CN115369367B - Conductive hydrophilic MAX phase coating on surface of medical cutter and preparation method and application thereof - Google Patents
Conductive hydrophilic MAX phase coating on surface of medical cutter and preparation method and application thereof Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 155
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
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Classifications
-
- 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
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
-
- 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
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
-
- 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
- C23C14/0635—Carbides
-
- 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
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The application discloses a conductive hydrophilic MAX phase coating on the surface of a medical cutter, a preparation method and application thereof. The preparation method comprises the following steps: adopting a direct current magnetron sputtering composite cathode arc coating technology, taking an M target as an arc target, taking an Al target as a direct current pulse magnetron sputtering target, taking methane and inert gas as working gases, and depositing to form an M-Al-C amorphous coating on the surface of a substrate; wherein M is selected from any one of Ti, V, cr, zr; and performing high-temperature steam heat treatment on the matrix deposited with the M-Al-C amorphous coating, so as to form a conductive hydrophilic MAX phase coating on the surface of the medical cutter. The preparation process of the conductive hydrophilic MAX phase coating provided by the application is simple and controllable, can be quantitatively produced, and meanwhile, the prepared conductive hydrophilic MAX phase coating has hydrophilic characteristic, so that adhesion between a cutter and tissues in the operation process is effectively prevented, and the conductive hydrophilic MAX phase coating has a good application prospect in the field of medical cutters.
Description
Technical Field
The application belongs to the technical field of metal surface protection, and particularly relates to a conductive hydrophilic MAX phase coating on the surface of a medical cutter, and a preparation method and application thereof.
Background
The medical device industry is one of the fastest growing industries worldwide and is a high point of competition among the large countries of science and technology in the world. The surgical knife is an indispensable tool in surgical operation, and modern high-tech products integrating the functions of cutting, hemostasis, illumination, electric waves and the like, such as a high-frequency electric knife, an argon knife, an ultrasonic knife, a LEEP knife, a sapphire knife, a surgical scissors and the like, have been developed at present. With the development of bionics, researches on surface modification of surgical knives have attracted interest to researchers, and development of a hydrophilic and lubricious coating is important for reducing adhesion between a knife and tissues, reducing damage to the body, preventing thrombosis and vasospasm, improving safety of surgery, and relieving pain of patients. The most prominent use of hydrophilic coatings in the medical device field is to improve or create lubricity, a characteristic of this wet slip that allows a catheter, guidewire or medical accessory to easily pass through a patient's narrow and tortuous anatomical path. More advanced, hydrophilic coatings may also be used in the field of drug release and biological interactions to release antibodies or active pharmaceutical ingredients to interact with body tissues in a specific manner.
The high-frequency electric knife is a surgical instrument for tissue cutting instead of a mechanical surgical knife, and can accurately and efficiently cut tissues and stop bleeding and sterilize wounds by contacting the tissue with the body through high-frequency high-voltage electricity generated by the tip of the electrode, so that the surgical time can be effectively shortened, the surgical complications can be reduced, and the surgical efficiency can be greatly improved. However, conventional stainless steel electrodes can adhere to liquefied fat and denatured proteins at high temperatures, which can affect the electrical conductivity of the electrotome and the adhering tissue can lead to incision bleeding, increasing the risk of surgery and patient pain.
Aiming at the surface tissue adhesion problem, PTFE (polytetrafluoroethylene) coating has been developed to modify the surface of an electrode cutter. The PTFE coating can obviously reduce the adhesion between the cutter and the tissue and effectively avoid the pollution of the cutter, but the traditional PTFE coating has poor conductive performance, and arc discharge is formed on the surface of the electrode under high-frequency current, so that the instantaneous high temperature of thousands DEG C can be generated, which is far higher than the use temperature of the coating, so that the coating is vaporized and decomposed, harmful substances such as hydrofluoric acid and the like are released, and the health of both doctors and patients is influenced.
The MAX phase is a group of hexagonal structures with thermodynamic stability and close-packed (P6 3 Lamellate high performance material of/mmc), wherein M is a precursor comprising a lanthanideThe transition group metal element, A is a group IIIA or IVA element, the most common are Al, si and Sn elements, and X is C or N element. The unique structure ensures that the ceramic has the advantages of excellent conductivity, machinability and the like of metal and simultaneously has the advantages of high ceramic melting point and good corrosion resistance. The excellent thermal stability and conductivity make the coating possess wide application prospect in the fields of electric coagulation knives, high-frequency surgical knives and the like, but the wettability of the MAX phase coating is poor at present, so that development of a hydrophilic MAX phase coating is needed to prevent adhesion between a knife and tissues in the surgical process and reduce the pain of patients.
