element in the Al-Si-N nano composite film can promote nucleation of the diamond film, inhibit generation of graphite phase, improve growth rate of the diamond film and reduce content of the graphite phase in the film. (4) The Al-Si-N nano composite film does not contain heavy metal elements and is harmless to human bodies. (5) The Al-Si-N nano composite film transition layer has good corrosion resistance, and when the diamond film is not very compact in growth, the transition layer can also play a role in protecting the stainless steel substrate from being corroded to a certain extent.
(IV) description of the drawings
FIG. 1 is an SEM photograph of the Al-Si-N nanocomposite film of example 1;
FIG. 2 is a Raman spectrum of the diamond film of example 1;
FIG. 3 is an SEM photograph of the diamond film of example 1;
FIG. 4 is a chart of nanoindentation test curves for the diamond film of example 1;
FIG. 5 is a Raman spectrum of the diamond film of example 2;
FIG. 6 is an SEM photograph of a diamond film of example 2;
FIG. 7 is a chart of nanoindentation test curves for the diamond film of example 2;
FIG. 8 is a Raman spectrum of the diamond film of example 3;
FIG. 9 is an SEM photograph of the diamond film of example 3;
fig. 10 is a nano-indentation test curve pattern of the diamond film of example 3.
(V) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
example 1:
sequentially polishing 3Cr13 stainless steel by using 400-3000# abrasive paper, ultrasonically oscillating the polished sample by using acetone and absolute ethyl alcohol for 20 minutes, quickly drying the sample for later use by using a nitrogen gun, and depositing an Al/Al-Si-N double-layer transition layer on the treated stainless steel sheet in PVD equipment. Si and Al target materials with the purity of 99.999 percent are respectively placed on two independent target supports, and the target base distance is 70 mm. The vacuum degree is better than 1.0 multiplied by 10-3Pa, introducing high-purity Ar gas, and the technological parameters of the Al deposition stage are as follows: the flow rate of Ar gas is 20sccm, the working pressure is 0.4Pa, the power of the Al target is 150W, and the deposition time is 5 minutes. The technological parameters for preparing the Al-Si-N nano composite film are as follows: the Al target power was 150W and the Si target power was 90W. The Ar gas flow rate was 15sccm, the N2 gas flow rate was 10sccm, the working gas pressure was 0.4Pa, the deposition time was 40 minutes, and the substrate temperature was 400 ℃. And (3) ultrasonically oscillating the prepared sample of the Al/Al-Si-N nano composite film transition layer in an acetone solution of diamond powder for 30min, carrying out seed crystal treatment, and then putting the sample into a hot wire CVD (chemical vapor deposition) cavity to prepare the diamond film. Acetone is taken as a carbon source, the acetone is brought into a reaction chamber by adopting a hydrogen bubbling mode, wherein the flow ratio of hydrogen to acetone is 200: 80, the power is 1800W, the air pressure is 1.5KPa, the deposition time is 15min, the bias current is 4A, and then the power is reduced to 1600W for continuous growth for 10 min. And after the growth is finished, slowly cooling the film in a hydrogen atmosphere to obtain the diamond film.
A scanning electron microscope with a desk tungsten filament was used to observe the surface morphology of Al-Si-N, as shown in FIG. 1. Thus obtaining a continuous compact Al-Si-N transition layer; the components of the diamond film were analyzed by Raman spectroscopy, and as shown in fig. 2, the diamond peak was significant, indicating that the diamond film was prepared. FIG. 3 is a surface topography of a diamond film, showing continuous densification of the diamond film; fig. 4 shows the nano indentation test corresponding to the diamond film, when the load is 4000mN, the indentation depth is about 80nm, and the hardness is calculated to be 76GPa, so that the diamond film with higher hardness is obtained. From the experimental results, we successfully prepare and obtain the continuous compact diamond film with higher hardness.
