CN110777341A - DLC/CNx/MeN/CNx nano multilayer film and preparation method thereof - Google Patents
DLC/CNx/MeN/CNx nano multilayer film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of film materials, and provides a DLC/CNx/Men/CNx nano multilayer film for solving the problems that the traditional DLC film has poor bonding strength with a substrate material and the wear resistance is reduced due to the fact that the bonding strength is improved by reducing stress, wherein the DLC/CNx/Men/CNx nano multilayer film comprises a substrate (1), a metal transition layer (2) and a nano multilayer film, wherein the metal transition layer and the nano multilayer film are sequentially deposited on the surface of the substrate, the nano multilayer film comprises a plurality of nano composite units (3), and the nano composite units sequentially comprise a DLC layer (4), a first gradient CNx layer (5), a metal nitride layer (6) and a second gradient CNx layer (7. The nano multilayer film effectively solves the problem of low film-substrate binding force of the traditional deposition method, reduces the internal stress and has excellent wear resistance; the preparation method has the advantages of simple steps, easily controlled process conditions, safe and pollution-free preparation process, low cost and easy realization of industrialization.
Description
Technical Field
The invention relates to the technical field of thin film materials, in particular to a DLC/CNx/Men/CNx nano multilayer film and a preparation method thereof.
Background
Diamond-like Carbon (DLC) films have a wide application prospect in the fields of mechanical parts, electronic devices, biomedicine, and the like due to their advantages of higher hardness, good wear resistance, biocompatibility, and the like. At present, the preparation technology of the DLC film mainly comprises magnetron sputtering deposition, chemical vapor deposition, magnetic filtration cathode vacuum arc deposition and the like, but the DLC film has obvious residual stress, so that the DLC film is easy to fall off from a substrate during bearing.
The bonding strength between the DLC film and the base material is poor, and a large part of the reason is that the difference between the coefficients of thermal expansion of the DLC film and the base material is large, which results in large internal stress in the DLC film. At present, methods for reducing the internal stress of the DLC film mainly include a doping method and a nano multilayer film technology. The doping method reduces the internal stress of the film by doping a metal (Ti, Cr, Al) or a non-metal element in the DLC film, but some studies have shown that, after doping the element, the hardness and elastic modulus of the DLC film are reduced with a reduction in stress, resulting in a decrease in the wear resistance of the film.
The nano-multilayer film is a thin film formed by alternately depositing materials of two or more components. When the thickness of the single-layer film is larger, the internal stress of the single-layer film is higher, so that the film is easier to peel off from the substrate. However, the multilayer film structure can relieve internal stress to a great extent, because when the number of the interface layers of the multilayer film is large, the stress can be absorbed more effectively, and the expansion of cracks is prevented, so that the bonding force between the film and the substrate is effectively improved, and each thinner layer leads to a compact structure, and the wear resistance is further improved.
Chinese patent literature discloses a metal carbide/diamond-like carbon (MeC/DLC) nano multilayer film material and a preparation method thereof, and application publication number is CN101081557A, the microhardness of the film prepared by the invention is high and reaches HV 2000-4500, the friction coefficient is as low as 0.10-0.25, and the film-base binding force is more than or equal to 60N. Yanar et al (Chinese surface engineering 2018,31(2):66-74) discovered that when studying magnetron sputtering method for preparing DLC/CNx multilayer films, the hardness of the multilayer films is significantly improved compared with single-layer films, but the binding force is still low, and further improvement is needed.
Disclosure of Invention
The invention provides the DLC/CNx/Men/CNx nano multilayer film which has small internal stress, high bonding strength with a base material and excellent wear resistance, in order to overcome the problems that the traditional DLC film has poorer bonding strength with the base material, and the wear resistance is reduced by reducing the stress and improving the bonding strength.
The invention also provides a preparation method of the DLC/CNx/MeN/CNx nano multilayer film, which has the advantages of simple steps, easy control of process conditions, safe and pollution-free preparation process, low cost and easy realization of industrialization.
