CN111826611A - AlTiN gradient hard coating and preparation method thereof - Google Patents
AlTiN gradient hard coating and preparation method thereof Download PDFInfo
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- CN111826611A CN111826611A CN202010713473.1A CN202010713473A CN111826611A CN 111826611 A CN111826611 A CN 111826611A CN 202010713473 A CN202010713473 A CN 202010713473A CN 111826611 A CN111826611 A CN 111826611A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- 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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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- 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
- C23C14/0641—Nitrides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- 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
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
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Abstract
The invention discloses an AlTiN gradient hard coating, which comprises a substrate, wherein a Cr priming layer is attached to the top of the substrate, a CrN transition layer is attached to the top of the Cr priming layer, a CrN + AlTiN transition layer is attached to the top of the CrN transition layer, and an AlTiN gradient layer is attached to the top of the CrN + AlTiN transition layer. The invention also provides a preparation method of the AlTiN gradient hard coating, which comprises the following steps: firstly, depositing a Cr bottom layer on the upper surface of a substrate by adopting arc ion plating; and then depositing a CrN transition layer on the Cr priming layer, then depositing a CrN + AlTiN transition layer on the CrN transition layer, and finally depositing an AlTiN gradient layer on the CrN + AlTiN transition layer by changing the bias voltage of four gradients. The AlTiN coating has high hardness and good film-substrate binding force. Therefore, the gradient AlTiN coating is adopted, so that the advantages of the AlTiN coating can be maintained, and the film-substrate binding force is improved.
Description
Technical Field
The invention belongs to the field of hard coating, and particularly relates to an AlTiN gradient hard coating and a preparation method thereof.
Background
AlTiN isThe novel Ti-based coating developed on the basis of TiN is called AlTiN to be different from TiAlN coating in coating with more Al content, has the characteristics of better hot hardness, high film-substrate binding force, high hardness, high oxidation temperature, small friction coefficient and the like, and is widely applied to the aspects of cutting tools, mold manufacturing, aeroengines, biomedicine and the like at present. The higher Al content ensures that the surface of the AlTiN coating can form compact, complete and continuous Al under the high-temperature condition2O3And a protective film, which can improve the high temperature oxidation resistance of the coating. Studies have shown that as the bias increases during deposition, the hardness of the coating increases, but at the same time the residual stress increases. Excessive residual stress can cause cracking of the coating and the substrate, thereby reducing the film-substrate bonding force.
In view of the above, there is a need to design an AlTiN gradient hard coating and a method for preparing the same, which changes the deposition bias by gradient to make the residual stress of the film layer near the substrate smaller and the hardness of the film layer near the surface larger. By reasonable design and the adoption of the gradient AlTiN coating, the advantages of the AlTiN coating can be maintained, and the film-substrate binding force is improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an AlTiN gradient hard coating and a preparation method thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
an AlTiN gradient hard coating is characterized in that: the Cr-AlTiN gradient film comprises a substrate, wherein a Cr bottoming layer is attached to the top of the substrate, a CrN transition layer is attached to the top of the Cr bottoming layer, a CrN + AlTiN transition layer is attached to the top of the CrN transition layer, and an AlTiN gradient layer is attached to the top of the CrN + AlTiN transition layer; cr accounting for 30 to 55 percent of the atomic percentage of each element in the CrN transition layer and N accounting for 45 to 70 percent of the atomic percentage of each element in the CrN transition layer; in the CrN + AlTiN transition layer, the atomic percent of each element in the CrN is 30-55% of Cr and 45-70% of N; the atomic percentages of the elements in the AlTiN are as follows: 30-40% of Al, 10-20% of Ti and 45-55% of N; the AlTiN gradient layer comprises the following elements in atomic percentage: 30-40% of Al, 10-20% of Ti and 45-55% of N, wherein the AlTiN gradient layer comprises 4 AlTiN coatings in deposition states, and the deposition bias voltage is 40-60A, 80-100A, 120-140A and 160-180A from bottom to top in sequence.
