CN115233224B - TC4 material with wear-resistant surface and low biotoxicity and preparation method thereof - Google Patents
TC4 material with wear-resistant surface and low biotoxicity and preparation method thereof Download PDFInfo
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- CN115233224B CN115233224B CN202210757715.6A CN202210757715A CN115233224B CN 115233224 B CN115233224 B CN 115233224B CN 202210757715 A CN202210757715 A CN 202210757715A CN 115233224 B CN115233224 B CN 115233224B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
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- 239000011248 coating agent Substances 0.000 claims abstract description 84
- 230000007704 transition Effects 0.000 claims abstract description 43
- 239000002131 composite material Substances 0.000 claims abstract description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 36
- 239000010703 silicon Substances 0.000 claims abstract description 36
- 238000004140 cleaning Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 30
- 239000011159 matrix material Substances 0.000 claims description 27
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000007747 plating Methods 0.000 claims description 12
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910003460 diamond Inorganic materials 0.000 claims description 7
- 239000010432 diamond Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005299 abrasion Methods 0.000 claims description 4
- 230000007423 decrease Effects 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 98
- 210000000988 bone and bone Anatomy 0.000 description 34
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 5
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- 239000010936 titanium Substances 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
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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
- 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
- C23C28/046—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 with at least one amorphous inorganic material layer, e.g. DLC, a-C:H, a-C:Me, the layer being doped or not
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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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- 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
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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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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- 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
- C23C28/048—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 with layers graded in composition or physical properties
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Abstract
The invention discloses a TC4 material with wear-resistant surface and low biotoxicity and a preparation method thereof. The silicon-doped diamond-like composite coating is formed by alternately superposing N silicon transition film layers and N silicon-doped diamond-like film layers on the surface of the TC4 substrate, so that the surface friction coefficient of the TC4 material can be effectively reduced, the wear resistance and hardness of the TC4 material can be improved, and the release of Al and V elements in the TC4 material after being implanted into a human body can be effectively reduced, thereby remarkably improving the biocompatibility of the TC4 material, and the Si-doped diamond-like composite coating has high binding force with the TC4 material and good stability and prolongs the service life of the TC4 material.
Description
Technical Field
The invention relates to a TC4 material, in particular to a TC4 material with a surface plated with a Si-doped diamond-like composite coating, and also relates to a preparation method thereof, belonging to the technical field of biomedical material preparation.
Background
TC4 (Ti 6Al 4V) has high specific strength, ideal fatigue strength, corrosion resistance, low elastic modulus, excellent formability and biocompatibility, and is widely applied to the biomedical field.
Although TC4 possesses many excellent properties, TC4 has many disadvantages in medical applications, TC4 is biologically inert and has poor wear resistance, which can easily cause bacterial infection, leading to implantation failure. TC4 can leak Al and V elements in the human body over a long period of time, causing cytotoxicity. TC4 has the disadvantage of low mechanical strength and is prone to complications such as breakage, loosening and the like.
If a proper biological coating is adopted on the surface of TC4, the biocompatibility can be improved, and film layers prepared on the surface of titanium alloy mainly by anodic oxidation and micro-arc oxidation are adopted in the prior art, but contain a large number of micropores and cracks and are easy to peel off in the friction process. The diamond-like coating has the advantages of good compactness, good corrosion resistance, good chemical stability and the like, but the diamond-like coating prepared on TC4 materials in the prior art has the problems of large internal stress, poor toughness and the like of the coating, and the problems of stripping and cracking of the coating in actual use occur.
Disclosure of Invention
Aiming at the defects existing in the prior art, the first aim of the invention is to provide a TC4 material with wear-resistant surface and low biological toxicity, the surface friction coefficient of the TC4 material can be effectively reduced, the wear resistance and hardness of the TC4 material can be improved, and the release of Al and V elements in the TC4 material after being implanted into a human body can be effectively reduced by plating a Si-doped diamond-like composite coating on the surface of the TC4 material, so that the biocompatibility of the TC4 material is obviously improved, the bonding force between the Si-doped diamond-like composite coating and the TC4 material is high, the stability is good, and the service life of the TC4 material is prolonged.