In order to achieve the purpose, the invention adopts the following technical scheme:
a DLC/CNx/MeN/CNx nano multilayer film comprises a substrate, a metal transition layer and a nano multilayer film, wherein the metal transition layer and the nano multilayer film are sequentially deposited on the surface of the substrate, the nano multilayer film is composed of a plurality of nano composite units, and the nano composite units sequentially comprise a DLC layer, a first gradient CNx layer, a metal nitride layer and a second gradient CNx layer from bottom to top.
According to the invention, the pure metal transition layer is deposited on the surface of the substrate, the DLC/CNx/MeN/CNx nano multilayer film is deposited, the appropriate metal transition layer is applied between the substrate and the nano multilayer film as an intermediate layer, the affinity of metal and carbon element is good, a chemical bonding interface can be formed between the metal transition layer and the diamond-like carbon film (DLC), the difference of the thermal expansion coefficient between the substrate and the diamond-like carbon film is relieved, the internal stress can be effectively reduced, the problem of low film-based bonding force in the traditional deposition method is improved, and the wear resistance is excellent. The crystal lattices of the metal nitride and the CNx coating are more easily matched, and the film-based bonding strength of the DLC/CNx nano coating on a common high-speed steel substrate can be effectively improved.
Preferably, the total thickness of the DLC/CNx/MeN/CNx nano multilayer film is 0.6-10 μm.
Preferably, the substrate is a high speed steel substrate.
Preferably, the metal transition layer is Ti or Cr. The Cr and Ti metals are preferably selected as the transition layer in the invention because the affinity of Cr, Ti and carbon elements is better, a chemical bonding interface can be formed between the transition layer and the diamond-like carbon film (DLC), and the difference of the thermal expansion coefficient between the substrate and the diamond-like carbon film is relieved, thereby reducing the internal stress of the film and improving the bonding strength of the film and the substrate.
Preferably, the metal nitride layer is a TiN layer or a CrN layer.
Preferably, the nitrogen content of the first gradient CNx layer increases gradually from 0 at.% to 18 at.%.
Preferably, the nitrogen content of the second gradient CNx layer gradually decreases from 18 at.% to 0 at.%.
The design of the gradient layer with gradually increased and decreased N content enables the gradient layer to have better mechanical compatibility with the DLC layer and the metal nitride layer, can better transit to the beginning of the next period, greatly reduces the tendency of interlayer stripping, and can obtain high hardness and interlayer bonding force. The nitrogen content is controlled to be 0-18 at.% because the nitrogen content of the CNx film layer obviously influences the hardness, elastic modulus, internal stress and other properties of the CNx film layer, too high nitrogen content causes too low hardness and elastic modulus of the CNx film layer, interlayer property matching is difficult, and the multilayer film cannot obtain excellent properties.
Preferably, the nano indentation hardness of the DLC layer is 20-32 GPa; the nano indentation hardness of the first gradient CNx layer and the second gradient CNx layer is 15-25 GPa; the nano indentation hardness of the metal nitride layer is 20-28 GPa.
Preferably, the thickness of the nano multilayer film is 20-250 nm; the thickness of the nano composite unit is 5-100 nm.