The invention also provides a preparation method of the AlTiN gradient hard coating, which is characterized by comprising the following steps: the method comprises the following steps: firstly, depositing a Cr bottom layer on the upper surface of a substrate by adopting arc ion plating; and then depositing a CrN transition layer on the Cr priming layer, then depositing a CrN + AlTiN transition layer on the CrN transition layer, and finally depositing an AlTiN gradient layer on the CrN + AlTiN transition layer by changing the bias voltage of four gradients.
As an optimized technical scheme, the method specifically comprises the following operation steps:
1) the substrate material was set on a rotating holder in a vacuum chamber, and the vacuum chamber was evacuated to a basic pressure of 1.0X 10-3Heating to 500-700 ℃ below Pa; then, the cavity of the vacuum chamber was filled with Ar having a purity of 99.99% to 1.0X 10-1-1.0 Pa; starting Ar ion glow discharge, and carrying out plasma etching on the surface of the base material for 30-40 minutes;
2) depositing a transition layer: firstly, carrying out Cr priming layer deposition for 2-5 minutes, and then introducing N2Igniting the Cr target by gas, setting the arc current to be 60-100A, and carrying out the reaction deposition of the CrN layer for 2-5 minutes; igniting the AlTi target, setting the arc current to be 60-100A, and carrying out reaction deposition on the CrN + AlTiN layer for 2-5 minutes;
3) depositing a gradient layer: closing the Cr target, igniting the AlTi target, adjusting the bias voltage, and depositing the gradient AlTiN coating for 15-30 minutes respectively under the bias voltages of 40-60A, 80-100A, 120-140A and 160-180A in sequence;
as an optimized technical scheme, the alloy targets used in the step 2) and the step 3) are 4 pure Cr targets and 4 AlTi targets, wherein the Al: the proportion of the atomic percent of Ti is 60-80%: 20-40%.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the beneficial effects that:
the AlTiN coating has high hardness and good film-substrate binding force at high temperature. Practice has shown that the higher the deposition voltage, the better the AlTiN hardness and wear resistance. The lower hardness AlTiN coating is deposited near the substrate with a lower voltage, which reduces the hardness difference and stress concentration at the interface, while the AlTiN coating deposited with a higher voltage on the surface in contact with the workpiece has a higher hardness and wear resistance. Therefore, the gradient AlTiN coating is adopted, so that the advantages of the AlTiN coating can be maintained, and the film-substrate binding force is improved.
The invention is further illustrated with reference to the figures and examples.
Drawings
FIG. 1 is a schematic view of the flow principle of the present invention.
FIG. 2 shows the surface morphology of the AlTiN gradient hard coating of the invention.
FIG. 3 is a picture of the adhesion test of the AlTiN gradient hard coating of the present invention.
Detailed Description
This example shows a method for preparing an AlTiN gradient hard coating layer for a cemented carbide milling cutter surface, and it should be noted that the scope of the present invention is not limited to the following examples.
Example 1:
as shown in figure 1, the AlTiN gradient hard coating comprises a substrate, a Cr priming layer is attached to the top of the substrate, a CrN transition layer is attached to the top of the Cr priming layer, a CrN + AlTiN transition layer is attached to the top of the CrN transition layer, and an AlTiN gradient layer is attached to the top of the CrN + AlTiN transition layer. The atomic percent of each element in the CrN transition layer is 45 percent of Cr and 55 percent of N. In the CrN + AlTiN transition layer, the atomic percent of each element in CrN is 45 percent of Cr and 55 percent of N, and the atomic percent of each element in AlTiN is as follows: 30% of Al, 16% of Ti and 54% of N. The AlTiN gradient layer comprises the following elements in atomic percentage: 30% of Al, 16% of Ti and 54% of N, wherein the AlTiN gradient layer comprises 4 AlTiN coatings in deposition states, and the deposition bias voltages are 40A, 80A, 120A and 160A from bottom to top in sequence.
The embodiment also provides a preparation method of the AlTiN gradient hard coating, which comprises the steps of firstly depositing a Cr priming coat on the upper surface of a substrate by adopting arc ion plating; and then depositing a CrN transition layer on the priming layer, then depositing a CrN + AlTiN transition layer on the CrN transition layer, and finally depositing an AlTiN gradient layer on the CrN + AlTiN transition layer by changing the bias voltage of the four gradients.