Example 2:
sequentially polishing 3Cr13 stainless steel by using 400-3000# abrasive paper, ultrasonically oscillating the polished sample by using acetone and absolute ethyl alcohol for 20 minutes, quickly drying the sample for later use by using a nitrogen gun, and depositing an Al/Al-Si-N double-layer transition layer on the treated stainless steel sheet in PVD equipment. Si and Al target materials with the purity of 99.999 percent are respectively placed on two independent target supports, and the target base distance is 70 mm. The vacuum degree is better than 1.0 multiplied by 10-3Pa, introducing high-purity Ar gas, and the technological parameters of the Al deposition stage are as follows: the flow rate of Ar gas is 20sccm, the working pressure is 0.4Pa, the power of the Al target is 150W, and the deposition time is 5 min. The technological parameters for preparing the Al-Si-N nano composite film are as follows: the Al target power was 150W and the Si target power was 120W. The Ar gas flow rate was 15sccm, the N2 gas flow rate was 10sccm, the working gas pressure was 0.4Pa, the deposition time was 40 minutes, and the substrate temperature was 400 ℃. And (3) ultrasonically oscillating the prepared sample of the Al/Al-Si-N nano composite film transition layer in an acetone solution of diamond powder for 30min, carrying out seed crystal treatment, and then putting the sample into a hot wire CVD (chemical vapor deposition) cavity to prepare the diamond film. Taking acetone as a carbon source, and carrying the acetone into a reaction chamber in a hydrogen bubbling mode, wherein the flow ratio of hydrogen to acetone is 200: 80, 1800W of power, 1.5KPa of air pressure, 15min of deposition time, 4A of bias current, and then reducing the power to 1600W to continue growing for 10 min. And after the growth is finished, slowly cooling the film in a hydrogen atmosphere to obtain the diamond film.
The components of the diamond film were analyzed by Raman spectroscopy, and as shown in fig. 5, the diamond peak was significant, indicating that the diamond film was prepared. The surface morphology of the diamond was observed by scanning electron microscopy with a desk tungsten filament, as shown in FIG. 6, indicating that a continuous and dense diamond film was obtained. The hardness of the diamond film was measured by nanoindentation, and as shown in fig. 7, when the load was 4000mN, the indentation depth was about 70nm, and the hardness was calculated to be 98GPa, which indicates that a diamond film with higher hardness was obtained. The experimental result shows that the continuous compact diamond film with higher hardness is obtained by the experiment.
Example 3:
sequentially polishing 3Cr13 stainless steel with 400-And (4) quickly drying for standby, and putting the processed stainless steel sheet into PVD equipment for deposition of an Al/Al-Si-N double-layer transition layer. Si and Al target materials with the purity of 99.999 percent are respectively placed on two independent target supports, and the target base distance is 70 mm. The vacuum degree is better than 1.0 multiplied by 10-3Pa, introducing high-purity Ar gas, and the technological parameters of the Al deposition stage are as follows: the flow rate of Ar gas is 20sccm, the working pressure is 0.4Pa, the power of the Al target is 150W, and the deposition time is 5 min. The technological parameters for preparing the Al-Si-N nano composite film are as follows: the Al target power was 200W and the Si target power was 60W. Ar gas flow rate was 15sccm, N2The gas flow rate was 10sccm, the working gas pressure was 0.4Pa, the deposition time was 40 minutes, and the substrate temperature was 400 ℃. And (3) ultrasonically oscillating the prepared sample of the Al/Al-Si-N nano composite film transition layer in an acetone solution of diamond powder for 30min, carrying out seed crystal treatment, and then putting the sample into a hot wire CVD (chemical vapor deposition) cavity to prepare the diamond film. Acetone is taken as a carbon source, the acetone is brought into a reaction chamber by adopting a hydrogen bubbling mode, wherein the flow ratio of hydrogen to acetone is 200: 80, the power is 1800W, the air pressure is 1.5KPa, the deposition time is 15min, the bias current is 4A, and then the power is reduced to 1600W for continuous growth for 10 min. And after the growth is finished, slowly cooling the film in a hydrogen atmosphere to obtain the diamond film.