A preparation method of DLC/CNx/MeN/CNx nano multilayer film comprises the following steps:
(1) pretreatment: ultrasonically cleaning a matrix in acetone and absolute ethyl alcohol in sequence, drying the matrix, removing oily and dirty impurities on the surface of the matrix, and keeping clean and dry;
(2) preparation work: loading the graphite target, the metal target and the pretreated substrate into a vacuum chamber of a vacuum coating machine, and adjustingThe base distance of the target is adjusted, and the air pressure in the vacuum chamber is pumped to 1.0 multiplied by 10
-3Introducing argon with the purity of 99.99% to keep the deposition pressure in the argon below Pa to be 0.6-1.2 Pa, and keeping the deposition temperature to be 150-350 ℃; the metal target is a Ti target or a Cr target; the thickness of each layer can be controlled by the deposition time;
(3) deposition of a metal transition layer: rotating the substrate above the metal target to form a metal transition layer on the surface of the substrate;
(4) deposition of nano-multilayer film:
a) transferring the substrate subjected to metal transition layer deposition to the position above the graphite target, adjusting the argon flow to be 30sccm, and plating a DLC layer; b) introduction of N
2Exposing the substrate treated in step a) to argon and N
2Plating a first gradient CNx layer in the mixed atmosphere; controlling N
2The flow is gradually increased from 0 to a set value;
c) transferring the substrate treated in step b) above a metal target under argon and N
2Plating a metal nitride layer in the mixed atmosphere;
d) transferring the substrate treated in step c) above a graphite target under argon and N
2Plating a second gradient CNx layer in the mixed atmosphere; and control N
2Gradually transitioning the flow from the set value to 0;
repeating the steps a) to d), and alternating for a plurality of periods to obtain the DLC/CNx/MeN/CNx nano multilayer film.
The deposition principle of the direct-current magnetron sputtering method adopted by the invention is as follows: the argon gas bombards the surface of the cathode metal target or the graphite target under the action of an electric field by plasma generated by abnormal glow discharge, atoms on the surface of the target are sputtered out and are ejected to the surface of the substrate along a certain direction under the action of the electric field, and a coating is formed on the surface of the substrate.
Preferably, in step b), the argon and N are
2In a mixed atmosphere of (2), N
2The flow set point was 1/2 for the argon flow.
Preferably, in step c): the argon and N
2In a mixed atmosphere of (2), N
2The mixing ratio of argon to argon was 1: 2.
As a preferenceIn step d), argon and N are used
2In a mixed atmosphere of (2), N
2The flow set point was 1/2 for the argon flow.
Therefore, the invention has the following beneficial effects:
(1) the DLC/CNx/MeN/CNx nano multilayer film effectively solves the problem of low film-substrate binding force of the traditional deposition method, reduces the internal stress and has excellent wear resistance;
(2) the preparation method has the advantages of simple steps, easily controlled process conditions, safe and pollution-free preparation process, low cost and easy realization of industrialization.
Drawings
FIG. 1 is a schematic structural diagram of a DLC/CNx/MeN/CNx nano-multilayer film of the present invention.
FIG. 2 is a graph showing the bonding force test results of the DLC/CNx/MeN/CNx nano-multilayer film prepared in example 1.
FIG. 3 is a graph showing the frictional wear of the DLC/CNx/MeN/CNx nano-multilayer film obtained in example 1.
In fig. 1: the nano-composite material comprises a substrate 1, a metal transition layer 2, a nano-composite unit 3, a DLC layer 4, a first gradient CNx layer 5, a metal nitride layer 6 and a second gradient CNx layer 7.
Detailed Description
The technical solution of the present invention is further specifically described below by using specific embodiments and with reference to the accompanying drawings.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
As shown in fig. 1, a DLC/CNx/MeN/CNx nano-multilayer film comprises a substrate 1, a metal transition layer 2 and a nano-multilayer film sequentially deposited on the surface of the substrate, wherein the nano-multilayer film is composed of a plurality of nano-composite units 3, and the nano-composite units sequentially comprise a DLC layer 4, a first gradient CNx layer 5, a metal nitride layer 6 and a second gradient CNx layer 7 from bottom to top.
