CN114807834A - CrAlN/CrAlSiN/TaC composite coating with low friction coefficient and high wear resistance and preparation method thereof - Google Patents
CrAlN/CrAlSiN/TaC composite coating with low friction coefficient and high wear resistance and preparation method thereof Download PDFInfo
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- 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
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
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- 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
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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
- C23C14/0635—Carbides
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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
- C23C14/0641—Nitrides
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- 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
- 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
- C23C28/04—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 only coatings of inorganic non-metallic material
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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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
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Abstract
The invention discloses a low-friction-coefficient and high-wear-resistance CrAlN/CrAlSiN/TaC composite coating and a preparation method thereof, wherein the preparation method comprises the following steps: 1) firstly, improving the surface hardness of TC4 titanium alloy by a plasma nitriding technology, 2) carrying out ion cleaning on the surface of TC4 titanium alloy before depositing a composite coating, 3) depositing a CrAlN transition layer for 10-30 min, 4) depositing a CrAlSiN intermediate layer for 60-120 min, and 5) finally depositing a TaC coating for 30-60 min. By controlling the deposition time and the substrate bias voltage, the composite coating with high hardness and excellent wear resistance is deposited on the surface of the TC4 titanium alloy subjected to plasma nitriding treatment, so that the surface hardness and wear resistance of the TC4 titanium alloy are obviously improved.
Description
Technical Field
The invention belongs to the field of coatings, and particularly relates to a low-friction-coefficient and high-wear-resistance CrAlN/CrAlSiN/TaC composite coating and a preparation method thereof.
Background
The titanium alloy has excellent comprehensive properties of low density, high specific strength, corrosion resistance and the like, is widely applied to the fields of aviation, aerospace, navigation, chemical engineering and the like, is known as third-generation metal, is an important structural metal, and is also an important strategic metal material. The storage capacity of titanium ore is the first world in China, but the manufacturing and application capacity of titanium alloy is far less than that of developed countries. Although titanium alloy has a very wide development market in China, the development of the titanium alloy is severely limited by the defects of low surface hardness, poor wear resistance, poor high-temperature oxidation resistance and the like of the titanium alloy.
The development of the novel titanium alloy has long time and huge cost, and the surface modification treatment of the titanium alloy can effectively utilize the advantages of the titanium alloy and make up for the defects of the titanium alloy. Common surface modification techniques are: (1) the laser cladding technology has the advantages of capability of generating a large amount of intermediate strengthening phases, flexible processing range, controllable laser energy, various cladding materials and the like, but the laser cladding is easy to form defects of air holes, oxidation, composition segregation, large residual stress and the like; (2) the plasma spraying technology has the advantages of simple process, low cost, capability of preparing a large-area thick coating and the like, but has the problems of high porosity of the coating, poor bonding strength between the coating and a substrate, low fatigue strength of materials and the like; (3) the micro-arc oxidation technology has excellent performances of high hardness, high temperature resistance, corrosion resistance, wear resistance and the like, but the coating has a loose porous structure and is poor in wear resistance and corrosion resistance; (4) the multi-arc ion plating technology has the advantages of vacuum coating environment, no pollution, high deposition speed, uniform film layer and the like. At present, the related reports of surface modification of titanium alloy by adopting the multi-arc ion plating technology are less, and especially the reports of preparing TaC coating by using the multi-arc ion plating technology are less.
The single-layer CrAlN coating has the advantages of high hardness, low friction coefficient and the like, the CrAlSiN coating has the characteristics of extremely high hardness, excellent wear resistance, high ductility and the like, and the TaC coating has the advantages of high wear resistance, corrosion resistance, low friction coefficient, good biocompatibility and the like. The composite coating of the three coatings is prepared on the surface of the TC4 titanium alloy, so that the advantages of the TC4 titanium alloy can be kept, and the surface hardness and the wear resistance of the TC4 titanium alloy can be obviously improved.
Disclosure of Invention
The invention aims to improve the hardness and wear resistance of titanium alloy and provides a low-friction-coefficient and high-wear-resistance CrAlN/CrAlSiN/TaC composite coating and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a low-friction-coefficient high-wear-resistance CrAlN/CrAlSiN/TaC composite coating and a preparation method thereof, and is characterized by comprising the following steps:
firstly, cutting a TC4 titanium alloy plate into samples with the sizes of 10mm multiplied by 4mm in a linear mode, then polishing by using sand paper and a polishing machine, and cleaning;
step two, performing plasma nitriding on the sample in the step one;
step three, vertically suspending the sample in the step two on a rotating stand in a multi-arc ion plating chamber to deposit a composite coating;
and step four, after the deposition is finished, turning off the power supply, stopping introducing the argon and the nitrogen, and taking out the sample after the sample is cooled to the room temperature along with the furnace.