The detailed operation steps are as follows:
1) the substrate material was set on a rotating holder in a vacuum chamber, and the vacuum chamber was evacuated to a basic pressure of 1.0X 10-3Heating to 600 ℃ below Pa; then, the cavity of the vacuum chamber was filled with Ar having a purity of 99.99% to 1.0X 10-1Pa; starting Ar ion glow discharge, and carrying out plasma etching on the surface of the base material for 35 minutes.
2) Depositing a transition layer: firstly, carrying out Cr priming layer deposition for 2-5 minutes, and then introducing N2Igniting the Cr target by gas, setting the arc current to be 60-100A, and carrying out the reaction deposition of the CrN layer for 2-5 minutes; and igniting the AlTi target, setting the arc current to be 60-100A, and carrying out the reaction deposition of the CrN + AlTiN layer for 2-5 minutes. The atomic percentage ratio of 4 pure Cr targets to 4 AlTi targets is 68%: 32 percent.
3) Depositing a gradient layer: the Cr target was turned off, the AlTi target was ignited, the bias was adjusted, and the gradient AlTiN coating was deposited for 20 minutes each at a bias of 40A, 80A, 120A, and 160A in sequence. Al in the AlTi target: the proportion of the atomic percentage of Ti is 68%: 32 percent.
Fig. 2 shows the surface morphology of the AlTiN gradient hard coating, and it can be seen that the coating surface is dense and has less large particles.
The AlTiN gradient hard coating prepared in this example was tested for binding force experiments. The indentation morphology is shown in fig. 3, from which it can be seen that the coating edge is smooth, without cracks and without any flaking phenomenon. As can be seen from the bond strength test standards, the bond strength rating of the coating to the substrate was HF1, the highest standard. Therefore, the AlTiN gradient hard coating has good bonding force with the substrate.
Example 2:
as shown in figure 1, the AlTiN gradient hard coating comprises a substrate, a Cr priming layer is attached to the top of the substrate, a CrN transition layer is attached to the top of the Cr priming layer, a CrN + AlTiN transition layer is attached to the top of the CrN transition layer, and an AlTiN gradient layer is attached to the top of the CrN + AlTiN transition layer. The atomic percent of each element in the CrN transition layer is 35 percent of Cr and 65 percent of N. In the CrN + AlTiN transition layer, the atomic percent of each element in CrN is 35% of Cr and 65% of N, and the atomic percent of each element in AlTiN is as follows: 35% of Al, 15% of Ti and 50% of N. The AlTiN gradient layer comprises the following elements in atomic percentage: 35% of Al, 15% of Ti and 50% of N, wherein the AlTiN gradient layer comprises 4 AlTiN coatings in deposition states, and the deposition bias voltages are 40A, 80A, 120A and 160A from bottom to top in sequence.
The embodiment also provides a preparation method of the AlTiN gradient hard coating, which comprises the steps of firstly depositing a Cr priming coat on the upper surface of a substrate by adopting arc ion plating; and then depositing a CrN transition layer on the priming layer, then depositing a CrN + AlTiN transition layer on the CrN transition layer, and finally depositing an AlTiN gradient layer on the CrN + AlTiN transition layer by changing the bias voltage of the four gradients.
The detailed operation steps are as follows:
1) the substrate material was set on a rotating holder in a vacuum chamber, and the vacuum chamber was evacuated to a basic pressure of 1.0X 10-3Heating to 550 ℃ below Pa; then, the cavity of the vacuum chamber was filled with Ar having a purity of 99.99% to 1.0X 10-1Pa; starting Ar ion glow discharge, and carrying out plasma etching on the surface of the base material for 35 minutes.
2) Depositing a transition layer: firstly, carrying out Cr priming layer deposition for 2-5 minutes, and then introducing N2Igniting the Cr target by gas, setting the arc current to be 60-100A, and carrying out the reaction deposition of the CrN layer for 2-5 minutes; and igniting the AlTi target, setting the arc current to be 60-100A, and carrying out the reaction deposition of the CrN + AlTiN layer for 2-5 minutes. The atomic percentage ratio of 4 pure Cr targets to 4 AlTi targets is 70%: 30 percent.