The invention also aims to provide a preparation method of the TC4 material with the surface wear resistance and low biological toxicity, which is used for preparing the silicon-doped diamond composite coating by combining an unbalanced intermediate frequency magnetron sputtering method and a direct current arc PECVD method, has the advantages of simple operation, easy and accurate control and the like, and is beneficial to industrial production.
In order to achieve the technical aim, the invention provides a TC4 material with wear-resistant surface and low biotoxicity, which is prepared by plating a silicon-doped diamond-like composite coating on the surface of a TC4 matrix; the silicon-doped diamond-like composite coating is formed by alternately superposing N silicon transition film layers and N silicon-doped diamond-like film layers; wherein N is an integer greater than or equal to 1.
Compared with the existing diamond-like coating, the silicon-doped diamond-like composite coating can effectively improve the comprehensive performance of the diamond-like film by introducing a proper amount of silicon element, such as improving the biocompatibility, friction performance and hardness of the diamond-like film, and the silicon transition layer and the silicon-doped diamond-like film are used for carrying out overlapped plating, so that the combination of the Si element doped in the diamond-like coating and atoms in the Si transition layer is tighter, the internal stress of the whole diamond-like coating is reduced, and the bonding force between the whole composite coating and a matrix is greatly improved. Meanwhile, the silicon-doped diamond-like composite coating can effectively prevent Al and V elements in the TC4 material from exuding in a human body, promote cell adhesion and proliferation, reduce friction force on the surface of the TC4 material and the like, and avoid the diffusion of grain boundary ions to surrounding tissues caused by the corrosion of the physiological environment on the surface of the TC4 material, thereby causing the degeneration of the properties of the implant material.
As a preferable scheme, the silicon-doped diamond-like composite coating is formed by alternately superposing 2-10 silicon transition film layers and 2-10 silicon-doped diamond-like film layers. The silicon-doped diamond-like composite coating is further preferably formed by alternately superposing 3-5 silicon transition film layers and 3-5 silicon-doped diamond-like film layers. If the film layers are too few, the purpose of improving the surface wear resistance and hardness of the TC4 material is difficult to achieve, and if the film layers are too many, the bonding capability between the composite coating and the TC4 material matrix can be reduced, so that the coating is easier to peel off.
As a preferable scheme, the thickness of each silicon transition layer in the silicon-doped diamond-like composite coating is in the range of 0.1-1.5 mu m, and the thickness of each silicon-doped diamond-like film layer is in the range of 0.3-3.5 mu m. Too low a thickness of the silicon transition film or too thick a thickness of the silicon-doped diamond-like film may reduce the bonding capability of the silicon-doped diamond-like film with the TC4 material, while too thick a thickness of the silicon transition film or too low a thickness of the silicon-doped diamond-like film may reduce the hardness and wear resistance.
According to the invention, the thickness of each film layer and the number of layers of the overlapped film layers are preferably regulated and controlled, so that the abrasion resistance, hardness and adhesive force of the coating can be effectively enhanced.
As a preferable scheme, the silicon doping amount of each silicon-doped diamond-like film layer in the silicon-doped diamond-like composite coating is gradually decreased from the inner layer to the outer layer. The silicon doping amount in each silicon-doped diamond-like film layer is reduced from the inner layer to the outer layer, so that the biocompatibility of the silicon-doped diamond-like film layer at the outermost layer can be better improved while the binding force between the whole composite coating and the TC4 material matrix is effectively improved.
As a preferable scheme, the total mass percentage content of silicon in the silicon-doped diamond-like composite coating is 2-40%, and the mass percentage content of silicon in the outermost silicon-doped diamond-like film layer is not higher than 10%. The silicon doping amount is increased within a proper range, so that the binding force between the composite coating and the TC4 material matrix can be effectively improved, and when the titanium mass percentage content in the outermost silicon-doped diamond-like film layer is higher than 10%, the biocompatibility of the silicon-doped diamond-like film layer is reduced, so that the silicon content of the whole silicon-doped diamond-like composite coating and the silicon-doped diamond-like film layer on the surface should be controlled within a proper range.
