CN115251893B - A carbon-based lung nodule localization needle and its preparation method - Google Patents
A carbon-based lung nodule localization needle and its preparation methodInfo
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- CN115251893B CN115251893B CN202210756728.1A CN202210756728A CN115251893B CN 115251893 B CN115251893 B CN 115251893B CN 202210756728 A CN202210756728 A CN 202210756728A CN 115251893 B CN115251893 B CN 115251893B
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- A61B5/06—Devices, other than using radiation, for detecting or locating foreign bodies ; Determining position of diagnostic devices within or on the body of the patient
- A61B5/061—Determining position of a probe within the body employing means separate from the probe, e.g. sensing internal probe position employing impedance electrodes on the surface of the body
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Abstract
本发明公开了一种碳基材料肺结节定位针头及其制备方法。定位针头以碳基材料为基体，在其表面制备热解碳(PyC)涂层和掺银DLC(DLC)复合涂层，PyC涂层提供连续界面，以提高掺银DLC复合涂层与碳基材料的结合能力，而掺银DLC复合涂层能够有效降低碳基材料的表面摩擦系数，提高其耐磨性和硬度，且可以改善定位针头在植入人体后由于碳基材料摩擦掉粉导致的人体不良反应，且掺银DLC涂层还赋予了碳基材料良好的表面生物相容性和抑菌杀菌性能，特别是掺银DLC复合涂层与碳基材料表面结合力高，稳定性好，可以延长其使用寿命。
This invention discloses a carbon-based lung nodule localization needle and its preparation method. The localization needle uses a carbon-based material as a substrate, on which a pyrolytic carbon (PyC) coating and a silver-doped DLC (DLC) composite coating are prepared. The PyC coating provides a continuous interface to improve the bonding ability between the silver-doped DLC composite coating and the carbon-based material. The silver-doped DLC composite coating effectively reduces the surface friction coefficient of the carbon-based material, improving its wear resistance and hardness. It also mitigates adverse reactions in the human body caused by frictional powdering of the carbon-based material after implantation. Furthermore, the silver-doped DLC coating imparts good surface biocompatibility and antibacterial properties to the carbon-based material. In particular, the silver-doped DLC composite coating exhibits high bonding strength and good stability with the carbon-based material surface, extending its service life.
Description
Technical Field
The invention relates to a carbon-based material lung nodule positioning needle, in particular to a lung nodule positioning needle which is provided with a PyC coating and a silver-doped DLC composite coating on the surface and is composed of a carbon-based material, and also relates to a preparation method thereof, belonging to the technical field of biomedical materials.
Background
At present, the incidence and death rate of lung cancer are increased year by year, and 80% of lung cancer is clinically found to be middle and late stage because early lung cancer is hidden, so lung cancer is the first place of malignant tumor death. The five-year survival rate of lung cancer is only 15%, and the early-stage lung cancer survival rate of timely treatment can reach 60-80%. With the popularity of low-dose helical CT lung cancer screening, increasingly pulmonary nodules are detected. Lung nodules are small focal, round-like shadows with increased imaging density, can be single or multiple, and do not accompany atelectasis, enlargement of the lung door and pleural effusion. Isolated lung nodules are asymptomatic, often single, well-defined, high density, soft tissue shadows of less than or equal to 3cm in diameter surrounded by air-bearing lung tissue.
With the total thoracoscopy (VATS) becoming the main means of diagnosis and treatment of pulmonary nodules, small pulmonary nodules have small volume, few solid components and soft texture, and cannot be accurately positioned by an observation or palpation method in the VATS, even if the pulmonary nodules with the size of less than or equal to 1cm after the chest opening operation fail more than 50% under the positioning methods of macroscopic observation and finger palpation. Therefore, the accurate positioning of the lung nodules under CT guidance is usually carried out before the operation in clinic, the accuracy of the lung nodule excision operation is increased, the minimum lung wedge excision is realized, the wound caused by the excision operation is reduced, and the life quality of patients is improved.
The common positioning means comprise the following technical routes of 1) puncturing before operation under CT guidance, injecting methylene blue around the nodule, marking by color, 2) medical colloid, puncturing before operation under CT guidance, injecting N-butyl-2-cyanoacrylate around the nodule to quickly solidify into colloid, positioning by forming a tumor by colloid, and 3) indwelling positioning needle, puncturing before operation under CT guidance, and positioning by indwelling positioning needle around the nodule.