Further, the sample in the first step is respectively placed in absolute ethyl alcohol, acetone and deionized water for ultrasonic cleaning for 10-15 min, and then taken out and dried;
further, the plasma nitriding temperature in the second step is 850-950 ℃, and heat preservation is carried out for 6-8 hours;
furthermore, the target materials required for depositing the composite coating in the third step are 2 CrAl targets, 2 AlSi targets, 2 pure Ta targets and 2 graphite targets, and the required working gas is argon and nitrogen;
further, the coating process in the third step comprises the following steps:
a. an ion cleaning process: vacuumizing the multi-arc ion plating vacuum cavity to 5.0 multiplied by 10 -4 Preheating the substrate to 350-450 ℃ below Pa, introducing 100-300 sccm of argon, and cleaning the surface of the sample for 10-15 min by negative bias of-600-800V;
and b, CrAlN transition layer deposition process: keeping the temperature in the chamber at 350-450 ℃, introducing 50-100 sccm argon and 200-400 sccm nitrogen, starting 2 pure CrAl targets, setting the target arc current at 80A, setting the negative bias of the substrate at-100 to-300V, and depositing for 10-30 min to obtain a CrAlN transition layer;
c, CrAlSiN intermediate layer deposition process: starting 2 AlSi targets, setting the target arc current as 100A, and depositing for 60-120 min to obtain a CrAlSiN intermediate layer;
and d, TaC layer deposition process: and closing all CrAl targets and all AlSi targets, closing nitrogen, introducing argon of 200sccm, opening 2 pure Ta targets and graphite targets, respectively setting the target arc currents as 100A and 90A, and depositing for 30-60 min to obtain the TaC coating.
The invention has the beneficial effects that:
(1) because the hardness of the matrix has great influence on the binding force and the plastic deformation resistance of the coating, if the hard coating is directly prepared on the TC4 titanium alloy with low hardness, the difference between the hardness and the expansion coefficient of the hard coating is too large, the service life of the coating can be reduced, and therefore, the surface hardness of the TC4 titanium alloy is improved by adopting a plasma nitriding technology before the composite coating is deposited;
(2) because the CrAlN and CrAlSiN coatings have high hardness and excellent wear resistance, the gradient structure formed by sequentially depositing the multiple coatings can combine the respective excellent performances of the two coatings, and higher interface bonding strength, hardness and wear resistance are obtained;
(3) the TaC coating has extremely low friction coefficient and excellent wear resistance, so that the surface quality of the composite coating can be obviously improved by preparing the TaC coating on the CrAlN/CrAlSiN gradient coating.
Drawings
FIG. 1 shows the average hardness of TC4 titanium alloy, nitride layer, single-layer CrAlN coating, single-layer CrAlSiN coating, and single-layer TaC coating.
FIG. 2 is a comparison of the coefficient of friction before and after the preparation of the coating.
FIG. 3 is a comparison of wear scar widths before and after preparation of the coating.
In the figure: 1 is the friction coefficient of TC4 titanium alloy, 2 is the friction coefficient after the coating is prepared, 3 is the width of TC4 titanium alloy grinding crack, and 4 is the width of the grinding crack after the coating is prepared.
Detailed Description
The present invention is further described below in conjunction with specific embodiments, which are illustrative based on the present invention and are not to be construed as limiting the invention.
Example 1:
the invention provides a low-friction-coefficient high-wear-resistance CrAlN/CrAlSiN/TaC composite coating and a preparation method thereof, wherein the preparation method comprises the following steps:
firstly, cutting a TC4 titanium alloy plate into samples with the sizes of 10mm multiplied by 4mm in a linear mode, then polishing by using sand paper and a polishing machine, and cleaning;
step two, performing plasma nitriding on the sample in the step one;
step three, vertically suspending the sample in the step two on a rotating stand in a multi-arc ion plating chamber to deposit a composite coating;
and step four, after the deposition is finished, turning off the power supply, stopping introducing the argon and the nitrogen, and taking out the sample after the sample is cooled to the room temperature along with the furnace.