The invention also provides a preparation method of the TC4 material with the wear-resistant surface and low biotoxicity, which comprises the steps of carrying out surface cleaning treatment on a TC4 matrix, and then plating a silicon transition film layer and a silicon-doped diamond-like film layer on the surface of the TC4 matrix alternately.
As a preferable scheme, the surface cleaning treatment process is as follows: sequentially carrying out ultrasonic washing on the TC4 matrix by adopting water and ethanol, wherein the ultrasonic washing temperature is 20-32 ℃ and the ultrasonic washing time is 10-30 min, and drying after washing is completed. The ultrasonic auxiliary solvent washing can effectively remove stains on the surface of the TC4 matrix, and is beneficial to improving the bonding capability between a film layer which is plated subsequently and the TC4 matrix.
As a preferable scheme, the silicon transition film layer is plated by an unbalanced medium-frequency magnetron sputtering method, and the conditions for plating the silicon transition film layer are as follows: ar gas flow rate is 60-100 sccm, vacuum degree is 1.0X10 -1 ～4.0×10 -1 Pa, si target power is 0.5-3 kW, ion source power is 0.5-2 kW, workpiece negative bias voltage is 100-800V, and coating time is 10-120 min. In the process of preparing the silicon film layer by unbalanced magnetron sputtering, the temperature can be controlled to be lower than 200 ℃, and the formed film coating layer is more compact, thereby being beneficial to improvementAnd the combination between the plated film layer and the matrix.
As a preferable scheme, the silicon-doped diamond-like film layer is plated by a method combining unbalanced medium-frequency magnetron sputtering and direct current arc PECVD, and the conditions for plating the silicon-doped diamond-like film layer are as follows: ar gas flow is 10-100 sccm, gas carbon source flow is 20-100 sccm, vacuum degree is 1.0X10 -1 ～4.0×10 -1 Pa, the power of the ion source is 0.5-3 kW, the power of the Si target is 0.5-2 kW, the negative bias voltage of the workpiece is 50-800V, the coating time is 30-600 min, and the Si target power when the silicon-doped diamond-like film layer is coated on any two adjacent layers is reduced by 0.1-0.3 kW compared with the Si target power when the silicon-doped diamond-like film layer is coated on the inner layer. The preferred gaseous carbon source is acetylene and the like. The silicon-doped diamond-like carbon film is plated by adopting a method combining unbalanced intermediate frequency magnetron sputtering and direct current arc PECVD, so that the content of doped silicon element can be better controlled under the condition of not changing the preparation process parameters of the diamond-like carbon film, and the content of silicon element is stably controlled within the range of 2-40% of the most effective range for improving the performance of the film.
The specific method for preparing the Si-doped diamond-like composite coating on the surface of the TC4 matrix comprises the following steps:
A. cleaning TC4 matrix: ultrasonically cleaning the TC4 matrix by using purified water and ethanol in sequence, wherein the cleaning temperature is 20-32 ℃, the cleaning time is 10-30 min, and drying is carried out for standby after cleaning.
B. Vacuumizing pretreatment of coating equipment: placing the cleaned TC4 substrate in a coating device 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 50-120 sccm, and the vacuum degree is 4.0X10 -1 ～7.0×10 -1 Pa, the negative bias voltage of the workpiece is 600-800V, and the degassing time is 10-30 min.
D. Ion source cleaning work piece: ar gas flow rate is 60-100 sccm, vacuum degree is 3.0X10 -1 ～6.0×10 -1 Pa, the power of the ion source is 0.5-1.5 kWThe negative bias voltage of the workpiece is 400-800V, and the cleaning time is 15-40 min.
E. Preparing a Si transition film layer: ar gas flow rate is 60-100 sccm, vacuum degree is 1.0X10 -1 ～4.0×10 -1 Pa, si target power is 0.5-3 kW, ion source power is 0.5-2 kW, workpiece negative bias voltage is 100-800V, and coating time is 10-120 min.
F. Preparing a Si-doped diamond-like film layer: ar gas flow is 10-100 sccm, acetylene gas flow is 20-100 sccm, vacuum degree is 1.0X10 -1 ～4.0×10 -1 Pa, the power of the ion source is 0.5-3 kW, the power of the Si target is 0.5-2 kW, the negative bias voltage of the workpiece is 50-800V, and the coating time is 30-600 min.