The early-stage clinical use of the coloring agent is more, but the coloring halation speed is too high, the requirement on the post-dyeing operation interval is strict, and the post-positioning operation color identification degree is low and the positioning failure is easy to cause for the patient with obvious carbon powder deposition. The medical colloid has pungent smell, can cause obvious pungent cough of patients after entering bronchus, and has the defect of coagulation in an injection needle tube. Therefore, the wire technology of the indwelling positioning needle is the external positioning technology of the lung micro-nodules and lung internal grinding glass-like lesions which are most widely applied clinically at present, mainly comprises nickel-titanium alloy microcoils, four-hook positioning needles, spring coils with unique dumbbell-shaped structures, stainless steel hooked metal guide wires and the like, and has certain defects, patients often have symptoms of pain and pleural irritation after positioning, sometimes the patients do not operate in time, the risks of shifting, falling and even breaking can be increased due to time, movement and other factors, and secondly, the common complications such as pneumothorax, bleeding and pain are easy to occur after positioning. And the positioning needle is left in the ventilation state, and the volume of the lung is changed in the collapse process of the lung, so that the positioning needle can further damage the lung. And the end of the metal wire is easy to break and is left in the body, and as the metal wire is very small and is not easy to find, once the metal wire breaks and is effectively treated in a short time, a huge medical accident of residual metal in the lung after operation can be caused.
The carbon-based material is a good biological material, but is fragile, and the local brittleness is obvious when the carbon-based material is especially applied to the preparation of small-size parts, the prepared positioning needle is easy to fall off to bring secondary injury, and in addition, the carbon-based material is an inert material but has the characteristic of being porous, so that the carbon-based material is easy to carry bacteria into human tissues in the use process to cause inflammation risk.
Disclosure of Invention
Aiming at the defects existing in the prior art, the first aim of the invention is to provide the carbon-based material lung nodule positioning needle, which is characterized in that a PyC coating and a silver-doped DLC composite coating are plated on the surface of the carbon-based material lung nodule positioning needle, so that the technical problems existing in the process of preparing the carbon-based material lung nodule positioning needle can be well solved, the silver-doped DLC composite coating can not only effectively reduce the friction coefficient of the carbon-based material surface and improve the wear resistance and the hardness of the carbon-based material surface, but also improve the adverse reaction of the carbon-based material surface caused by friction powder removal after the carbon-based material lung nodule positioning needle is implanted into a human body, and the silver-doped DLC composite coating also endows the carbon-based material surface with good biocompatibility and antibacterial and bactericidal properties, in particular, the silver-doped DLC composite coating has high surface binding force with the carbon-based material surface and good stability, and can prolong the service life.
The invention further aims at providing a preparation method of the carbon-based pulmonary nodule positioning needle, which is simple to operate, easy to control accurately and beneficial to industrial production.
The invention provides a carbon-based pulmonary nodule positioning needle which comprises an insertion needle or an embedded needle, wherein the insertion needle comprises a needle rod, the front end of the needle rod is a conical tip, the tail of the needle rod is a pin rod, a lead hole is formed in the needle rod or the pin rod, the front end of the needle rod is a conical tip or a blunt tip, the tail of the needle rod is a pin rod, the pin rod is provided with a lead hole, and the pulmonary nodule positioning needle consists of a carbon-based material coating and a silver-doped DLC composite coating on the surface of the carbon-based material coating.
The PyC coating and the silver-doped DLC composite coating are plated on the surface of the lung nodule positioning needle, so that the defects that the carbon-based material is easy to fall off to cause secondary injury due to local brittleness of a small-size piece prepared by the carbon-based material and the carbon-based material is easy to carry bacteria into human tissues to cause inflammation and the like in the using process can be well overcome. The PyC coating is mainly deposited on the surface of the carbon-based material matrix, can block holes on the surface of the carbon-based material matrix, provides a continuous interface to endow the surface with breakage resistance, is beneficial to improving the binding force with the silver-doped DLC composite coating, has good biocompatibility, surface hardness and friction performance, has antibacterial property, can effectively improve the comprehensive performance of the DLC coating compared with the traditional DLC coating by introducing metallic silver, such as improving the biocompatibility, friction performance and hardness of the DLC coating, and simultaneously, performs overlapped plating with the silver-doped DLC coating by virtue of the silicon transition layer, so that the atomic combination of silver elements doped in the DLC coating and atoms in the silicon transition layer is tighter, the internal stress of the whole composite coating is reduced, and the binding force between the whole composite coating and the carbon-based material matrix is greatly improved. And the silver-doped DLC composite coating is plated on the surface of the carbon-based material lung nodule positioning needle head, so that adverse reaction of the carbon-based material lung nodule positioning needle head on a human body caused by powder friction after the carbon-based material lung nodule positioning needle head is implanted into the human body can be avoided.
