CN115233172A - Carbon-based material with wear-resistant surface and high biocompatibility and preparation method thereof - Google Patents
Carbon-based material with wear-resistant surface and high biocompatibility and preparation method thereof Download PDFInfo
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- CN115233172A CN115233172A CN202210758136.3A CN202210758136A CN115233172A CN 115233172 A CN115233172 A CN 115233172A CN 202210758136 A CN202210758136 A CN 202210758136A CN 115233172 A CN115233172 A CN 115233172A
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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
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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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
- 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
- C23C14/0605—Carbon
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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
- 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
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- 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
- C23C16/24—Deposition of silicon only
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- 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
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- 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
- C23C16/44—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 method of coating
- C23C16/50—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 method of coating using electric discharges
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- 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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Abstract
The titanium-doped diamond-like carbon coating also endows the carbon-based material with good surface biocompatibility and hardness, particularly the titanium-doped diamond-like carbon coating has high binding force with the surface of the carbon-based material, good stability and prolonged service life.
Description
Technical Field
The invention relates to a surface modified carbon-based material, in particular to a carbon-based material with wear-resistant surface and high biocompatibility, and a preparation method thereof, belonging to the technical field of preparation of biomedical materials.
Background
The carbon material has good biocompatibility, wherein the carbon fiber, the pyrolytic carbon, the carbon nanotube and the composite material thereof are applied to the aspects of heart valves, bones, growth stents, tumor drugs, biosensors and the like. Particularly, carbon-based materials taking carbon fibers, fabrics and the like as reinforcements have the characteristics of light weight, good chemical stability, mechanical properties similar to those of human bones, good fatigue resistance, strong designability, certain plasticity and the like, and are considered as ideal materials for preparing artificial implants. However, carbon-based materials also have some drawbacks in clinical applications. The particles falling off from the surface of the material due to abrasion can be absorbed by peripheral macrophages or lymphocytes, although the functions of peripheral tissues are not damaged, the particles can still cause inflammatory reaction of the tissues, and some larger particles falling off can flow along with body fluid and deposit on the body surface to form a 'black skin effect', thereby affecting the beauty. Although the carbon-based material is an inert material, the porous characteristic of the carbon-based material is easy to carry bacteria into human tissues during the use process to cause the risk of inflammation. Therefore, the surface wear resistance of the carbon-based material is improved, and the carbon-based material is favorable for further popularization and application in the field of biomedicine.
Disclosure of Invention
In view of the defects of the prior art, a first object of the present invention is to provide a carbon-based material with wear-resistant surface and high biocompatibility, wherein the carbon-based material is coated with a titanium-doped diamond-like composite coating, so that the surface friction coefficient of the carbon-based material can be effectively reduced, the wear resistance of the carbon-based material can be improved, the adverse reaction of the carbon-based material to a human body caused by powder falling due to friction after the carbon-based material is implanted into the human body can be improved, the titanium-doped diamond-like composite coating also provides the carbon-based material with good surface biocompatibility and hardness, and particularly, the titanium-doped diamond-like composite coating has high surface binding force with the carbon-based material, good stability, and a service life of the carbon-based material can be prolonged.
The invention also aims to provide a preparation method of the carbon-based material with wear-resistant surface and high biocompatibility, the method combines the unbalanced intermediate frequency magnetron sputtering method and the direct current arc PECVD to prepare the titanium-doped diamond-like carbon composite coating, and the method has simple operation, is easy to accurately control and is beneficial to industrial production.
In order to realize the technical purpose, the invention provides a carbon-based material with wear-resistant surface and high biocompatibility, which is composed of a carbon-based material and a titanium-doped diamond-like carbon composite coating on the surface of the carbon-based material; the titanium-doped diamond-like carbon composite coating is formed by alternately superposing N layers of silicon transition film layers and N layers of titanium-doped diamond-like carbon film layers; wherein N is an integer greater than or equal to 1.
Compared with the existing diamond-like carbon coating, the titanium-doped diamond-like carbon composite coating plated on the surface of the carbon-based material can effectively improve the comprehensive performance of the diamond-like carbon coating by introducing the metallic titanium, such as improving the surface biocompatibility, friction performance and hardness of the diamond-like carbon coating, and the titanium element doped in the diamond-like carbon coating is more tightly combined with atoms in the silicon transition layer by overlapping plating the silicon transition layer and the titanium-doped diamond-like carbon coating, so that the internal stress of the whole composite coating is reduced, and the binding force between the whole composite coating and the carbon material substrate is greatly improved. Meanwhile, the titanium-doped diamond-like composite coating is plated on the surface of the carbon-based material, so that adverse reaction of a human body caused by powder falling due to friction after the carbon-based material is implanted into the human body can be avoided.