G. And D, alternately preparing Si transition film layers and Si-doped diamond-like film layers according to the processes of the steps D and E, along with the preparation of each Si transition film layer, reducing the Si target power in the preparation of the next Si-doped diamond-like film layer by 0.1-0.3 kW compared with the Si target power in the preparation of the last Si-doped diamond-like film layer until the periodic gradient coating of the Si transition film layer/the Si-doped diamond-like film layer is completed, and after the film coating is completed, reducing the temperature in the furnace to room temperature, and taking out the TC4 matrix.
The TC4 matrix of the present invention, e.g., TC4 bone screws.
The preparation method adopts equipment which is HCSH-DLC650 equipment of vacuum technology Co Ltd, PVD850-DLC equipment of Dongguan south China New material research Co Ltd, or DLC-800 equipment of Qingdao excellent hundred vacuum equipment Co Ltd, and is film plating equipment which combines unbalanced intermediate frequency magnetron sputtering and direct current arc PECVD technology.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
according to the method, the surface modification treatment is carried out on the TC4 material, the silicon-doped diamond-like composite coating is plated on the surface of the traditional TC4 material by combining an unbalanced intermediate frequency magnetron sputtering method and a direct current arc PECVD method, the method is simple to operate and easy to control accurately, industrial production is facilitated, the gradient Si-doped diamond-like coating can be plated on the surface of the TC4 material by adopting the method combining the unbalanced intermediate frequency magnetron sputtering method and the direct current arc PECVD method, the content of the Si-doped element can be controlled better under the condition that technological parameters of the diamond-like coating are not changed, and the content of the Si element is controlled to be 2% -40% of the most effective range for improving the performance of the film.
The silicon-doped diamond-like composite coating is formed by alternately superposing a plurality of silicon transition film layers and a plurality of silicon-doped diamond-like film layers, si element is doped in the silicon-doped diamond-like composite coating, atoms in the silicon transition layer are combined more tightly, the internal stress of the silicon-like coating is reduced, the bonding force between the coating and a substrate 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 superposition layer number and the like, and the bonding critical load of the silicon-doped diamond-like composite coating and the substrate can reach more than 15N, and the hardness of the composite coating is more than 15 GPa.
According to the invention, the Si-doped diamond-like composite coating is prepared on the surface of the TC4 material, so that the biocompatibility of the bone screw can be effectively improved, the escape of toxic Al and V elements in the TC4 bone screw can be prevented, and the diffusion of crystal boundary ions in the bone screw material to surrounding tissues caused by the corrosion of physiological environment after the TC4 bone screw is implanted into a human body can be effectively avoided, so that the degeneration of the nature of the implanted material is caused, and the toxicity to cells is increased. The diamond-like carbon coating doped with Si has obviously improved biocompatibility of TC4 material, and compared with a substrate without the coating, the film prepared by the method has the advantages of improved endothelial cell proliferation rate and reduced cytotoxicity.
Drawings
Fig. 1 is an SEM image of microscopic morphology of a Si-doped diamond-like coating on the surface of a TC4 material according to example 1 of the present invention, and it can be seen from the image that the Si-doped diamond-like composite coating is uniform and consistent with the flatness of the TC4 material substrate.
FIG. 2 is a schematic diagram of the structure of a coating layer of Si-doped diamond-like carbon on the surface of TC4 material in example 2 of the present invention.
Detailed Description
In order that the invention may be more readily understood, a detailed description of the invention will be presented below in conjunction with specific embodiments, which are provided herein to illustrate the invention in further detail and not to limit the scope of the claims.
And (3) performance detection: the mechanical properties of the coatings were tested by nanoindentation and nanoscratching in the examples below; the friction coefficient of the membrane layer is measured by adopting a ball-and-disc friction tester, and the improvement of the biocompatibility of the coating on the matrix is checked by adopting an endothelial cell proliferation experiment, and the cytotoxicity is checked by adopting a cytotoxicity experiment of L929 mouse fibroblasts.
The following examples are illustrative of the use of conventional typical TC4 bone screws as the matrix material.