As a preferable scheme, the silver-doped DLC composite coating is formed by alternately superposing n silicon transition film layers and n silicon-doped DLC film layers, wherein n=2-10. If the film layer is too few, the aim 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 many, the bonding capability between the composite coating and the carbon-based material matrix is reduced, so that the coating is easier to peel off.
As a preferable scheme, the silver doping amount of each silver-doped DLC film layer in the silver-doped DLC composite coating is gradually decreased from the inner layer to the outer layer. The silver doping amount in each silver-doped DLC film layer is reduced from the inner layer to the outer layer, so that the binding force between the whole composite coating and the carbon-based material matrix can be effectively improved, and meanwhile, the biocompatibility of the silver-doped DLC film layer on the outermost layer can be better improved.
As a preferable scheme, the thickness of the PyC coating is 10-50 μm. The PyC coating is too thin to form a complete continuous coating, the surface roughness of the coating is increased due to too thick, and the coating is easy to fall off.
As a preferable scheme, the thickness of the silicon transition layer is 0.1-1.5 mu m.
As a preferable scheme, the thickness of the silver-doped DLC film layer is 0.3-3.5 mu m. Too low a thickness of the silicon transition film or too thick a thickness of the silver-doped DLC film may reduce the binding ability of the silver-doped DLC film to the carbon-based material, while too thick a thickness of the silicon transition film or too low a thickness of the silver-doped DLC film may reduce the hardness and wear resistance, etc.
As a preferable scheme, the silver mass percentage content in the silver-doped DLC composite coating is 1% -20%, and the silver mass percentage content in the outermost silver-doped DLC film layer is not higher than 10%. The addition of silver in a proper range can effectively improve the binding force between the composite coating and the carbon-based material, and when the silver mass percentage content in the outermost silver-doped DLC film layer is higher than 10%, the biocompatibility of the composite coating is reduced and normal cells are poisoned, so that the silver content of the whole silver-doped DLC composite coating and the silver-doped DLC film layer on the surface should be controlled in a proper range.
As a preferable scheme, the diameter of the needle rod is 1.5-2 mm, the diameter of the pin rod is 1.0-1.5 mm, the diameter of the lead hole is 0.2-0.5 mm, and the taper of the conical tip is more than 30 degrees.
The invention also provides a preparation method of the carbon-based material lung nodule positioning needle, which comprises the steps of forming a needle blank by machining the carbon-based material, depositing a PyC coating on the surface of the blank, and plating a silver-doped DLC composite coating.
As a preferable scheme, the PyC coating is generated by a chemical vapor deposition method, wherein the condition of the chemical vapor deposition method is that the deposition is carried out for 10-50 hours at the temperature of 1000-1800 ℃ under the condition of introducing a gas carbon source. Gaseous carbon sources are common hydrocarbon gases such as methane, propane, and the like.
As a preferable scheme, the silver-doped DLC composite coating is plated by a combination method of unbalanced intermediate frequency magnetron sputtering and direct current arc PECVD, firstly, a silicon transition film layer is plated by an unbalanced intermediate frequency magnetron sputtering method, then, the silver-doped DLC film layer is plated by a combination method of unbalanced intermediate frequency magnetron sputtering and direct current arc PECVD, and the silver-doped DLC film layer is plated alternately.
As a more preferable scheme, the plating condition of the silicon transition film layer is that Ar gas flow is 60-100 sccm, silicon target power is 0.5-3 kW, vacuum degree is 1.0X10- 1～4.0×10-1 Pa, ion source power is 0.5-2 kW, workpiece negative bias voltage is 50-400V, and plating time is 10-80 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, so that the combination between the coated film layer and the substrate is improved.
As a more preferable scheme, the plating conditions of the silver-doped DLC film layer are that Ar gas flow is 20-100 sccm, gas carbon source flow is 10-100 sccm, vacuum degree is 1.0X10- 1～4.0×10-1 Pa, ion source power is 0.5-3 kW, silver palladium power is 0.1-1 kW, silver target purity is not less than 99.9wt%, workpiece negative bias voltage is 50-600V, plating time is 30-540 min, and silver target power when plating an outer silver-doped DLC film layer is reduced by 0.1-0.3 kW compared with silver target power when plating an inner silver-doped DLC film layer. According to the invention, the silver-doped DLC film is plated by adopting a method combining unbalanced intermediate frequency magnetron sputtering and direct current arc PECVD, so that the content of doped silver element can be better controlled under the condition of not changing the preparation process parameters of the DLC film, and the mass percentage content of silver element is stably controlled within the range of 1% -15% of the most effective range for improving the performance of the film. Gaseous carbon sources such as acetylene and the like.