As a preferred scheme, the titanium-doped diamond-like carbon composite coating is formed by alternately overlapping 2-10 silicon transition film layers and 2-10 titanium-doped diamond-like carbon film layers. The titanium-doped diamond-like carbon composite coating is further preferably formed by alternately overlapping 2-5 silicon transition film layers and 2-5 titanium-doped diamond-like carbon film layers. If the film layer is too small, the purpose of improving the wear resistance and hardness of the surface of the carbon-based material is difficult to achieve, and if the film layer is too large, the bonding capability between the composite coating and the carbon-based material matrix is reduced, so that the coating is more prone to peeling.
As a preferable scheme, the thickness of each silicon transition layer in the titanium-doped diamond-like carbon composite coating is in the range of 0.1-1.5 μm, and the thickness of each titanium-doped diamond-like carbon film layer is in the range of 0.3-3.5 μm. Too low thickness of the silicon transition film layer or too thick thickness of the titanium-doped diamond-like film layer can reduce the combination capability of the titanium-doped diamond-like film layer and the carbon-based material, and too thick thickness of the silicon transition film layer or too low thickness of the titanium-doped diamond-like film layer can reduce the hardness, the wear resistance and the like.
According to the invention, the thickness of each film layer and the number of the stacked film layers are optimally regulated, so that the abrasion resistance, the hardness and the adhesive force of the whole composite coating on the surface of the carbon-based material can be effectively enhanced.
As a preferable scheme, the titanium doping amount of each titanium-doped diamond-like film layer in the titanium-doped diamond-like composite coating is gradually decreased from the inner layer to the outer layer. The titanium doping amount of each titanium-doped diamond-like film layer is gradually reduced from the inner layer to the outer layer, so that the biocompatibility of the outermost titanium-doped diamond-like film layer can be better improved while the binding force between the whole composite coating and the carbon-based material substrate is effectively improved.
As a preferred scheme, the titanium-doped diamond-like carbon composite coating contains 5-50% by mass of titanium, and the outermost titanium-doped diamond-like carbon film layer in the titanium-doped diamond-like carbon composite coating contains no more than 10% by mass of titanium. The titanium doping amount is increased within a proper range, so that the bonding force between the composite coating and the carbon-based material can be effectively improved, and when the titanium mass percentage in the outermost titanium-doped diamond-like film layer is higher than 10%, the biocompatibility of the outermost titanium-doped diamond-like film layer is reduced, so that the titanium content of the whole titanium-doped diamond-like composite coating and the titanium-doped diamond-like film layer on the surface should be controlled within a proper range.
The invention also provides a preparation method of the carbon-based material with wear-resistant surface and high biocompatibility, which comprises the step of plating a silicon transition film layer and a titanium-doped diamond-like carbon film layer on the surface of the carbon-based material alternately after the surface of the carbon-based material is cleaned.
As a preferable scheme, the surface cleaning treatment process comprises the following steps: and (3) sequentially adopting water and ethanol to carry out ultrasonic washing on the carbon-based material, wherein the temperature of the ultrasonic washing is 20-32 ℃, and the time is 10-30 min. The carbon-based material is washed by the ultrasonic-assisted solvent, so that the stains on the surface of the carbon-based material can be effectively removed, and the bonding capability between a subsequently plated film layer and a substrate can be improved. The water is preferably purified water, such as deionized water, and the ethanol is preferably anhydrous ethanol.
As a preferred scheme, the silicon transition film layer is plated by an unbalanced intermediate frequency magnetron sputtering method, and the conditions for plating the silicon transition film layer are as follows: ar gas flow is 60-100 sccm, silicon target power is 0.5-3 kW, and vacuum degree is 1.0 × 10 -1 ～4.0×10 -1 Pa, the ion source power is 0.5-2 kW, the negative bias voltage of the workpiece is 50-400V, and the plating time is 10-80 min. The temperature can be controlled to be lower than 200 ℃ in the process of preparing the silicon film layer by the unbalanced magnetron sputtering, and the formed coating layer is more compact and is beneficial to improving the combination between the coated film layer and the substrate.