Disclosure of Invention
The application mainly aims to provide a conductive hydrophilic MAX phase coating on the surface of a medical cutter, and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose of the application, the technical scheme adopted by the application comprises the following steps:
the embodiment of the application provides a preparation method of a conductive hydrophilic MAX phase coating on the surface of a medical cutter, which comprises the following steps:
providing a medical cutter as a substrate;
adopting a direct current magnetron sputtering composite cathode arc coating technology, taking an M target as an arc target, taking an Al target as a direct current pulse magnetron sputtering target, taking methane and inert gas as working gases, and depositing and forming an M-Al-C amorphous coating on the surface of the substrate; wherein M is selected from any one of Ti, V, cr, zr;
and performing high-temperature steam heat treatment on the matrix deposited with the M-Al-C amorphous coating, so as to form a conductive hydrophilic MAX phase coating on the surface of the medical cutter.
The embodiment of the application also provides the conductive hydrophilic MAX phase coating on the surface of the medical cutter prepared by the preparation method, and the conductive hydrophilic MAX phase coating has a layered structure
The embodiment of the application also provides the application of the conductive hydrophilic MAX phase coating on the surface of the medical cutter in the modified electrocoagulation cutter or high-frequency surgical knife.
The embodiment of the application also provides a surface modification method of the medical cutter, which comprises the following steps: the conductive hydrophilic MAX phase coating is prepared on the surface of the medical cutter by adopting the method.
Compared with the prior art, the application has the beneficial effects that:
(1) According to the application, through carrying out high-temperature steam heat treatment on the amorphous M-Al-C amorphous coating, a hydrophilic MAX phase coating (with a contact angle smaller than 60 ℃) is obtained, and the prepared coating can effectively prevent adhesion between a cutter and tissues in the operation process, does not generate harmful substances, reduces damage and adhesion of medical instruments to tissues and organs, greatly improves operation efficiency and safety, and can also reduce injury to human bodies and pain of patients; meanwhile, the conductive hydrophilic MAX phase coating prepared by the application has excellent mechanical property and corrosion resistance;
(2) The application utilizes the DC magnetron sputtering composite cathode arc coating device and combines the subsequent high-temperature steam heat treatment to obtain the hydrophilic MAX phase coating, the deposited coating is compact and uniform, the binding force is strong, the preparation process is simple and controllable, the cost performance is high, the industrial production and the application can be carried out, and the adhesion problem of medical instruments and tissue blood in body fluid environment can be solved.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a schematic illustration of a process for preparing a conductive hydrophilic MAX phase coating for a medical tool surface in accordance with an exemplary embodiment of the present application;
FIG. 2a is a high temperature steam heat treated Ti in example 1 of the present application 2 A surface topography of the AlC coating;
FIG. 2b is a diagram of Ti after vacuum annealing treatment in comparative example 1 of the present application 2 A surface topography of the AlC coating;
FIG. 3a is a high temperature steam heat treated Ti in example 1 of the present application 2 Contact angle of AlC coating with waterA schematic diagram;
FIG. 3b is a diagram of Ti after vacuum annealing treatment in comparative example 1 of the present application 2 Schematic of the contact angle of AlC coating with water;
FIG. 4 is a V after the high temperature steam heat treatment in example 2 of the present application 2 Schematic cross-sectional morphology and thickness of AlC coating;
FIG. 5 is an XRD contrast pattern of MAX phase coatings prepared in example 1 and comparative example 1 of the present application;
fig. 6 is a graph showing the contact angle of the coatings prepared in comparative example 1, example 2 and example 3 according to the present application, and a graph showing the morphology of the medical tool after performing the surgical environment test.
Detailed Description
In view of the shortcomings of the prior art, the inventor of the present application has long studied and put forward a great deal of practice, and the technical solution of the present application will be clearly and completely described below, and it is obvious that the described embodiments are some, but not all, embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Specifically, as one aspect of the technical scheme of the application, the preparation method of the conductive hydrophilic MAX phase coating on the surface of the medical cutter comprises the following steps:
providing a medical cutter as a substrate;
adopting a direct current magnetron sputtering composite cathode arc coating technology, taking an M target as an arc target, taking an Al target as a direct current pulse magnetron sputtering target, taking methane and inert gas as working gases, and depositing and forming an M-Al-C amorphous coating on the surface of the substrate; wherein M is selected from any one of Ti, V, cr, zr;
and performing high-temperature steam heat treatment on the matrix deposited with the M-Al-C amorphous coating, so as to form a conductive hydrophilic MAX phase coating on the surface of the medical cutter.