The carbon-based material of the present invention is produced by a conventional method, and the following is exemplified:
1) The carbon fiber preform is formed by needling a carbon fiber and a carbon fiber net tire in a laminated mode, wherein the carbon fiber is a 1k carbon fiber bundle with the width of 3mm, a 2k carbon fiber bundle with the width of 5mm, a 3k carbon fiber bundle with the width of 8mm, a 6k carbon fiber bundle with the width of 15mm or a 12k carbon fiber with the width of 25mm, or a combination of the carbon fiber and the carbon fiber net tire, the carbon fiber net tire is 10-40 g/m 2, and the density of a net layer is 20-40 layers/cm.
2) And preparing matrix carbon or matrix carbon and silicon carbide from the carbon fiber preform by adopting chemical vapor deposition and/or liquid phase dipping-cracking, wherein the deposition density is 1.3-2.5 g/cm 3.
The process for preparing the matrix carbon by chemical vapor deposition comprises the steps of placing a carbon fiber preform into a deposition furnace, introducing a carbon-containing gas source (natural gas, methane, propylene, propane and the like, nitrogen or hydrogen is diluent gas, and the flow ratio of the carbon source gas to the diluent gas is 1:0-3) at the temperature of 800-1350 ℃ and depositing for 50-250 hours.
The process for preparing the matrix carbon by dipping-cracking comprises the steps of vacuum pressurizing and dipping, solidifying and cracking (resin: 900-1050 ℃ and normal pressure; asphalt: 750-850 ℃ and 50-200 MPa) and the like densification of a carbon fiber preform through resin (furan, phenolic aldehyde, furone and the like) or asphalt (petroleum asphalt and coal asphalt). The impregnation pressure is 2.0-6.0 MPa, the impregnation time is 2-10 h, the curing temperature is 160-230 ℃, the curing time is 10-50 h, and the cracking time is 2-20 h.
The process for preparing the silicon carbide matrix by chemical vapor deposition comprises the steps of placing a carbon fiber preform into a deposition furnace, and depositing for 30-120 h at the temperature of 1000-1300 ℃ by introducing an air source (trichloromethylsilane, hydrogen is carrier gas and diluent gas, and the flow ratio of the trichloromethylsilane to the hydrogen is 1:1-20).
The preparation process of the silicon carbide substrate by liquid phase impregnation-pyrolysis comprises the steps of vacuum pressurizing impregnation, solidification treatment, pyrolysis and other densification processes of a carbon fiber preform through a silicon-containing precursor (polycarbosilane PCS, polymethylsilane PMS). The impregnation pressure is 1.0-6.0 MPa, the impregnation time is 2-10 h, the curing temperature is 120-240 ℃, the curing time is 10-60 h, the cracking temperature is 750-1150 ℃ and the time is 2-20 h, and the ceramming temperature is 1150-1650 ℃ and the time is 2-10 h.
The lead hole of the lung nodule positioning needle head can be used for fixing connecting wires, such as nylon, non-degradable silk threads and the like.
The silver-doped diamond-like composite coating is prepared by adopting HCSH-DLC650 equipment which is collected by Guangdong to be vacuum technology, inc. or PVD850-DLC equipment which is used by Dongguan, south China new material research, inc. or DLC-800 equipment which is used by Qingdao, utility and vacuum equipment, inc. and is a film plating equipment which is formed by combining unbalanced intermediate frequency magnetron sputtering and direct current arc PECVD technology.
The preparation method of the lung nodule positioning needle head comprises the following steps:
1) The carbon-based material is processed into a positioning needle head blank through the procedures of mechanical cutting, polishing and the like.
2) And preparing a pyrolytic carbon coating PyC on the surface of the blank, wherein the thickness of the pyrolytic carbon coating is 10-50 mu m, and the PyC coating is generated by chemical vapor deposition under the generation condition that a gaseous carbon source (such as natural gas, methane and other common gaseous carbon sources) is adopted, and the pyrolytic carbon coating is deposited for 10-50 h at the temperature of 1000-1800 ℃.