As a preferred scheme, the titanium-doped diamond-like film layer is plated by a method combining unbalanced intermediate frequency magnetron sputtering and direct current arc PECVD; the conditions for plating the titanium-doped diamond-like carbon film layer are as follows: ar gas flow rate is 20-100 sccm, gas carbon source flow rate is 10-100 sccm, and vacuum degree is 1.0 × 10 -1 ～4.0×10 -1 Pa, the power of an ion source is 0.5-3 kW, the power of a titanium target is 0.3-1.5 kW, the purity of the titanium target is not lower than 99.9wt%, the negative bias voltage of a workpiece is 50-800V, the coating time is 30-540 min, and in the process of coating any two adjacent layers of titanium-doped diamond-like film layers, the power of the titanium target when the outer layer of the titanium-doped diamond-like film layer is coated is reduced by 0.1-0.3 kW compared with the power of the titanium target when the inner layer of the titanium-doped diamond-like film layer is coated. The preferred gaseous carbon source is a common gaseous carbon source such as acetylene. The titanium-doped diamond-like film layer is plated by adopting a method combining unbalanced intermediate frequency magnetron sputtering and direct current arc PECVD (plasma enhanced chemical vapor deposition), so that the content of doped titanium element can be better controlled under the condition of not changing the preparation process parameters of the diamond-like film layer, and the mass percentage content of the titanium element in the whole composite coating is stably controlled to be the most effective in improving the performance of the film layerThe effective range is 5-50%.
The specific method of the carbon-based material with wear-resistant surface and high biocompatibility of the invention comprises the following steps:
A. cleaning the carbon-based material: the carbon-based material is subjected to ultrasonic cleaning by adopting purified water and ethanol successively, the cleaning temperature is 20-32 ℃, the cleaning time is 10-30 min, and the carbon-based material is dried for later use after being cleaned.
B. Vacuum-pumping pretreatment of coating equipment: and (3) placing the cleaned carbon-based material in coating equipment combining unbalanced intermediate frequency magnetron sputtering and direct current arc PECVD, and vacuumizing to working vacuum degree.
C. Removing impurity gas in the furnace: ar gas is introduced into the vacuum chamber, the gas flow is 50-120 sccm, the vacuum degree is 4.0 multiplied by 10 -1 ～7.0×10 -1 Pa, negative bias voltage of 400-800V and degassing time of 10-30 min.
D. Cleaning a workpiece by an ion source: ar gas flow of 60-100 sccm and vacuum degree of 3.0 × 10 -1 ～6.0×10 -1 Pa, ion source power of 0.5-2 kW, negative bias voltage of 400-800V and cleaning time of 15-40 min.
E. Preparing a silicon transition film layer: ar gas flow of 60-100 sccm and vacuum degree of 1.0 × 10 -1 ～4.0×10 -1 Pa, the power of the silicon target is 0.5-3 kW, the power of the ion source is 0.5-2 kW, the negative bias voltage of the workpiece is 50-400V, and the coating time is 10-80 min.
F. Preparing a titanium-doped diamond-like film layer: ar gas flow of 20-100 sccm, acetylene gas flow of 10-100 sccm, and vacuum degree of 1.0 × 10 -1 ～4.0×10 -1 Pa, the ion source power is 0.5-3 kW, the titanium target power is 0.3-1.5 kW, the titanium target purity is not less than 99.9wt%, the negative bias voltage of the workpiece is 50-800V, and the plating time is 30-540 min.
G. And E, preparing the silicon transition film layer and the titanium-doped diamond-like carbon film layer alternately according to the processes of the step E and the step F, along with the preparation of each silicon transition layer, reducing the power of a titanium target by 0.1-0.3 kW in the preparation process of the next titanium-doped diamond-like carbon film layer compared with the power of the titanium target in the preparation process of the previous titanium-doped diamond-like carbon film layer until the periodic gradient coating of the silicon transition film layer/the titanium-doped diamond-like carbon film layer is finished, and taking out the carbon-based material when the temperature in the furnace is reduced to room temperature after the coating is finished.
The carbon-based material is a carbon nano tube, a nano carbon material such as graphene, a carbon fiber reinforced matrix carbon and/or silicon carbide composite material, graphite and the like which are conventional in the field.