In some preferred embodiments, a schematic flow chart of the preparation of the conductive hydrophilic MAX phase coating on the surface of the medical tool is shown in fig. 1.
In some preferred embodiments, M is selected from any one of V, zr, and is not limited thereto.
In some preferred embodiments, the preparation method specifically comprises: at a vacuum level of 1.0X10 -2 And (3) heating the reaction cavity to 400-900 ℃ at a heating rate of 5-10 ℃/min under Pa, then introducing steam and keeping the pressure of the reaction cavity at 1 atmosphere, and performing high-temperature steam heat treatment on the matrix deposited with the M-Al-C amorphous coating for 0.5-20 h to obtain the conductive hydrophilic MAX phase coating.
Further, the high-temperature steam heat treatment atmosphere is a vacuum steam atmosphere.
Further, the vacuum degree was 1.0X10 -2 ～1.0×10 -3 Pa。
Further, after the pure water vapor was introduced, the pressure in the furnace was maintained at 1 atmosphere.
In some preferred embodiments, when the M-Al-C amorphous coating is deposited, the substrate bias voltage is-50 to-200V, the methane gas flow rate is 15-30 sccm, the inert gas flow rate is 150-200 sccm, the deposition temperature is 30-200 ℃, and the deposition time is 0.5-3 h.
Further, the gas pressure of the mixed gas of methane and inert gas is 1-3 Pa.
In some preferred embodiments, the average power of sputtering of the Al target is 2000-3500W when depositing the M-Al-C amorphous coating.
In some preferred embodiments, the current of the M target is 30 to 70A when the M-Al-C amorphous coating is deposited.
In some preferred embodiments, the thickness of the M-Al-C amorphous coating is 2 to 10 μm.
In some preferred embodiments, the substrate is spaced from the Al target by 10 to 15cm and the substrate is spaced from the M target by 15 to 20cm when the M-Al-C amorphous coating is deposited.
In some preferred embodiments, the medical cutter includes an electrocoagulation cutter or a high frequency scalpel, and is not limited thereto.
In some preferred embodiments, the material of the medical cutter includes any one of titanium, titanium alloy, and stainless steel, and is not limited thereto.
In some preferred embodiments, the method of making further comprises: pretreating a substrate before coating;
the pretreatment comprises the steps of bombarding a matrix with argon ions for etching treatment;
the etching treatment adopts the process conditions that: the cavity temperature is 100-200 ℃, the cavity pressure is 0.3-0.6 Pa, the argon flow is 20-50 sccm, the substrate bias voltage is-50 to-200V, the anode ion beam current is 0.15-0.4A, and the etching time is 10-30 min;
further, the target is subjected to pretreatment before coating; the pretreatment comprises the step of carrying out pre-sputtering cleaning treatment on the target;
the process for cleaning the target material comprises the following steps: the cavity temperature is 100-200 ℃, the cavity pressure is 1-2.5 Pa, the argon flow is 50-200 sccm, the direct current pulse magnetron sputtering power is 1000-2000W, the arc cathode current is 40-60A, and the cleaning time is 5-20 min.
In some more specific embodiments, the method for preparing the conductive hydrophilic MAX phase coating on the surface of the medical tool comprises:
(1) Sequentially cleaning and drying a substrate in alcohol and acetone, and then placing the substrate on a rotatable base frame;
(2) Before coating, the impurities and pollutants in the cavity are volatilized through the heating cavity;
(3) Argon is introduced into the vacuum cavity through an anode ion source before coating, and ionized argon ions are utilized to etch the substrate;
(4) Depositing an M-Al-C amorphous coating on the surface of a substrate by using a direct current magnetron sputtering composite cathode arc coating device and using an M element single-substance target as an arc target material and an Al element single-substance target as a pulse magnetron sputtering target material and using a methane and argon mixed gas as a working gas;
(5) And (3) placing the matrix deposited with the M-Al-C amorphous coating in a tubular furnace for high-temperature steam heat treatment to obtain the MAX phase coating.
In another aspect of the embodiment of the application, a conductive hydrophilic MAX-phase coating on the surface of the medical tool manufactured by the manufacturing method is provided, and the conductive hydrophilic MAX-phase coating has a layered structure.