3) Further preparing a silver-doped DLC composite coating on the blank, wherein the silver-doped DLC composite coating is a silicon transition layer-silver-doped DLC gradient film layer, placing the cleaned blank in a film plating device combining unbalanced intermediate frequency magnetron sputtering and direct current arc PECVD, vacuumizing to a working vacuum degree, removing impurity gas in a furnace, and cleaning a workpiece by using an ion source; then plating a silicon transition film layer by an unbalanced intermediate frequency magnetron sputtering method, plating a silver-doped DLC film layer by an unbalanced intermediate frequency magnetron sputtering-direct current arc PECVD phase combination method, alternately plating, and cooling to room temperature and taking out the carbon-based material after the temperature in the furnace is reduced to room temperature in the process of alternately preparing the silicon transition film layer and the silver-doped DLC film layer along with the preparation of each silicon transition film layer, wherein the power of a silver target in the preparation of the silver-doped DLC film layer of the next layer is reduced by 0.1-0.3 kW compared with that of the silver-doped DLC film layer of the last layer until the periodic gradient coating of the silicon transition film layer/the silver-doped DLC film layer is completed;
The blank is cleaned by adopting purified water and ethanol sequentially, the cleaning temperature is 20-32 ℃, the cleaning time is 10-30 min, and the blank is dried for standby after cleaning.
The process for removing impurity gas in the furnace comprises the steps of introducing Ar gas into a vacuum chamber, wherein the gas flow is 50-120 sccm, the vacuum degree is 4.0X10- 1～7.0×10-1 Pa, the negative bias voltage of a workpiece is 400-800V, and the degassing time is 10-30 min.
The process for cleaning the workpiece by the ion source comprises the steps of enabling Ar gas flow to be 60-100 sccm, vacuum degree to be 3.0X10- 1～6.0×10-1 Pa, ion source power to be 0.9-1.2 kW, workpiece negative bias voltage to be 400-800V and cleaning time to be 15-40 min.
The preparation process of the silicon transition film layer comprises the steps of enabling Ar gas flow to be 60-100 sccm, enabling silicon target power to be 0.5-3 kW, enabling silicon vacuum degree to be 1.0X10- 1～4.0×10-1 Pa, enabling ion source power to be 0.5-2 kW, enabling negative bias voltage of a workpiece to be 50-400V, and enabling deposition time to be 10-80 min.
The silver-doped DLC film preparation process comprises the steps of 20-100 sccm of Ar gas flow, 10-100 sccm of gas carbon source flow, 1.0X10- 1～4.0×10-1 Pa of vacuum degree, 0.5-3 kW of ion source power, 0.1-1 kW of silver-palladium power, not less than 99.9wt% of Ag target purity, 50-600V of workpiece negative bias voltage and 30-540 min of deposition time;
4) Finally, the lung nodule locating needle head product is prepared.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
The invention uses carbon-based material as matrix, and combines the vapor deposition, the unbalanced intermediate frequency magnetron sputtering method and the direct current arc PECVD method to plate the PyC coating and the silver-doped DLC composite coating on the surface of the carbon-based material to obtain the lung nodule positioning needle head, the method has simple operation, easy accurate control and contribution to industrialized production, particularly, by adopting a method combining unbalanced intermediate frequency magnetron sputtering and direct current arc PECVD, the gradient silver-doped DLC coating can be plated on the surface of the carbon-based material, the content of the doped silver element can be better controlled under the condition of not changing the technological parameters of the DLC coating, and the content of the silver element can be stably controlled within the range of 1-20% which is most effective in improving the performance of the film.
The silver-doped DLC composite coating in the lung nodule positioning needle is formed by alternately superposing N silicon transition film layers and N silver-doped DLC film layers, and the silver-doped DLC composite coating is more tightly combined with atoms in the silicon transition layer by doping silver elements in the DLC coating, so that the internal stress of the whole silver-doped DLC coating is reduced, the binding force between the whole composite coating and a carbon-based material is greatly improved, and the composite coating with better performances such as abrasion resistance, hardness, adhesive force and the like can be obtained by controlling the preparation process parameters of the film layers, the superposition layer number and the like, and the combination critical load of the silver-doped DLC composite coating and the carbon-based material can reach more than 10N.
The silver-doped DLC composite coating is prepared on the surface of the lung nodule positioning needle, 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, the adverse reaction of the matrix on the human body caused by friction powder removal of the carbon-based material after the carbon-based material is implanted into the human body is improved, and compared with the carbon-based material without the silver-doped DLC composite coating, the powder removal phenomenon after friction is obviously improved, and the friction coefficient is obviously reduced.
The lung nodule positioning needle head provided by the invention takes the carbon-based material as a matrix, the carbon material has good biocompatibility and long detention time, and the carbon-based coating has anticoagulation, so that bleeding caused by metal foreign bodies can be reduced.
The front part of the nose cone of the lung nodule positioning needle is provided with a flat head, so that lung tissues are not easy to damage, the tumor is prevented from being pierced, and the risk of metastasis of the exfoliated tumor cells is increased.