The equipment adopted by the invention for preparing the titanium-doped diamond-like carbon composite coating is HCSH-DLC650 equipment of Guangdong Hui vacuum science and technology company Limited, or PVD850-DLC equipment of south China New Material research company Limited in Dongguan city, or DLC-800 equipment of Qingdao Youbuyu vacuum technology company Limited, and the equipment is coating equipment combining unbalanced intermediate frequency magnetron sputtering and direct current arc PECVD technology.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the invention carries out surface modification treatment on the carbon-based material, plates the titanium-doped diamond-like composite coating on the surface of the existing carbon-based material by combining the unbalanced intermediate frequency magnetron sputtering method and the direct current arc PECVD method, has simple operation, easy and accurate control and is beneficial to industrial production, and particularly, the method combining the unbalanced intermediate frequency magnetron sputtering method and the direct current arc PECVD method can plate the gradient titanium-doped diamond-like coating on the surface of the carbon-based material, can better control the content of doped titanium element under the condition of not changing the process parameters of the diamond-like coating, and stably controls the mass percentage content of the titanium element in the interval of 5-50 percent which can improve the most effective performance of the film layer.
The titanium-doped diamond-like carbon composite coating is formed by alternately superposing N layers of silicon transition film layers and N layers of titanium-doped diamond-like carbon film layers, titanium elements are doped into the diamond-like carbon coating, the titanium elements are combined with atoms in the silicon transition layers more tightly, the internal stress of the whole composite coating is reduced, the binding force between the whole composite coating and a carbon-based material is greatly improved, the composite coating with better performances such as abrasion resistance, hardness and adhesive force can be obtained by controlling the preparation process parameters of the film layers, the number of superposed layers and the like, the combined critical load of the titanium-doped diamond-like carbon composite coating and the carbon-based material can reach more than 10N, and the hardness of the composite coating is more than 10 GPa.
According to the invention, the titanium-doped diamond-like carbon composite coating is prepared on the surface of the carbon-based material, so that the friction coefficient of the surface of the carbon-based material can be effectively reduced, the wear resistance of the carbon-based material is improved, and the adverse reaction of a human body caused by friction powder falling after the matrix is implanted into the human body is improved.
Drawings
FIG. 1 is a graph of the coefficient of friction of a modified carbon-based material of a titanium-doped diamond-like composite coating prepared in example 1; it can be seen from the figure that the titanium-doped diamond-like composite coating can obviously reduce the friction coefficient of the carbon-based material compared with the friction coefficient of the carbon-based material of 0.18.
FIG. 2 is an SEM image of a trace of the titanium doped diamond-like composite coating modified carbon-based material prepared in example 1 after friction; it can be seen from the figure that the wear scar is very shallow and the matrix is essentially not worn.
Detailed Description
In order that the present invention may be more clearly understood, the following detailed description of the present invention is given in conjunction with specific embodiments, which are given here only for the purpose of further elaboration of the present invention and do not limit the scope of the claims of the present invention.
And (3) performance detection: the mechanical properties of the coatings were tested by nanoindentation and nanoindentation methods in the following examples; the friction coefficient of the film layer was measured using a ball-and-disk friction tester, the improvement of the biocompatibility of the coating to the substrate was examined using endothelial cell proliferation experiments, and the cytotoxicity was examined using L929 mouse fibroblast cytotoxicity experiments.
In the following examples, a typical carbon fiber reinforced matrix carbon composite material is used as a matrix material.
Example 1
Preparing a Ti-doped diamond-like coating on the surface of a carbon-based material substrate, and operating according to the following steps:
A. has a density of 1.6g/cm 3 Cleaning the carbon/carbon composite material substrate, wherein the cleaning step comprises the following steps: and ultrasonically cleaning the carbon-based material matrix by adopting purified water and ethanol successively, wherein the cleaning temperature is 28 ℃, the cleaning time is 20min, and drying for later use after cleaning.
B. And putting the cleaned carbon-based material substrate into coating equipment combining unbalanced intermediate frequency magnetron sputtering and direct current arc PECVD, and vacuumizing to the working vacuum degree.
C. Removing impurity gas in the furnace: ar gas is introduced into the vacuum chamber, the gas flow is 100sccm, the vacuum degree is 5.0 multiplied by 10 -1 Pa, negative bias voltage of the workpiece is 800V, and degassing time is 20min.