The components of the diamond film were analyzed by Raman spectroscopy, and as shown in fig. 8, the diamond peak was significant, indicating that the diamond film was prepared. The surface morphology of the diamond was observed by scanning electron microscopy with a desk tungsten filament, as shown in FIG. 9, indicating that a continuous and dense diamond film was obtained. The hardness of the diamond film was tested using nanoindentation, as shown in fig. 10. When the load was 4000mN, the indentation depth was about 70nm, and the hardness was 97GPa by calculation, and it was found that a diamond film having a high hardness was obtained. The experimental result shows that the continuous compact diamond film with higher hardness is obtained by the experiment.
Claims (4)
1. A method for preparing a diamond film on a transition layer on the surface of stainless steel is characterized by comprising the following steps:
(1) preparing an Al layer with the thickness of 100-1000nm on the surface of the stainless steel by adopting a magnetron sputtering method; (2) method using reactive sputteringPreparing an Al-Si-N nano composite film on the Al layer of the stainless steel obtained in the step (1) by the method, wherein the thickness of the Al-Si-N nano composite film is 500-700 nm; (3) depositing a diamond film on the Al-Si-N nano composite film obtained in the step (2) by using hot wire chemical vapor deposition equipment, wherein the step (2) is as follows: after the step (1) is finished, adjusting the power of the Al target to be 100-200W and the power of the Si target to be 5-200W; ar gas and N are introduced2Gas, Ar gas flow is 15-20ml/min, N2The air flow is 2-10ml/min, the working air pressure is controlled to be 0.3-1Pa, the deposition time is 30-60min, the substrate temperature is 200-400 ℃, and an Al-Si-N nano composite film with the thickness of 500-700nm is prepared on the stainless steel sputtered with the Al layer obtained in the step (1).
2. The method according to claim 1, wherein the specific steps in the step (1) are: putting stainless steel into physical vapor deposition equipment, respectively placing Si and Al target materials on two independent target supports, wherein the target base distance is 70-75mm, and the vacuum degree is less than 1.0 multiplied by 10-3Pa, introducing high-purity Ar gas, wherein the flow rate of the Ar gas is 15-20ml/min, the working pressure is 0.3-1Pa, the power of the Al target is 100-200W, the power of the Si target is 0W, the deposition time is 5-30 minutes, and preparing an Al layer with the thickness of 100-1000nm on the surface of the stainless steel.
3. The method according to claim 1, wherein the specific steps in the step (3) are: ultrasonically oscillating the stainless steel of the Al/Al-Si-N nano composite film obtained in the step (2) in an acetone solution of diamond powder for 20-60 minutes, and carrying out seed crystal treatment; then placing the film into a cavity of hot wire chemical vapor deposition equipment to deposit a diamond film on the Al/Al-Si-N nano composite film, taking acetone as a carbon source, and carrying the acetone into a reaction chamber by adopting a hydrogen bubbling mode, wherein the flow ratio of hydrogen to acetone is 200: 80, the power is 1800-plus-2000W, the air pressure is 1-3Pa, the deposition time is 10-30min, the bias flow is 4A, then reducing the power to 1500-plus-1600W to continue to grow for 10-30min, and slowly cooling the film in a hydrogen atmosphere after the growth is finished to obtain the diamond film.
4. The method of claim 1, wherein: the stainless steel is pretreated stainless steel, the pretreatment is that the stainless steel is sequentially polished by 400-3000# abrasive paper, the polished stainless steel is respectively ultrasonically vibrated for 20-60 minutes by acetone and absolute ethyl alcohol, and is quickly dried by a nitrogen gun for later use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711205732.4A CN107937914B (en) | 2017-11-27 | 2017-11-27 | Method for preparing diamond film on transition layer on surface of stainless steel |
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| CN110629194B (en) * | 2019-10-31 | 2021-11-02 | 浙江工业大学 | Method for preparing diamond film on stainless steel surface by taking Cr/CrAlN as transition layer |
| CN114411117B (en) * | 2021-12-31 | 2024-05-03 | 浙江工业大学 | Method for preparing diamond film with micro-texture surface on stainless steel |
| CN116240544A (en) * | 2023-02-07 | 2023-06-09 | 广东工业大学 | Method for preparing PVD (physical vapor deposition) composite CVD diamond coating and prepared coating and cutter |
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