Further, the sample in the first step is respectively placed in absolute ethyl alcohol, acetone and deionized water for ultrasonic cleaning for 10-15 min, and then taken out and dried;
further, the plasma nitriding temperature in the second step is 850 ℃, and heat preservation is carried out for 6 hours;
furthermore, the target materials required for depositing the composite coating in the third step are 2 CrAl targets, 2 AlSi targets, 2 pure Ta targets and 2 graphite targets, and the required working gas is argon and nitrogen;
further, the coating process in the third step comprises the following steps:
a. an ion cleaning process: vacuumizing the multi-arc ion plating vacuum cavity to 5.0 multiplied by 10 -4 Preheating the substrate to 350 ℃ below Pa, introducing 300sccm argon, and cleaning the surface of the sample for 15min by negative bias of-600V;
and b, CrAlN transition layer deposition process: keeping the temperature in the chamber at 350 ℃, introducing 100sccm argon and 200sccm nitrogen, starting 2 pure CrAl targets, setting the target arc current at 80A and the matrix negative bias at-100V, and depositing for 10min to obtain a CrAlN transition layer;
c, CrAlSiN intermediate layer deposition process: starting 2 AlSi targets, setting the target arc current as 100A, and depositing for 80min to obtain a CrAlSiN intermediate layer;
and d, TaC layer deposition process: and closing all CrAl targets and all AlSi targets, closing nitrogen, introducing argon of 200sccm, opening 2 pure Ta targets and graphite targets, wherein the target arc currents are 100A and 90A respectively, and depositing for 30min to obtain the TaC coating.
Example 2:
the invention provides a low-friction-coefficient high-wear-resistance CrAlN/CrAlSiN/TaC composite coating and a preparation method thereof, wherein the preparation method comprises the following steps:
firstly, cutting a TC4 titanium alloy plate into samples with the sizes of 10mm multiplied by 4mm in a linear mode, then polishing by using sand paper and a polishing machine, and cleaning;
step two, performing plasma nitriding on the sample in the step one;
step three, vertically suspending the sample in the step two on a rotating stand in a multi-arc ion plating chamber to deposit a composite coating;
and step four, after the deposition is finished, turning off the power supply, stopping introducing the argon and the nitrogen, and taking out the sample after the sample is cooled to the room temperature along with the furnace.
Further, the sample in the first step is respectively placed in absolute ethyl alcohol, acetone and deionized water for ultrasonic cleaning for 10-15 min, and then taken out and dried;
further, the plasma nitriding temperature in the second step is 850 ℃, and heat preservation is carried out for 6 hours;
furthermore, the target materials required for depositing the composite coating in the third step are 2 CrAl targets, 2 AlSi targets, 2 pure Ta targets and 2 graphite targets, and the required working gas is argon and nitrogen;
further, the coating process in the third step comprises the following steps:
a. an ion cleaning process: vacuumizing the multi-arc ion plating vacuum cavity to 5.0 multiplied by 10 -4 Preheating the substrate to 350 ℃ below Pa, introducing argon of 300sccm, and cleaning the surface of the sample for 15min by negative bias of-600V;
and b, CrAlN transition layer deposition process: keeping the temperature in the chamber at 350 ℃, introducing 100sccm argon and 200sccm nitrogen, starting 2 pure CrAl targets, setting the target arc current at 80A and the matrix negative bias voltage at-200V, and depositing for 20min to obtain a CrAlN transition layer;
c, CrAlSiN intermediate layer deposition process: simultaneously starting 2 AlSi targets, setting the arc current of the targets as 100A, and depositing for 100min to obtain a CrAlSiN intermediate layer;
and d, TaC layer deposition process: and closing all CrAl targets and all AlSi targets, closing nitrogen, introducing argon of 200sccm, opening 2 pure Ta targets and graphite targets, wherein the target arc currents are 100A and 90A respectively, and depositing for 45min to obtain the TaC coating.
Example 3:
the invention provides a low-friction-coefficient high-wear-resistance CrAlN/CrAlSiN/TaC composite coating and a preparation method thereof, wherein the preparation method comprises the following steps:
firstly, cutting a TC4 titanium alloy plate into samples with the sizes of 10mm multiplied by 4mm in a linear mode, then polishing by using sand paper and a polishing machine, and cleaning;
step two, performing plasma nitriding on the sample in the step one;
step three, vertically suspending the sample in the step two on a rotating stand in a multi-arc ion plating chamber to deposit a composite coating;
and step four, after the deposition is finished, turning off the power supply, stopping introducing the argon and the nitrogen, and taking out the sample after the sample is cooled to the room temperature along with the furnace.