The surface layer of the lung nodule positioning needle is a coating containing Ag, has remarkable antibacterial property, effectively reduces the infection probability, and can improve the antibacterial property of the lung nodule positioning needle coating on the surface of the carbon-based material by 15-40%.
Drawings
Fig. 1 is a physical view of a carbon-based material inserted lung nodule positioning needle.
Fig. 2 is a physical view of a carbon-based material embedded lung nodule positioning needle.
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.
Performance test the mechanical properties of the coatings were tested by nanoindentation and nanoscratch in the examples below, the coefficient of friction of the film was measured using a ball-and-disc friction tester, and the improvement of the biocompatibility of the coating to the substrate was examined using endothelial cell proliferation experiments and e.
The following specific examples and comparative examples illustrate the preparation of the carbon-based material as follows:
1) The carbon fiber preform is formed by needling a carbon fiber bundle with a width of 25mm and a carbon fiber net tire lamination of 20g/m 2, and the density of the net layer is 22 layers/cm.
2) And (3) placing the carbon fiber preform into a deposition furnace, and introducing propylene and nitrogen (the flow ratio of the propylene to the nitrogen is 1:2) at the temperature of 950 ℃ to deposit for 150 hours to prepare a carbon-based material blank with the density of 1.5g/cm 3.
Example 1
1) The carbon-based material blank is processed into a positioning needle head blank through the working procedures of mechanical cutting, polishing and the like, as shown in figure 1, wherein the length of the needle head is 12mm, the diameter of a needle rod is 1.8mm, a lead wire hole is positioned on the needle rod, the diameter of the lead wire hole is 0.5mm, the length of a pin rod is 5mm, the diameter of the pin rod is 1.3mm, and the angle of a cone tip is 40 degrees.
2) Adopting methane and nitrogen as gas sources (the flow ratio of the methane to the nitrogen is 1:5), and depositing for 20 hours at the temperature of 1500 ℃, wherein a PyC coating is prepared on the surface of the blank, and the thickness of the pyrolytic carbon coating is 30 mu m;
3) Further preparing a silver-doped DLC composite coating on the step 2), wherein the silver-doped DLC composite coating is a silicon transition layer-Ag-doped DLC gradient film layer, and the silver-doped DLC composite coating comprises the following specific steps:
A. And cleaning the blank, namely sequentially performing ultrasonic cleaning on the blank by using purified water and ethanol, wherein the cleaning temperature is 28 ℃, the cleaning time is 20 minutes, and drying is performed for standby after the cleaning is finished.
B. placing the cleaned blank substrate into a film plating device combining unbalanced intermediate frequency magnetron sputtering and direct current arc PECVD, and vacuumizing to the working vacuum degree.
C. And (3) removing impurity gas in the furnace, namely introducing Ar gas into the vacuum chamber, wherein the gas flow is 100sccm, the vacuum degree is 5.0X10- 1 Pa, the negative bias voltage of the workpiece is 800V, and the degassing time is 20min.
D. the ion source cleans the workpiece, wherein Ar gas flow is 80sccm, vacuum degree is 4.0X10- 1 Pa, ion source power is 1kW, workpiece negative bias voltage is 800V, and cleaning time is 30min.
E. And preparing a silicon transition film layer, wherein Ar gas flow is 60sccm, vacuum degree is 2.0X10- 1 Pa, silicon target power is 1kW, ion source power is 0.9kW, workpiece negative bias voltage is 150V, and film coating time is 10min.
F. The silver-doped DLC film is prepared by the steps of Ar gas flow of 60sccm, acetylene gas flow of 80sccm, vacuum degree of 2.0X10- 1 Pa, ion source power of 1.2kW, silver target power of 0.4kW, workpiece negative bias voltage of 400V and film plating time of 60min.
G. And E, alternately preparing a silicon transition film layer and a silver-doped DLC film layer according to the processes of the steps E and F, wherein along with the preparation of each silicon transition film layer, the silver target power in the preparation of the silver-doped DLC film layer of the next layer is reduced by 0.1kW compared with that in the preparation of the silver-doped DLC film layer of the last layer until the periodic gradient coating of the silicon transition film layer/the silver-doped DLC film layer is completed, the total number of layers of the gradient coating of the silicon transition film layer/the silver-doped DLC film layer is 6, the silver content of the whole film layer is 1.2%, the thickness of each silicon transition film layer is 0.15 mu m, and the thickness of each silver-doped DLC film layer is at least 0.3 mu m.