D. Cleaning a workpiece by an ion source: ar gas flow of 80sccm and vacuum degree of 4.0X 10 -1 Pa, the ion source power is 1kW, the negative bias voltage of the workpiece is 800V, and the cleaning time is 30min.
E. Preparing a silicon transition film layer: ar gas flow of 50sccm and vacuum degree of 2.0X 10 -1 Pa, the power of a silicon target is 1.5kW, the power of an ion source is 1kW, the negative bias voltage of a workpiece is 200V, and the coating time is 30min.
F. Preparing a titanium-doped diamond film layer: ar gas flow rate of 80sccm, acetylene gas flow rate of 100sccm, and vacuum degree of 2.0 × 10 -1 Pa, the ion source power is 1kW, the titanium target power is 1.2kW, the titanium target purity is 99.9wt%, the workpiece negative bias voltage is 600V, and the coating time is 90min.
G. And E, alternately preparing a silicon transition film layer and a titanium-doped diamond-like carbon film layer according to the processes of the step E and the step F, along with the preparation of each silicon transition film layer, reducing the power of a titanium target in the preparation of the next titanium-doped diamond-like carbon film layer by 0.2kW compared with the power of the titanium target in the preparation of the previous titanium-doped diamond-like carbon film layer until the silicon transition layer/titanium-doped diamond-like carbon film layer periodic gradient coating is finished, and after the coating is finished, taking out the carbon-based material after the temperature in the furnace is reduced to the room temperature.
The total number of the obtained periodic coating layers of the silicon transition film layer/the titanium-doped diamond-like carbon film layer is 4, the mass percent of titanium in the whole film layer is 27%, the thickness of each silicon transition film layer is 0.3 mu m, and the thickness of each titanium-doped diamond-like carbon film layer is at least 0.48 mu m.
The titanium-doped diamond-like coating prepared by the embodiment has high bonding force with a carbon-based material, the bonding critical load is 10N, the hardness is 12GPa, the surface friction coefficient is 0.08, and the wear rate is 2.3 multiplied by 10 -7 mm 3 N · m. Compared with the carbon-based material without the coating, the carbon-based material with the titanium-doped diamond-like carbon coating plated on the surface has the advantages that the endothelial cell proliferation rate is increased from 70 to 80% in an endothelial cell proliferation experiment, and the survival rate of L929 cells is increased from 23% to 85% in a cytotoxicity experiment.
Example 2
Preparing a Ti-doped diamond-like coating on the surface of a carbon-based substrate, and operating according to the following steps:
A. has a density of 1.6g/cm 3 Cleaning the carbon/carbon composite material substrate, wherein the cleaning step comprises the following steps: and ultrasonically cleaning the carbon-based material matrix by adopting purified water and ethanol successively, wherein the cleaning temperature is 28 ℃, the cleaning time is 20min, and drying for later use after cleaning.
B. And putting the cleaned carbon-based material substrate into coating equipment combining unbalanced intermediate frequency magnetron sputtering and direct current arc PECVD, and vacuumizing to the working vacuum degree.
C. Removing impurity gas in the furnace: ar gas is introduced into the vacuum chamber, the gas flow is 100sccm, the vacuum degree is 5.0 multiplied by 10 -1 Pa, negative bias voltage of the workpiece is 800V, and degassing time is 20min.
D. Cleaning a workpiece by an ion source: ar gas flow of 80sccm and vacuum degree of 4.0X 10 -1 Pa, the power of an ion source is 1kW, the negative bias voltage of the workpiece is 800V, and the cleaning time is 30min.
E. Preparing a silicon transition film layer: ar gas flow of 50sccm and vacuum degree of 2.0X 10 -1 Pa, the power of the silicon target is 1.5kW, the power of the ion source is 1kW, the negative bias voltage of the workpiece is 200V, and the coating time is 30min.
F. Preparing a titanium-doped diamond-like coating: ar gas flow rate is 60sccm, acetylene gas flow rate is 100sccm, and vacuum degree is 2.0 × 10 -1 Pa, the power of an ion source is 1.4kW, the power of a titanium target is 0.8kW, the purity of the titanium target is 99.9wt%, and a workpiece is loadedThe bias voltage is 600V, and the coating time is 60min.