Example 1
(1) Matrix pretreatment: ultrasonic cleaning high-speed steel substrate in acetone and absolute ethyl alcohol for 20min, removing surface oil stain, cleaning, blow-drying and loading on a sample table;
(2) preparation of the experiment: loading graphite target, metal target and pretreated high-speed steel substrate into deposition chamber of vacuum coating machine, regulating the distance between target and sample table to 60mm, and pumping the pressure in the deposition chamber to 1.0 × 10
-3After Pa, heating the high-speed steel to stabilize the temperature at 200 ℃;
(3) deposition of a Cr metal transition layer: introducing high-purity argon into the deposition chamber, controlling the flow of the argon to stabilize the pressure in the vacuum chamber at 0.8Pa, selecting Cr as a metal transition layer, adjusting the power of a pure metal Cr target to 80W, adding 200V of negative bias, and depositing a pure metal Cr layer on a self-rotating sample table for 7.5 min;
(4) preparing a DLC/CNx/CrN/CNx nano multilayer film:
a) introducing high-purity argon into the deposition chamber, stabilizing the pressure in the chamber at 0.8Pa, depositing a DLC layer on the Cr transition layer by using 60W of graphite target sputtering power and 100V of negative bias, and depositing for 36 min;
b) depositing a first gradient CNx layer on the DLC layer by using 55W of graphite target sputtering power and negative bias voltage of 100V, gradually introducing high-purity nitrogen, and controlling the flow to increase from 0sccm to 15sccm at a constant speed within 31 min;
c) depositing a CrN layer on the CNx layer by using a metal target sputtering power of 80W and a negative bias voltage of 200V, wherein the deposition time is 1.5 min;
d) and depositing a second gradient CNx layer on the CrN layer by using 55W of graphite target sputtering power and a negative bias voltage of 100V, and controlling the flow of high-purity nitrogen to be reduced to 0sccm from 15sccm at a constant speed within 31 min. Then, deposition in the next cycle was started, and the cycle number of the multilayer film was controlled to 10 cycles, and the film thickness of the multilayer film was about 1.2 μm.
Through the steps, the DLC/CNx/CrN/CNx nano multilayer film deposited on the high-speed steel matrix is finally obtained. The bonding force test results are shown in fig. 2, and it can be seen that a strong acoustic emission signal begins to appear when the load is added to 61N, indicating that the multilayer film is broken and the bonding force of the multilayer film is 61N. The friction factor curve is shown in fig. 3, and it can be seen that the friction factor is relatively stable, and the average friction factor of the multilayer film obtained by averaging the instant friction factors over the entire period of time is 0.118.
Example 2
(1) Matrix pretreatment: the same as example 1;
(2) preparation of the experiment: the same as example 1;
(3) deposition of a Ti transition layer: introducing high-purity argon into the deposition chamber, and controlling the flow of the argon to stabilize the pressure in the vacuum chamber at 0.8 Pa; adjusting the power of the pure metal Ti target to 80W, adding 200V negative bias, and depositing a pure metal Ti layer on the autorotation sample table for 10 min;
(4) preparing a DLC/CNx/TiN/CNx nano multilayer film:
a) introducing high-purity argon into the deposition chamber, stabilizing the pressure in the chamber at 0.8Pa, depositing a DLC layer on the Ti transition layer by using a graphite target sputtering power of 60W and a negative bias of 100V, and depositing for 36 min;
c) depositing a first gradient CNx layer on the DLC layer by using 55W of graphite target sputtering power and negative bias voltage of 100V, gradually introducing high-purity nitrogen, and controlling the flow to increase from 0sccm to 15sccm at a constant speed within 31 min;
d) and depositing a TiN layer on the high-speed steel substrate by using 80W of metal Ti target sputtering power and negative bias voltage of 200V for 2 min. Depositing a second gradient CNx layer on the TiN layer by using 55W of graphite target sputtering power and negative bias voltage of 100V; the flow rate of the high-purity nitrogen gas is controlled to be reduced to 0sccm from 15sccm at a constant speed within 31 min. The number of cycles of the multilayer film was controlled to 10 cycles, and the film thickness of the multilayer film was about 1.2. mu.m.
Through the steps, the DLC/CNx/TiN/CNx nano multilayer film deposited on the high-speed steel substrate is finally obtained.