The silver-doped DLC coating prepared by the embodiment has high binding force with the carbon-based material lung nodule positioning needle head, the binding force is 12N, the abrasion rate of the surface of the carbon-based material lung nodule positioning needle head is reduced, the friction coefficient is 0.06, and the abrasion rate is 5.7X10 -7mm3/N.m. The antibacterial property of the carbon-based material lung nodule positioning needle is effectively improved, compared with an uncoated carbon-based material lung nodule positioning needle, the escherichia coli survival rate of the carbon-based material lung nodule positioning needle with the silver-doped DLC coating prepared in the embodiment is reduced from 100% to 81% in an escherichia coli survival experiment, and the endothelial cell proliferation rate is improved from 70% to 87% in an endothelial cell proliferation experiment.
Example 2
1) The carbon-based material blank is processed into a positioning needle head blank through the working procedures of mechanical cutting, polishing and the like, as shown in figure 2, wherein the length of the needle head is 10mm, the diameter of a needle rod is 1.5mm, the length of a pin rod is 3mm, the diameter of the pin rod is 1.1mm, a lead hole is positioned on the pin rod, the diameter of the lead hole is 0.4mm, and the cone tip angle is 36 degrees.
2) Adopting methane and nitrogen as gas sources (the flow ratio of the methane to the nitrogen is 1:5), and depositing for 20 hours at the temperature of 1500 ℃, wherein a PyC coating is prepared on the surface of the blank, and the thickness of the pyrolytic carbon coating is 30 mu m;
3) Further preparing a silver-doped DLC composite coating on the step 2), wherein the silver-doped DLC composite coating is a silicon transition layer-Ag-doped DLC gradient film layer, and the silver-doped DLC composite coating comprises the following specific steps:
The silver-doped DLC composite coating in the step 3) is plated as follows:
A. And cleaning the blank, namely sequentially performing ultrasonic cleaning on the blank by using purified water and ethanol, wherein the cleaning temperature is 28 ℃, the cleaning time is 20 minutes, and drying is performed for standby after the cleaning is finished.
B. Placing the cleaned blank in a film plating device combining unbalanced intermediate frequency magnetron sputtering and direct current arc PECVD, and vacuumizing to the working vacuum degree.
C. And (3) removing impurity gas in the furnace, namely introducing Ar gas into the vacuum chamber, wherein the gas flow is 100sccm, the vacuum degree is 5.0X10- 1 Pa, the negative bias voltage of the workpiece is 800V, and the degassing time is 20min.
D. the ion source cleans the workpiece, wherein Ar gas flow is 80sccm, vacuum degree is 4.0X10- 1 Pa, ion source power is 1kW, workpiece negative bias voltage is 800V, and cleaning time is 30min.
E. And preparing a silicon transition film layer, wherein Ar gas flow is 60sccm, vacuum degree is 2.0X10- 1 Pa, silicon target power is 1kW, ion source power is 0.9kW, workpiece negative bias voltage is 150V, and film coating time is 10min.
F. The silver-doped DLC film is prepared by the steps of Ar gas flow of 60sccm, acetylene gas flow of 100sccm, vacuum degree of 2.0X10- 1 Pa, ion source power of 1.2kW, silver target power of 0.8kW, negative bias voltage of 600V of a workpiece and film plating time of 60min.
G. And E, alternately preparing a silicon transition film layer and a silver-doped DLC film layer according to the processes of the steps E and F, wherein along with the preparation of each silicon transition film layer, the silver target power in the preparation of the silver-doped DLC film layer of the next layer is reduced by 0.15kW compared with that in the preparation of the silver-doped DLC film layer of the last layer until the periodic gradient coating of the silicon transition film layer/the silver-doped DLC film layer is completed, the total number of layers of the gradient coating of the silicon transition film layer/the silver-doped DLC film layer is 4, the silver content of the whole film layer is 3.8%, the thickness of each silicon transition layer is 0.15 mu m, and the thickness of each silver-doped DLC film layer is at least 0.45 mu m.
The silver-doped DLC coating prepared by the embodiment has high binding force with the carbon-based material lung nodule positioning needle head, the binding force is 15N, the abrasion rate of the surface of the carbon-based material lung nodule positioning needle head is reduced, the friction coefficient is 0.03, and the abrasion rate is 3.4X10 -7mm3/N.m. The antibacterial property of the carbon-based material lung nodule positioning needle is effectively improved, compared with an uncoated carbon-based material lung nodule positioning needle, the escherichia coli survival rate of the carbon-based material lung nodule positioning needle with the silver-doped DLC coating prepared in the embodiment is reduced from 100% to 82% in an escherichia coli survival experiment, and the endothelial cell proliferation rate is improved from 70% to 90% in an endothelial cell proliferation experiment.