G. And E, preparing the silicon transition film layer and the titanium-doped diamond-like carbon film layer alternately according to the processes in the steps E and F, along with the preparation of each silicon transition layer, reducing the power of a titanium target by 0.2kW when the power of the titanium-doped diamond-like carbon film layer in the next layer is prepared compared with the power of the titanium target when the titanium-doped diamond-like carbon film layer in the previous layer is prepared until the silicon transition layer/the titanium-doped diamond-like carbon film layer is coated in a periodic gradient manner, and taking out the carbon-based material when the temperature in the furnace is reduced to the room temperature after the coating is finished.
The total number of the obtained periodic coating layers of the silicon transition film layer/the titanium-doped diamond-like film layer is 6, the mass percentage content of titanium in the whole film layer is 19%, the thickness of each silicon transition film layer is 0.3 mu m, and the thickness of each titanium-doped diamond-like film layer is at least 0.33 mu m.
The titanium-doped diamond-like coating prepared by the embodiment has high bonding force with a carbon-based material, the bonding critical load is 12N, the hardness is 13GPa, the surface friction coefficient is 0.10, and the wear rate is 3.1 multiplied by 10 -7 mm 3 N · m. Compared with the carbon-based material without the coating, the carbon-based material with the titanium-doped diamond-like carbon coating plated on the surface has the advantages that the endothelial cell proliferation rate is increased from 70% to 77% in the endothelial cell proliferation experiment, and the survival rate of L929 cells is increased from 23% to 83% in the cytotoxicity experiment.
Example 3
The operation steps are completely the same as those of the embodiment 1, and the only difference is that the total number of the prepared periodic coating of the silicon transition film layer/the titanium-doped diamond-like film layer is 12, the titanium content of the whole film layer is 21 percent, the thickness of each silicon transition film layer is 0.3 mu m, and the thickness of each titanium-doped diamond-like film layer is at least 0.48 mu m.
The titanium-doped diamond-like coating prepared by the embodiment has high bonding force with a carbon-based material, the bonding critical load is 14N, the hardness is 15GPa, the surface friction coefficient is 0.09, and the wear rate is 2.8 multiplied by 10 -7 mm 3 N · m. Effectively improves the surface biocompatibility of the carbon-based material, and compared with the carbon-based material without the coating, the carbon-based material with the titanium-doped diamond-like carbon coating plated on the surface in the embodiment has endothelial cell proliferation experimentThe cell proliferation rate is improved from 70% to 85%, and the L929 cell survival rate is improved from 23% to 89% in a cytotoxicity experiment.
Example 4
The operation steps are completely the same as those of the embodiment 1, and the only difference is that the power of the titanium target in the preparation process of each titanium-doped diamond-like film layer is the same, and the power of the titanium target is 1.2kW. The total number of the obtained periodic coating layers of the silicon transition film layer/the titanium-doped diamond-like carbon film layer is 4, the titanium content of the whole film layer is 38 percent, the thickness of each silicon transition film layer is 0.3 mu m, and the thickness of each titanium-doped diamond-like carbon film layer is 0.52 mu m.
The titanium-doped diamond-like coating prepared by the embodiment has high bonding force with a carbon-based material, the bonding critical load is 9N, the hardness is 13GPa, the surface friction coefficient is 0.06, and the wear rate is 2.5 multiplied by 10 -7 mm 3 N · m. Compared with the carbon-based material without the coating, the carbon-based material with the titanium-doped diamond-like carbon coating plated on the surface has the advantages that the endothelial cell proliferation rate is increased from 70% to 78% in an endothelial cell proliferation experiment, and the survival rate of L929 cells is increased from 23% to 84% in a cytotoxicity experiment.
Comparative example 1
The only difference between this comparative example and example 1 is that: the titanium-doped diamond-like carbon film with the same total thickness is directly prepared on the surface of the carbon-based material without preparing a silicon transition film.
The titanium-doped diamond-like composite coating without the silicon transition film layer prepared in the comparative example is directly peeled off from the carbon-based material substrate, and the binding force is poor.
Comparative example 2
The only difference between this comparative example and example 1 is that: the diamond-like carbon film layer is not doped with titanium element.