Comparative example 1 (without first gradient CNx layer)
Comparative example 1 differs from example 1 in that: the step (4) is the preparation of the DLC/CrN/CNx nano multilayer film:
introducing high-purity argon into the deposition chamber, and stabilizing the pressure in the chamber at 0.8 Pa; and (3) depositing a DLC layer on the Cr transition layer by using a graphite target sputtering power of 60W and a negative bias voltage of 100V for 36 min. And depositing a metal nitride layer on the DLC for 2min by using a metal Cr target sputtering power of 80W and a negative bias voltage of 200V. Depositing a gradient second gradient CNx layer on the metal layer by using 55W of graphite target sputtering power and negative bias voltage of 100V; the flow rate of the high-purity nitrogen gas is controlled to be reduced to 0sccm from 15sccm at a constant speed within 31 min. The periodicity of the multilayer film is controlled to be 10 periods, and the film thickness of the multilayer film is about 950 nm;
the rest steps and the process conditions are completely the same.
Comparative example 2 (Single CNx layer and no gradient)
Comparative example 1 differs from example 1 in that: step (4) preparing DLC/CrN/CNx nano multilayer film: introducing high-purity argon into the deposition chamber, and stabilizing the pressure in the chamber at 0.8 Pa. And (3) depositing a DLC layer on the Cr transition layer by using a graphite target sputtering power of 60W and a negative bias voltage of 100V for 36 min. And depositing a metal nitride layer on the DLC layer by using a metal Cr target sputtering power of 80W and a negative bias voltage of 200V for 1 min. And then a CNx layer is deposited on the metal layer by using a graphite target sputtering power of 55W, a negative bias voltage of 100V and a nitrogen flow rate of 15 sccm. The periodicity of the multilayer film is controlled to be 10 periods, and the film thickness of the multilayer film is about 950 nm; the rest process conditions are completely the same.
COMPARATIVE EXAMPLE 3 (No Metal transition layer)
Comparative example 3 differs from example 1 in that step (3) is not present and the remaining steps and process conditions are exactly the same.
Comparative example 4 (two CNx layers and no gradient)
Comparative example 4 differs from example 1 in that in step (4), the nitrogen flow in b) and d) was maintained at 15sccm, and the rest of the steps and process conditions were exactly the same.
The films prepared in examples 1 and 2 and comparative examples 1 to 4 were tested for performance using the following test methods:
the WS-2005 type coating adhesion scratch tester is used for measuring the bonding strength of the film, and the test conditions are as follows: the loading rate was 100N/min, the scratch length 4mm, and the scratch rate 4 mm/min.
The hardness of the film was measured using a Nano-Indenter G200 nanoindenter, and a continuous stiffness method was used.
The WTM-1E type ball disc type friction and wear testing machine tests the friction coefficient of the film, and the smaller the friction coefficient is, the higher the wear resistance is. TestingConditions are as follows: ball-disk friction pair, Si
3N
4Ball, diameter 3mm, normal load 0.5N, relative sliding rate 0.11m/s, test duration 10 min.
The results are shown in table 1:
TABLE 1 test results
As can be seen from Table 1, the DLC/CNx/MeN/CNx nano-multilayer film of the invention has higher film-substrate binding force, higher hardness and excellent wear resistance. As can be seen from comparing the data of comparative example 1 and example 1, the absence of the first gradient CNx layer results in a decrease in the bonding force and hardness because the mechanical compatibility of the DLC layer and the first gradient CNx layer is superior to the direct contact of the DLC layer and the CrN layer, the presence of the first gradient CNx layer reduces the internal stress and enhances the interface strengthening effect; as can be seen by comparing the data of comparative example 2 and example 1, only one CNx layer without concentration gradient resulted in a sharp decrease in hardness and bonding force because the gradient CNx layer was designed to reduce the large difference in mechanical properties between DLC and CrN, and the CNx layer without concentration gradient had a lower hardness than the gradient CNx layer; comparing the data of comparative example 3 and example 1, it can be seen that the film-substrate binding force is obviously reduced and the tribological performance is also affected after the metal transition layer is absent; as can be seen from comparing the data of comparative example 4 and example 1, the gradient design of the CNx layer is critical, and the nano-multilayer film with fixed nitrogen content only, without the gradient design, results in significant reduction of the bonding force and hardness.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (10)
1. A DLC/CNx/MeN/CNx nano multilayer film is characterized by comprising a substrate (1), a metal transition layer (2) and a nano multilayer film, wherein the metal transition layer and the nano multilayer film are sequentially deposited on the surface of the substrate, the nano multilayer film is composed of a plurality of nano composite units (3), and the nano composite units sequentially comprise a DLC layer (4), a first gradient CNx layer (5), a metal nitride layer (6) and a second gradient CNx layer (7) from bottom to top.