Example 3
The procedure was exactly the same as in example 2, except that the total number of layers of the gradient coating of the silicon transition film layer/silver-doped DLC film layer was 12, the silver content of the overall film layer was 2.1%, the thickness of each silicon transition layer was 0.15. Mu.m, and the thickness of each silver-doped DLC film layer was at least 0.39. Mu.m.
The silver-doped DLC coating prepared by the embodiment has high binding force with the carbon-based material lung nodule positioning needle head, the binding force is 11N, the abrasion rate of the surface of the carbon-based material lung nodule positioning needle head is reduced, the friction coefficient is 0.04, and the abrasion rate is 3.9X10 -7mm3/N.m. The antibacterial property of the carbon-based material lung nodule positioning needle is effectively improved, compared with an uncoated carbon-based material lung nodule positioning needle, the escherichia coli survival rate of the carbon-based material lung nodule positioning needle with the silver-doped DLC coating prepared in the embodiment is reduced from 100% to 80% in an escherichia coli survival experiment, and the endothelial cell proliferation rate is improved from 70% to 88% in an endothelial cell proliferation experiment.
Example 4
The procedure was exactly the same as in example 2, except that the silver target power was the same in the preparation of each silver-doped DLC film, the silver target power was 0.8kW, the overall film silver content was 4.9%, the thickness of each silicon transition layer was 0.15 μm, and the thickness of each silver-doped DLC film was 0.51 μm.
The silver-doped DLC coating prepared by the embodiment has high binding force with the carbon-based material lung nodule positioning needle head, the binding force is 11N, the abrasion rate of the surface of the carbon-based material lung nodule positioning needle head is reduced, the friction coefficient is 0.05, and the abrasion rate is 4.2X10 -7mm3/N.m. The antibacterial property of the carbon-based material lung nodule positioning needle is effectively improved, compared with an uncoated carbon-based material lung nodule positioning needle, the survival rate of the escherichia coli in an escherichia coli survival experiment of the carbon-based material lung nodule positioning needle with the silver-doped DLC coating prepared in the embodiment is reduced by 79% from 100%, and the proliferation rate of endothelial cells in an endothelial cell proliferation experiment is improved from 70% to 85%.
Comparative example 1
The only difference between this comparative example and example 1 is that no silicon transition film layer was prepared and the silver-doped DLC coating of the same total thickness was prepared directly on the surface of the carbon-based pulmonary nodule positioning needle.
The silver-doped DLC coating without the silicon transition friction layer prepared in the comparative example is directly peeled off from the carbon-based material lung nodule positioning needle head, and has poor binding force.
Comparative example 2
The only difference between this comparative example and example 1 is that no silver element was incorporated in the DLC film layer.
The silicon transition film layer/non-silver-doped DLC film layer composite coating prepared in the comparative example has lower binding force with the carbon-based material lung nodule positioning needle. The value was 4N, the friction coefficient was 0.10, and the wear rate was 9.8X10 -7mm3/N.m. The survival rate of the escherichia coli in the escherichia coli survival experiment of the lung nodule positioning needle made of the carbon-based material with the coating in the example is reduced from 100% to 98%, and the proliferation rate of the endothelial cells in the endothelial cell proliferation experiment is increased from 70% to 74%.
Table 1 comparison of performance test results
Claims (6)
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| CN111908935A (en) * | 2020-01-19 | 2020-11-10 | 湖南碳康生物科技有限公司 | Carbon-based composite material bone screw and preparation method thereof |
| CN113893042A (en) * | 2021-11-15 | 2022-01-07 | 上海市同济医院 | Pulmonary nodule puncture location cover package |
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| WO2003070288A2 (en) * | 2001-10-12 | 2003-08-28 | Inframat Corporation | Coated implants and methods of coating implants |
| EP2259805B1 (en) * | 2008-02-29 | 2016-08-17 | Smith & Nephew, Inc. | Gradient coating for biomedical applications |
| EP2747158A1 (en) * | 2012-12-24 | 2014-06-25 | Université Pierre et Marie Curie (Paris 6) | Biocompatible carbon based electrode, its use and preparation process |
| CN104046948B (en) * | 2014-05-26 | 2016-02-24 | 浙江大学 | Surface modification radio frequency ablation needle and application thereof |
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| CN104073762A (en) * | 2014-06-23 | 2014-10-01 | 中国科学院宁波材料技术与工程研究所 | Method for improving surface smoothness of radiofrequency ablation treatment needle |
| CN111908935A (en) * | 2020-01-19 | 2020-11-10 | 湖南碳康生物科技有限公司 | Carbon-based composite material bone screw and preparation method thereof |
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