Example 1
A. Cleaning TC4 bone screws, wherein the cleaning steps are as follows: ultrasonically cleaning TC4 bone screws by using purified water and ethanol in sequence, wherein the cleaning temperature is 25 ℃, the cleaning time is 25 minutes, and drying is carried out for standby after cleaning.
B. Placing the cleaned TC4 bone screw in a coating device 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, and the vacuum degree is 5.0X10 -1 Pa, the negative bias voltage of the workpiece is 800V, and the degassing time is 20min.
D. Ion source cleaning work piece: ar gas flow rate was 80sccm, vacuum degree was 4.0X10 -1 Pa, the ion source power is 1kW, the workpiece negative bias voltage is 800V, and the cleaning time is 30min.
E. Preparing a Si transition film layer: ar gas flow was 60sccm, vacuum was 2.0X10 -1 Pa, si target power is 1kW, ion source power is 0.9kW, workpiece negative bias voltage is 600V, and coating time is 60min.
F. Preparing a Si-doped diamond-like film layer: ar gas flow rate was 30sccm, acetylene gas flow rate was 80sccm, and vacuum degree was 2.0X10 -1 Pa, the ion source power is 1.5kW, the Si target power is 1.6kW, the negative bias voltage of the workpiece is 600V, and the coating time is prolonged60min.
G. And D, alternately preparing Si transition film layers and Si-doped diamond-like film layers according to the processes of the steps D and E, wherein along with the preparation of each Si transition film layer, the power of a silicon target in the preparation of the next Si-doped diamond-like film layer is reduced by 0.2kW compared with that of the Si target in the preparation of the last Si-doped diamond-like film layer, so that the total number of gradient periodic coating layers of the Si transition film layers/the Si-doped diamond-like film layers is 6, the Si content of the overall coating is 15%, the thickness of each Si transition film layer is 0.31 mu m, and the thickness of each Si-doped diamond-like film layer is at least 0.37 mu m.
The Si-doped diamond-like composite coating prepared in the embodiment has high binding force with TC4 bone screws, the binding critical load is 18N, the matrix hardness is 15GPa, and the surface friction coefficient is 0.12. The biocompatibility of the surface of the TC4 bone screw is effectively improved, compared with an uncoated TC4 bone screw, the endothelial cell proliferation rate of the TC4 bone screw with the surface plated with the Si-like diamond coating in the embodiment is improved from 80% to 87% in an endothelial cell proliferation experiment, and the survival rate of L929 cells is improved from 20 to 85% in a cytotoxicity experiment.
Example 2
A. Cleaning TC4 bone screws, wherein the cleaning steps are as follows: ultrasonically cleaning TC4 bone screws by using purified water and ethanol in sequence, wherein the cleaning temperature is 25 ℃, the cleaning time is 25 minutes, and drying is carried out for standby after cleaning.
B. Placing the cleaned TC4 bone screw in a coating device 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, and the vacuum degree is 5.0X10 -1 Pa, the negative bias voltage of the workpiece is 800V, and the degassing time is 20min.
D. Ion source cleaning work piece: ar gas flow rate was 80sccm, vacuum degree was 4.0X10 -1 Pa, the ion source power is 1kW, the workpiece negative bias voltage is 800V, and the cleaning time is 30min.
E. Preparing a Si transition film layer: ar gas flow was 60sccm, vacuum was 2.0X10 -1 Pa, si target power of 1kW, ion source power of 0.9kW, the negative bias voltage of the workpiece is 600V, and the coating time is 60min.
F. Preparing a Si-doped diamond-like film layer: ar gas flow rate was 30sccm, acetylene gas flow rate was 80sccm, and vacuum degree was 2.0X10 -1 Pa, the ion source power is 1.5kW, the Si target power is 1.8kW, the workpiece negative bias voltage is 600V, and the deposition time is 60min.