2. The DLC/CNx/MeN/CNx nano-multilayer film as claimed in claim 1, wherein the total thickness of the DLC/CNx/MeN/CNx nano-multilayer film is 0.6-10 μm.
3. The DLC/CNx/MeN/CNx nano-multilayer film according to claim 1, wherein the substrate is a high speed steel substrate.
4. The DLC/CNx/MeN/CNx nano-multilayer film as claimed in claim 1, wherein the metal transition layer is Ti or Cr; the metal nitride layer is a TiN layer or a CrN layer.
5. The DLC/CNx/MeN/CNx nano-multilayer film according to claim 1, characterized in that the nitrogen content of the first gradient CNx layer gradually increases from 0 at.% to 18 at.%.
6. The DLC/CNx/MeN/CNx nano-multilayer film according to claim 1, characterized in that the nitrogen content of the second gradient CNx layer gradually decreases from 18 at.% to 0 at.%.
7. The DLC/CNx/MeN/CNx nano-multilayer film as claimed in claim 1, wherein the DLC layer has a nano-indentation hardness of 20-32 GPa; the nano indentation hardness of the first gradient CNx layer and the second gradient CNx layer is 15-25 GPa; the nano indentation hardness of the metal nitride layer is 20-28 GPa.
8. The DLC/CNx/MeN/CNx nano-multilayer film as claimed in claim 1, wherein the nano-multilayer film has a thickness of 20-250 nm; the thickness of the nano composite unit is 5-100 nm.
9. A method for preparing DLC/CNx/MeN/CNx nano-multilayer film according to any of claims 1 to 8, characterized by comprising the following steps:
(1) pretreatment: ultrasonically cleaning a matrix in an acetone solution and absolute ethyl alcohol in sequence, drying the matrix, removing oily and dirty impurities on the surface of the matrix, and keeping the matrix clean and dry;
(2) preparation work: loading graphite target, metal target and pretreated substrate into vacuum chamber of vacuum coating machine, regulating target base distance, and pumping air pressure in vacuum chamber to 1.0 × 10
-3Introducing argon with the purity of 99.99% to keep the deposition pressure in the argon below Pa to be 0.6-1.2 Pa, and keeping the deposition temperature to be 150-350 ℃; the metal target is a Ti target or a Cr target;
(3) deposition of a metal transition layer: rotating the substrate above the metal target to form a metal transition layer on the surface of the substrate;
(4) deposition of nano-multilayer film:
a) transferring the substrate subjected to metal transition layer deposition to the position above the graphite target, adjusting the argon flow to be 30sccm, and plating a DLC layer;
b) introduction of N
2Exposing the substrate treated in step a) to argon and N
2Plating a first gradient CNx layer in the mixed atmosphere; controlling N
2The flow is gradually increased from 0 to a set value;
c) transferring the substrate treated in step b) above a metal target under argon and N
2Plating a metal nitride layer in the mixed atmosphere;
d) transferring the substrate treated in step c) above a graphite target under argon and N
2Plating a second gradient CNx layer in the mixed atmosphere; and control N
2Gradually transitioning the flow from the set value to 0;
and (d) repeating the steps a) to d), thus obtaining the DLC/CNx/MeN/CNx nano multilayer film.