Further, the conductive hydrophilic MAX phase coating is of a compact lamellar structure without columnar growth defects.
Further, the large particles on the surface of the conductive hydrophilic MAX phase coating are oxidized into fine oxides.
In some preferred embodiments, the conductive hydrophilic MAX phase coating surface has a contact angle with water of less than 60 °.
In some preferred embodiments, the conductivity of the conductive hydrophilic MAX phase coating is 0.1 to 0.6 μΩ.m.
In some preferred embodiments, the thickness of the conductive hydrophilic MAX phase coating is 2-10 μm.
In some preferred embodiments, the conductive hydrophilic MAX phase coating comprises Ti 2 AlC、Ti 3 AlC 2 、Ti 4 AlC 3 、V 2 AlC、Cr 2 AlC、Zr 2 AlC、Zr 3 AlC 2 Any one of these, and is not limited thereto.
Further, the conductive hydrophilic MAX phase coating comprises V 2 AlC、Zr 2 AlC、Zr 3 AlC 2 Any one of these, and is not limited thereto.
In some preferred embodiments, the phase structure of the conductive hydrophilic MAX phase coating is predominantly pure MAX phase, in a close-packed hexagonal structure.
Further, the content of the MAX phase in the conductive hydrophilic MAX phase coating is more than 90 weight percent.
Further, the atomic percent of M, al to C in the conductive hydrophilic MAX phase coating is 2:1:1 or 3:1:2 or 4:1:3.
Forming a compact layered structure without columnar growth defects on the surface of a metal matrix
Another aspect of the embodiments of the present application also provides the use of the conductive hydrophilic MAX phase coating on the surface of the medical tool described above in modifying an electrocoagulation blade or a high frequency surgical blade.
Another aspect of an embodiment of the present application also provides a medical tool provided with the aforementioned conductive hydrophilic MAX phase coating.
Another aspect of the embodiments of the present application also provides a surface modification method of a medical cutter, including: the conductive hydrophilic MAX phase coating is prepared on the surface of the medical cutter by adopting the method.
The technical scheme of the present application is further described in detail below with reference to several preferred embodiments and the accompanying drawings, and the embodiments are implemented on the premise of the technical scheme of the present application, and detailed implementation manners and specific operation processes are given, but the protection scope of the present application is not limited to the following embodiments.
The experimental materials used in the examples described below, unless otherwise specified, were all commercially available from conventional biochemicals.
The analytical method used in the present application is as follows:
determining the phase composition and phase structure of the coating by means of an X-ray powder diffractometer;
observing the surface morphology, the cross-sectional morphology and the thickness of the coating by means of a field emission scanning electron microscope;
the hydrophilic and hydrophobic properties of the coatings were analyzed by means of an OCA20 contact angle meter.
And (3) performing operation environment test on the medical cutter deposited with the conductive hydrophilic MAX phase coating, and observing the adhesion condition of the surface of the cutter and the tissue.
Example 1
Placing the polished, cleaned and dried 304 stainless steel electrode cutter on a rotatable base frame, and vacuumizing the cavity to 2×10 -3 Pa, heating the cavity to 150 ℃; to a vacuum degree of less than 3×10 -5 Pa, introducing 30sccm argon, setting the current of the ion beam to be 0.2A and the bias voltage to be-150V, and etching the substrate for 30min; then changing the argon flow to 200sccm, the magnetron sputtering power to 2000W, the electric arc target current to 70A, and cleaning the target for 20min; then argon is introduced with the flow of 200sccm, the flow of methane is 25sccm, the power of an Al target is adjusted to 3300W, the current of a Ti target is 60A, the bias voltage is-200V, and Ti-Al is depositedC coating for 60min, the thickness of the coating being about 4. Mu.m. Then the medical cutter with deposited Ti-Al-C coating is placed in a tube furnace, the vacuum degree is 2 multiplied by 10 -3 Pa, heating to 700 ℃ at a heating rate of 10 ℃/min, introducing pure water vapor, maintaining the pressure in the furnace at 1 atmosphere, and performing high-temperature vapor heat treatment for 1.5h to obtain hydrophilic Ti 2 AlC MAX phase coating.
FIG. 2a shows Ti after the high temperature steam heat treatment of the present example 2 The surface morphology of AlC coating, the corrugated morphology of the surface being typical of MAX phase, the Ti-rich macroparticles due to arcing can also be clearly observed, as compared with the vacuum annealing heat treated Ti of FIG. 2b 2 Compared with AlC phase coating, after high-temperature steam heat treatment, large particles on the surface of the coating are split outwards from the middle and are decomposed into smaller particles.