The bonding force between the silicon transition film layer/titanium undoped diamond-like film layer composite coating prepared in the comparative example and the carbon-based material substrate is low, the value is 6N, the hardness is 9GPa, the friction coefficient is 0.12, and the wear rate is 5.2 multiplied by 10 -7 mm 3 N · m. The endothelial cell proliferation rate in the endothelial cell proliferation experiment for the carbon-based material with the coating prepared in this comparative example was 70%The survival rate of the L929 cells is improved from 23% to 80% in a cytotoxicity experiment. .
TABLE 1 comparison of Performance test results
Claims (9)
1. A carbon-based material with wear-resistant surface and high biocompatibility is characterized in that: the coating is composed of a carbon-based material and a titanium-doped diamond-like composite coating on the surface of the carbon-based material; the titanium-doped diamond-like carbon composite coating is formed by alternately superposing N layers of silicon transition film layers and N layers of titanium-doped diamond-like carbon film layers; wherein N is an integer greater than or equal to 1.
2. The carbon-based material with abrasion-resistant surface and high biocompatibility according to claim 1, wherein: the titanium-doped diamond-like carbon composite coating is formed by alternately overlapping 2-10 silicon transition film layers and 2-10 titanium-doped diamond-like carbon film layers.
3. The carbon-based material with wear-resistant surface and high biocompatibility as claimed in claim 2, wherein: the thickness of each silicon transition layer in the titanium-doped diamond-like carbon composite coating is within the range of 0.1-1.5 mu m, and the thickness of each titanium-doped diamond-like carbon film layer is within the range of 0.3-3.5 mu m.
4. The carbon-based material with abrasion-resistant surface and high biocompatibility according to claim 1, wherein: the titanium doping amount of each titanium-doped diamond-like film layer in the titanium-doped diamond-like composite coating is gradually decreased from the inner layer to the outer layer.
5. The carbon-based material with wear-resistant surface and high biocompatibility as recited in any one of claims 1 to 4, wherein: the titanium-doped diamond-like carbon composite coating comprises 5-50% by mass of titanium and the outermost titanium-doped diamond-like carbon film layer in the titanium-doped diamond-like carbon composite coating is not higher than 10% by mass of titanium.
6. The method for preparing a surface abrasion-resistant and highly biocompatible carbon-based material according to any one of claims 1 to 5, wherein: after the surface of the carbon-based material is cleaned, a silicon transition film layer and a titanium-doped diamond-like film layer are alternately plated on the surface of the carbon-based material.
7. The method for preparing the carbon-based material with the wear-resistant surface and the high biocompatibility as recited in claim 6, wherein the method comprises the following steps: the surface cleaning treatment process comprises the following steps: and (3) sequentially adopting water and ethanol to carry out ultrasonic washing on the carbon-based material, wherein the temperature of the ultrasonic washing is 20-32 ℃, and the time is 10-30 min.
8. The method for preparing the carbon-based material with the wear-resistant surface and the high biocompatibility according to the claim 6, is characterized in that: the silicon transition film layer is plated by an unbalanced intermediate frequency magnetron sputtering method, and the conditions for plating the silicon transition film layer are as follows: ar gas flow is 60-100 sccm, silicon target power is 0.5-3 kW, vacuum degree is 1.0 multiplied by 10 -1 ～4.0×10 -1 Pa, the power of the ion source is 0.5-2 kW, the negative bias voltage of the workpiece is 50-400V, and the coating time is 10-80 min.
9. The method for preparing the carbon-based material with the wear-resistant surface and the high biocompatibility according to the claim 6, is characterized in that: the titanium-doped diamond-like film layer is plated by a method combining unbalanced intermediate frequency magnetron sputtering and direct current arc PECVD; the conditions for plating the titanium-doped diamond-like carbon film layer are as follows: ar gas flow is 20-100 sccm, gas carbon source flow is 10-100 sccm, vacuum degree is 1.0 × 10 -1 ～4.0×10 -1 Pa, the power of the ion source is 0.5-3 kW, the power of the titanium target is 0.3-1.5 kW, the purity of the titanium target is not lower than 99.9wt%, the negative bias voltage of the workpiece is 50-800V, and the coating time is30-540 min, and in the process of plating any two adjacent titanium-doped diamond-like film layers, the power of a titanium target when plating the outer titanium-doped diamond-like film layer is reduced by 0.1-0.3 kW compared with the power of the titanium target when plating the inner titanium-doped diamond-like film layer.
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