G. And D, alternately preparing Si transition film layers and Si-doped diamond-like film layers according to the processes of the steps D and E, wherein along with the preparation of each Si transition film layer, the power of a silicon target in the preparation of the next Si-doped diamond-like film layer is reduced by 0.2kW compared with that of the Si target in the preparation of the last Si-doped diamond-like film layer, so that the total number of gradient periodic coating layers of the Si transition film layers/the Si-doped diamond-like film layers is 10, the Si content of the overall coating is 19%, the thickness of each Si transition film layer is 0.31 mu m, and the thickness of each Si-doped diamond-like film layer is at least 0.4 mu m.
The Si-doped diamond-like composite coating prepared in the embodiment has high binding force with TC4 bone screws, the binding critical load is 21N, the matrix hardness is 20GPa, and the surface friction coefficient is 0.17. The biocompatibility of the surface of the TC4 bone screw is effectively improved, compared with an uncoated TC4 bone screw, the endothelial cell proliferation rate of the TC4 bone screw with the surface plated with the Si-like diamond coating in the embodiment is improved from 80% to 85% in an endothelial cell proliferation experiment, and the survival rate of L929 cells is improved from 20% to 87% in a cytotoxicity experiment.
Example 3
A. Cleaning TC4 bone screws, wherein the cleaning steps are as follows: ultrasonically cleaning TC4 bone screws by using purified water and ethanol in sequence, wherein the cleaning temperature is 25 ℃, the cleaning time is 25 minutes, and drying is carried out for standby after cleaning.
B. Placing the cleaned TC4 bone screw in a coating device 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, and the vacuum degree is 5.0X10 -1 Pa, the negative bias voltage of the workpiece is 800V, and the degassing time is 20min.
D. Ion source cleanerWashing a workpiece: ar gas flow rate was 80sccm, vacuum degree was 4.0X10 -1 Pa, the ion source power is 1kW, the workpiece negative bias voltage is 800V, and the cleaning time is 30min.
E. Preparing a Si transition film layer: ar gas flow was 60sccm, vacuum was 2.0X10 -1 Pa, si target power of 1.3kW, ion source power of 0.9kW, workpiece negative bias voltage of 800V, and coating time of 60min.
F. Preparing a Si-doped diamond-like film layer: ar gas flow rate was 30sccm, acetylene gas flow rate was 50sccm, and vacuum degree was 2.0X10 -1 Pa, the ion source power is 1.5kW, the Si target power is 1.8kW, the negative bias voltage of the workpiece is 800V, and the coating time is 60min.
G. And D, alternately preparing Si transition film layers and Si-doped diamond-like film layers according to the processes of the steps D and E, wherein along with the preparation of each Si transition film layer, the power of a silicon target in the preparation of the next Si-doped diamond-like film layer is reduced by 0.2kW compared with that of the Si target in the preparation of the last Si-doped diamond-like film layer, so that the total number of gradient periodic coating layers of the Si transition film layers/the Si-doped diamond-like film layers is 8, the Si content of the whole film layer is 21%, the thickness of each Si transition film layer is 0.39 mu m, and the thickness of each Si-doped diamond-like film layer is at least 0.41 mu m.
The Si-doped diamond-like composite coating prepared in the embodiment has high binding force with TC4 bone screws, the binding critical load is 23N, the matrix hardness is 22GPa, and the surface friction coefficient is 0.14. The biocompatibility of the surface of the TC4 bone screw is effectively improved, compared with an uncoated TC4 bone screw, the endothelial cell proliferation rate of the TC4 bone screw with the surface plated with the Si-like diamond coating in the embodiment is improved from 80% to 84% in an endothelial cell proliferation experiment, and the survival rate of L929 cells is improved from 20% to 89% in a cytotoxicity experiment.
Example 4
The procedure is identical to that of example 1, the only difference being that: the Si target power in the process of preparing the Si-doped diamond-like film layer is 1.6kW. The Si content of the whole coating is 31%, the thickness of each Si transition film layer is 0.31 mu m, and the thickness of each Si-doped diamond-like film layer is 0.43 mu m.
The Si-doped diamond-like composite coating prepared in the embodiment has high binding force with TC4 bone screws, the binding critical load is 17N, the matrix hardness is 14GPa, and the surface friction coefficient is 0.11. The biocompatibility of the surface of the TC4 bone screw is effectively improved, compared with an uncoated TC4 bone screw, the endothelial cell proliferation rate of the TC4 bone screw with the surface plated with the Si-like diamond coating in the embodiment is improved from 80% to 85% in an endothelial cell proliferation experiment, and the survival rate of L929 cells is improved from 20 to 83% in a cytotoxicity experiment.