10. The method for producing DLC/CNx/MeN/CNx nano-multilayer film according to claim 9, wherein,
in step b), the argon and N
2In a mixed atmosphere of (2), N
2The flow set point was 1/2 for argon flow;
step (ii) ofc) The method comprises the following steps: the argon and N
2In a mixed atmosphere of (2), N
2The mixing ratio of the argon to the argon is 1: 2;
in step d), said argon and N
2In a mixed atmosphere of (2), N
2The flow set point was 1/2 for the argon flow.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112267097A (en) * | 2020-09-28 | 2021-01-26 | 广东鼎泰高科技术股份有限公司 | Composite coating of printed circuit board drill point and preparation method thereof |
| CN114686829A (en) * | 2020-12-29 | 2022-07-01 | 苏州吉恒纳米科技有限公司 | Wear-resistant, fatigue-resistant and repeated impact-resistant coating and production process thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081557A (en) * | 2007-06-26 | 2007-12-05 | 广州有色金属研究院 | Metallic carbide/adamantine (MeC/DLC) nanometer multi-layer film material and method for preparing the same |
| JP2008254144A (en) * | 2007-04-06 | 2008-10-23 | Osg Corp | Hard film and hard film coated tool |
| WO2009151404A1 (en) * | 2008-06-09 | 2009-12-17 | Nanofilm Technologies International Pte Ltd | A novel coating having reduced stress and a method of depositing the coating on a substrate |
| CN101804708A (en) * | 2010-04-09 | 2010-08-18 | 浙江大学 | Ti-TiN-CNx gradient multilayer film and preparation method thereof |
| CN102080207A (en) * | 2010-12-25 | 2011-06-01 | 深圳市广大纳米工程技术有限公司 | DLC (diamond-like carbon)/TiAlN (titanium aluminium nitride)/CrN (chromium nitride)/Cr (chromium) multilayer superhard film coating and preparation method thereof |
| DE102015204803A1 (en) * | 2015-03-17 | 2016-09-22 | Magna International Inc. | Coated steel component, method of manufacturing the steel component and manufacturing plant |
-
2019
- 2019-07-22 CN CN201910661891.8A patent/CN110777341B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008254144A (en) * | 2007-04-06 | 2008-10-23 | Osg Corp | Hard film and hard film coated tool |
| CN101081557A (en) * | 2007-06-26 | 2007-12-05 | 广州有色金属研究院 | Metallic carbide/adamantine (MeC/DLC) nanometer multi-layer film material and method for preparing the same |
| WO2009151404A1 (en) * | 2008-06-09 | 2009-12-17 | Nanofilm Technologies International Pte Ltd | A novel coating having reduced stress and a method of depositing the coating on a substrate |
| CN101804708A (en) * | 2010-04-09 | 2010-08-18 | 浙江大学 | Ti-TiN-CNx gradient multilayer film and preparation method thereof |
| CN102080207A (en) * | 2010-12-25 | 2011-06-01 | 深圳市广大纳米工程技术有限公司 | DLC (diamond-like carbon)/TiAlN (titanium aluminium nitride)/CrN (chromium nitride)/Cr (chromium) multilayer superhard film coating and preparation method thereof |
| DE102015204803A1 (en) * | 2015-03-17 | 2016-09-22 | Magna International Inc. | Coated steel component, method of manufacturing the steel component and manufacturing plant |
Non-Patent Citations (2)
| Title |
|---|
| NAKAMURA, MASASHI ET AL: "Wear and Friction Characteristics of AlN/Diamond-Like Carbon Hybrid Coatings on Aluminum Alloy", 《JOURNAL OF MATERIALS ENGINEERING AND PERFORMANCE》 * |
| 杨芳儿等: "DLC 层厚度对CNx/DLC 多层膜结构及摩擦学性能的影响", 《硅酸盐学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112267097A (en) * | 2020-09-28 | 2021-01-26 | 广东鼎泰高科技术股份有限公司 | Composite coating of printed circuit board drill point and preparation method thereof |
| CN114686829A (en) * | 2020-12-29 | 2022-07-01 | 苏州吉恒纳米科技有限公司 | Wear-resistant, fatigue-resistant and repeated impact-resistant coating and production process thereof |
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