Further, the sample in the first step is respectively placed in absolute ethyl alcohol, acetone and deionized water for ultrasonic cleaning for 10-15 min, and then taken out and dried;
further, the plasma nitriding temperature in the second step is 850 ℃, and heat preservation is carried out for 6 hours;
furthermore, the target materials required for depositing the composite coating in the third step are 2 CrAl targets, 2 AlSi targets, 2 pure Ta targets and 2 graphite targets, and the required working gas is argon and nitrogen;
further, the coating process in the third step comprises the following steps:
a. an ion cleaning process: vacuumizing the multi-arc ion plating vacuum cavity to 5.0 multiplied by 10 -4 Preheating the substrate to 350 ℃ below Pa, introducing argon of 300sccm, and cleaning the surface of the sample for 15min by negative bias of-600V;
and b, CrAlN transition layer deposition process: keeping the temperature in the chamber at 350 ℃, introducing 100sccm argon and 200sccm nitrogen, starting 2 pure CrAl targets, setting the target arc current at 80A and the matrix negative bias voltage at-300V, and depositing for 30min to obtain a CrAlN transition layer;
c, CrAlSiN intermediate layer deposition process: simultaneously starting 2 AlSi targets, setting the target arc current as 100A, and depositing for 120min to obtain a CrAlSiN intermediate layer;
and d, TaC layer deposition process: and closing all CrAl targets and all AlSi targets, closing nitrogen, introducing argon of 200sccm, opening 2 pure Ta targets and graphite targets, wherein the target arc currents are 100A and 90A respectively, and depositing for 60min to obtain the TaC coating.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.
Claims (5)
1. A low-friction-coefficient and high-wear-resistance CrAlN/CrAlSiN/TaC composite coating and a preparation method thereof are characterized by comprising the following steps:
firstly, cutting a TC4 titanium alloy plate into samples with the sizes of 10mm multiplied by 4mm in a linear mode, then polishing by using sand paper and a polishing machine, and cleaning;
step two, performing plasma nitriding on the sample in the step one;
step three, vertically suspending the sample in the step two on a rotating stand in a multi-arc ion plating chamber to deposit a composite coating;
and step four, after the deposition is finished, turning off the power supply, stopping introducing the argon and the nitrogen, and taking out the sample after the sample is cooled to the room temperature along with the furnace.
2. The CrAlN/CrAlSiN/TaC composite coating with the low friction coefficient and the high wear resistance and the preparation method thereof as claimed in claim 1, is characterized in that a sample in the first step is respectively placed in absolute ethyl alcohol, acetone and deionized water for ultrasonic cleaning for 10-15 min, and then taken out and dried.
3. The CrAlN/CrAlSiN/TaC composite coating with low friction coefficient and high wear resistance and the preparation method thereof according to claim 1, characterized in that the plasma nitriding temperature is 850-950 ℃, and the heat preservation is carried out for 6-8 hours.
4. The CrAlN/CrAlSiN/TaC composite coating with low friction coefficient and high wear resistance and the preparation method thereof as claimed in claim 1, wherein the target materials required for depositing the composite coating in the third step are 2 CrAl targets, 2 AlSi targets, 2 pure Ta targets and 2 graphite targets, and the required working gas is argon and nitrogen.
5. The CrAlN/CrAlSiN/TaC composite coating with low friction coefficient and high wear resistance and the preparation method thereof as claimed in claims 1 and 4, wherein the coating process in the third step is as follows:
a. an ion cleaning process: vacuumizing the multi-arc ion plating vacuum cavity to 5.0 multiplied by 10 -4 Preheating the substrate to 350-450 ℃ below Pa, introducing 100-300 sccm of argon, and cleaning the surface of the sample for 10-15 min by negative bias of-600-800V;
a CrAlN transition layer deposition process: keeping the temperature in the chamber at 350-450 ℃, introducing 50-100 sccm argon and 200-400 sccm nitrogen, starting 2 pure CrAl targets, setting the target arc current at 80A, setting the negative bias of the substrate at-100 to-300V, and depositing for 10-30 min to obtain a CrAlN transition layer;
c, CrAlSiN intermediate layer deposition process: starting 2 AlSi targets, setting the target arc current as 100A, and depositing for 60-120 min to obtain a CrAlSiN intermediate layer;
and d, TaC layer deposition process: and closing all CrAl targets and all AlSi targets, closing nitrogen, introducing argon of 200sccm, opening 2 pure Ta targets and graphite targets, respectively setting the target arc currents as 100A and 90A, and depositing for 30-60 min to obtain the TaC coating.
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