Comparative example 1
The only difference between this comparative example and example 1 is that: and the Si-doped diamond-like composite coating is directly prepared on the surface of the TC4 bone screw without preparing the Si transition film layer.
The Si-doped diamond-like composite coating of the Si-free transition film layer prepared in the comparative example is directly peeled off from the TC4 bone screw substrate, and the bonding force is poor.
Comparative example 2
The only difference between this comparative example and example 1 is that: si element is not doped in the diamond-like carbon film layer.
The Si transition film layer/undoped silicon diamond-like composite coating prepared in the comparative example has lower bonding force with the substrate, the value of 8N, the hardness of 13GPa and the friction coefficient of 0.15. The endothelial cell proliferation rate in the endothelial cell proliferation experiment of the TC4 bone screw with the coating prepared in this comparative example was increased from 80% to 82%, and the L929 cell survival rate in the cytotoxicity experiment was increased from 20 to 81%. .
Table 1 comparison of performance test results
Claims (3)
1. A preparation method of a TC4 material with wear-resistant surface and low biotoxicity is characterized by comprising the following steps: after the TC4 matrix is subjected to surface cleaning treatmentAlternately plating a silicon transition film layer and a silicon-doped diamond-like film layer on the surface of the TC4 matrix; the surface cleaning treatment process comprises the following steps: sequentially carrying out ultrasonic washing on the TC4 matrix by adopting water and ethanol, wherein the ultrasonic washing temperature is 20-32 ℃ and the ultrasonic washing time is 10-30 min, and drying after washing is completed; the silicon-doped diamond film is plated by a method combining unbalanced intermediate frequency magnetron sputtering and direct current arc PECVD, wherein the conditions of plating the silicon-doped diamond film are that Ar gas flow is 10-100 sccm, gas carbon source flow is 20-100 sccm, and vacuum degree is 1.0X10 -1 ~4.0×10 -1 Pa, the ion source power is 0.5-3 kW, the Si target power is 0.5-2 kW, the negative bias voltage of the workpiece is 50-800V, the coating time is 30-600 min, and the Si target power when the silicon-doped diamond-like film layer is plated on any two adjacent layers is reduced by 0.1-0.3 kW compared with the Si target power when the silicon-doped diamond-like film layer is plated on the inner layer in the plating process; the critical load of the combination of the silicon-doped diamond-like composite coating and the TC4 matrix is 17-23N.
2. The method for preparing the TC4 material with the abrasion-resistant surface and low biotoxicity according to claim 1, wherein the method comprises the following steps of: the silicon transition film layer is plated by an unbalanced medium-frequency magnetron sputtering method, wherein the condition of plating the silicon transition film layer is that Ar gas flow is 60-100 sccm, and vacuum degree is 1.0x10 -1 ~4.0×10 -1 Pa, si target power is 0.5-3 kW, ion source power is 0.5-2 kW, workpiece negative bias voltage is 100-800V, and coating time is 10-120 min.
3. A TC4 material having a surface resistant to abrasion and low biotoxicity prepared by the method of claim 1 or 2, characterized in that: alternately plating a silicon transition film layer and a silicon-doped diamond-like film layer on the surface of the TC4 matrix; the silicon-doped diamond-like composite coating is formed by alternately superposing 2-10 silicon transition film layers and 2-10 silicon-doped diamond-like film layers; the silicon doping amount of each silicon-doped diamond-like film layer in the silicon-doped diamond-like composite coating gradually decreases from the inner layer to the outer layer; the total mass percentage content of silicon in the silicon-doped diamond-like composite coating is 2-40%, and the mass percentage content of silicon in the outermost silicon-doped diamond-like film layer is not higher than 10%; the thickness of each silicon transition layer in the silicon-doped diamond-like composite coating is within the range of 0.1-1.5 mu m, and the thickness of each silicon-doped diamond-like film layer is within the range of 0.3-3.5 mu m.
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