3) Depositing a gradient layer: the Cr target was turned off, the AlTi target was ignited, the bias was adjusted, and the gradient AlTiN coating was deposited for 20 minutes each at a bias of 40A, 80A, 120A, and 160A in sequence. Al in the AlTi target: the proportion of the atomic percent of Ti is 70%: 30 percent.
Fig. 2 shows the surface morphology of the AlTiN gradient hard coating, and it can be seen that the coating surface is dense and has less large particles.
The AlTiN gradient hard coating prepared in this example was tested for binding force experiments. The indentation morphology is shown in fig. 3, from which it can be seen that the coating edge is smooth, without cracks and without any flaking phenomenon. As can be seen from the bond strength test standards, the bond strength rating of the coating to the substrate was HF1, the highest standard. Therefore, the AlTiN gradient hard coating has good bonding force with the substrate.
Example 3:
as shown in figure 1, the AlTiN gradient hard coating comprises a substrate, a Cr priming layer is attached to the top of the substrate, a CrN transition layer is attached to the top of the Cr priming layer, a CrN + AlTiN transition layer is attached to the top of the CrN transition layer, and an AlTiN gradient layer is attached to the top of the CrN + AlTiN transition layer. The atomic percent of each element in the CrN transition layer is 50 percent of Cr and 50 percent of N. In the CrN + AlTiN transition layer, the atomic percent of each element in CrN is 50% of Cr and 50% of N, and the atomic percent of each element in AlTiN is as follows: 40% of Al, 20% of Ti and 40% of N. The AlTiN gradient layer comprises the following elements in atomic percentage: the Al content is 40%, the Ti content is 20%, the N content is 40%, and the AlTiN gradient layer comprises 4 AlTiN coatings in deposition states, and the deposition bias voltages are 40A, 80A, 120A and 160A from bottom to top in sequence.
The invention also provides a preparation method of the AlTiN gradient hard coating, which comprises the steps of firstly depositing a Cr priming coat on the upper surface of the substrate by arc ion plating; and then depositing a CrN transition layer on the priming layer, then depositing a CrN + AlTiN transition layer on the CrN transition layer, and finally depositing an AlTiN gradient layer on the CrN + AlTiN transition layer by changing the bias voltage of the four gradients.
The detailed operation steps are as follows:
1) the substrate material was set on a rotating holder in a vacuum chamber, and the vacuum chamber was evacuated to a basic pressure of 1.0X 10-3Heating to 500-700 ℃ below Pa; then, filling the cavity of the vacuum chamber to 1.0Pa by using Ar with the purity of 99.99 percent; starting Ar ion glow discharge, and carrying out plasma etching on the surface of the base material for 35 minutes.
2) Depositing a transition layer: firstly, carrying out Cr priming layer deposition for 2-5 minutes, and then introducing N2Igniting the Cr target by gas, setting the arc current to be 60-100A, and carrying out the reaction deposition of the CrN layer for 2-5 minutes; while igniting the AlTi target, settingArc current is 60-100A, and the reaction deposition of the CrN + AlTiN layer is carried out for 2-5 minutes. The atomic percentage ratio of 4 pure Cr targets to 4 AlTi targets is 80%: 20 percent.
3) Depositing a gradient layer: the Cr target was turned off, the AlTi target was ignited, the bias was adjusted, and the gradient AlTiN coating was deposited for 20 minutes each at a bias of 40A, 80A, 120A, and 160A in sequence. Al in the AlTi target: the proportion of the atomic percent of Ti is 80%: 20 percent.
Fig. 2 shows the surface morphology of the AlTiN gradient hard coating, and it can be seen that the coating surface is dense and has less large particles.
The AlTiN gradient hard coating prepared in this example was tested for binding force experiments. The indentation morphology is shown in fig. 3, from which it can be seen that the coating edge is smooth, without cracks and without any flaking phenomenon. As can be seen from the bond strength test standards, the bond strength rating of the coating to the substrate was HF1, the highest standard. Therefore, the AlTiN gradient hard coating has good bonding force with the substrate.
The three embodiments are the best three embodiments in the experimental process. Experiments with other parameters, within the scope of the invention, can produce coatings with composite requirements using the process of the invention.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. An AlTiN gradient hard coating is characterized in that: the Cr-AlTiN gradient film comprises a substrate, wherein a Cr bottoming layer is attached to the top of the substrate, a CrN transition layer is attached to the top of the Cr bottoming layer, a CrN + AlTiN transition layer is attached to the top of the CrN transition layer, and an AlTiN gradient layer is attached to the top of the CrN + AlTiN transition layer;
cr accounting for 30 to 55 percent of the atomic percentage of each element in the CrN transition layer and N accounting for 45 to 70 percent of the atomic percentage of each element in the CrN transition layer;
in the CrN + AlTiN transition layer, the atomic percent of each element in the CrN is 30-55% of Cr and 45-70% of N; the atomic percentages of the elements in the AlTiN are as follows: 30-40 at.% of Al, 10-20 at.% of Ti and 45-55 at.% of N;
the AlTiN gradient layer comprises the following elements in atomic percentage: 30-40 at.% of Al, 10-20 at.% of Ti and 45-55 at.% of N, wherein the AlTiN gradient layer comprises 4 AlTiN coatings in deposition states, and the deposition bias voltage is 40-60A, 80-100A, 120-140A and 160-180A from bottom to top in sequence.
2. The method for preparing an AlTiN gradient hard coating according to claim 1, wherein: the method comprises the following steps: firstly, depositing a Cr bottom layer on the upper surface of a substrate by adopting arc ion plating; and then depositing a CrN transition layer on the Cr priming layer, then depositing a CrN + AlTiN transition layer on the CrN transition layer, and finally depositing an AlTiN gradient layer on the CrN + AlTiN transition layer by changing the bias voltage of four gradients.
3. The method for preparing an AlTiN gradient hard coating according to claim 2, wherein: the method specifically comprises the following operation steps:
1) the substrate material was set on a rotating holder in a vacuum chamber, and the vacuum chamber was evacuated to a basic pressure of 1.0X 10-3Heating to 500-700 ℃ below Pa; then, the cavity of the vacuum chamber was filled with Ar having a purity of 99.99% to 1.0X 10-1-1.0 Pa; starting Ar ion glow discharge, and carrying out plasma etching on the surface of the base material for 30-40 minutes;
2) depositing a transition layer: firstly, carrying out Cr priming layer deposition for 2-5 minutes, and then introducing N2Igniting the Cr target by gas, setting the arc current to be 60-100A, and carrying out the reaction deposition of the CrN layer for 2-5 minutes; igniting the AlTi target, setting the arc current to be 60-100A, and carrying out reaction deposition on the CrN + AlTiN layer for 2-5 minutes;
3) depositing a gradient layer: closing the Cr target, igniting the AlTi target, adjusting the bias voltage, and depositing the gradient AlTiN coating for 15-30 minutes respectively under the bias voltages of 40-60A, 80-100A, 120-140A and 160-180A in sequence;
4. the method for preparing an AlTiN gradient hard coating according to claim 3, wherein: the alloy targets used in the step 2) and the step 3) are 4 pure Cr targets and 4 AlTi targets, wherein Al: the proportion of the atomic percent of Ti is 60-80%: 20-40%.
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2020
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| CN106676470A (en) * | 2017-01-09 | 2017-05-17 | 福建工程学院 | AlTiON hot work die steel composite gradient coating and preparation method thereof |
| CN108796432A (en) * | 2018-09-12 | 2018-11-13 | 广东工业大学 | A kind of AlTiN coatings and preparation method thereof |
| CN109023266A (en) * | 2018-10-19 | 2018-12-18 | 广东工业大学 | A kind of microbit and preparation method thereof being deposited with AlTiN coating |
| CN109518139A (en) * | 2018-12-13 | 2019-03-26 | 北京金轮坤天特种机械有限公司 | A kind of titanium fire flame retardant coating and preparation method thereof |
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