FIG. 3a shows Ti after the high temperature steam heat treatment of the present example 2 The contact angle picture of AlC coating and water, the contact angle is 52.95 degrees, is a hydrophilic coating.
Hydrophilic Ti in this example 2 The AlC MAX phase coating has the hardness of 15GPa, the elastic modulus of 260GPa and the weight gain of 0.19+/-0.4 mg/cm after being corroded for 75 hours under water environment 2 The resistivity was 0.2. Mu. Ω. M.
Example 2
In the embodiment, the substrate is a 304 stainless steel medical cutter, and the surface of the substrate is hydrophilic V 2 The preparation method of the AlC MAX phase coating comprises the following steps:
placing the polished, cleaned and dried 304 stainless steel electrode cutter on a rotatable base frame, and vacuumizing the cavity to 2×10 -3 Pa, heating the cavity to 150 ℃; to a vacuum degree of less than 3×10 -5 Pa, introducing 30sccm argon, setting the current of the ion beam to be 0.2A and the bias voltage to be-150V, and etching the substrate for 30min; then changing the argon flow to 200sccm, the magnetron sputtering power to 2000W, the electric arc target current to 70A, and cleaning the target for 20min; then argon is introduced with the flow of 200sccm, the flow of methane is 25sccm, the power of an Al target is regulated to 3100W, the current of a V target is regulated to 60A, the bias voltage is regulated to-200V, and a V-Al-C coating is deposited for 180min, wherein the thickness of the coating is about 7.73 mu m. Then the medical knife with the V-Al-C coating deposited is placed in a tube furnace, and the vacuum degree is 2 multiplied by 10 -3 Pa, at 1Heating to 400 ℃ at a heating rate of 0 ℃/min, introducing pure water vapor, maintaining the pressure in the furnace at 1 atmosphere, and performing high-temperature vapor heat treatment for 20 hours to obtain a coating with a contact angle of 55.41 DEG with water.
FIG. 4 shows the cross-sectional morphology and thickness of the coating after the high temperature steam treatment, the coating is compact and defect-free, the film-based bonding force is strong, and the thickness of the coating is about 7.73 μm.
Example 3
In the embodiment, the matrix is a 304 stainless steel medical cutter, and the surface of the matrix is hydrophilic Cr 2 The preparation method of the AlC MAX phase coating comprises the following steps:
placing the polished, cleaned and dried 304 stainless steel electrode cutter on a rotatable base frame, and vacuumizing the cavity to 2×10 -3 Pa, heating the cavity to 150 ℃; to a vacuum degree of less than 3×10 -5 Pa, introducing 30sccm argon, setting the current of the ion beam to be 0.2A and the bias voltage to be-150V, and etching the substrate for 30min; then changing the argon flow to 200sccm, the magnetron sputtering power to 2000W, the electric arc target current to 70A, and cleaning the target for 20min; then argon is introduced with the flow of 200sccm, the flow of methane is 15sccm, the power of an Al target is regulated to 3100W, the current of a Cr target is regulated to 60A, the bias voltage is regulated to-200V, and a Cr-Al-C coating is deposited for 180min, wherein the thickness of the coating is about 7.52 mu m. Then placing the medical cutter with the deposited Cr-Al-C coating in a tube furnace, wherein the vacuum degree is 2 multiplied by 10 - 3 Pa, heating to 900 ℃ at a heating rate of 10 ℃/min, introducing pure water vapor, maintaining the pressure in the furnace at 1 atmosphere, and carrying out high-temperature vapor heat treatment for 0.5h to obtain a coating with a contact angle of 58.40 degrees with water.
Example 4
This embodiment differs from embodiment 1 only in that: the medical tool with the amorphous Ti-Al-C coating deposited in this example had a high temperature steam heat treatment temperature of 900℃and a holding time of 0.5h, and the contact angle of the coating with water was 57.45 ℃.
The surface morphology of the coatings prepared in examples 2 to 4 was similar to that of example 1, and the large surface particles were decomposed to different extents.
The coatings prepared in examples 2 to 4 all had contact angles with water of less than 60 °, and were hydrophilic coatings similar to example 1.
Comparative example 1
In the embodiment, the substrate is a 304 stainless steel medical cutter, and the preparation method of the substrate surface coating is as follows:
placing the polished, cleaned and dried 304 stainless steel electrode cutter on a rotatable base frame, and vacuumizing the cavity to 2×10 -3 Pa, heating the cavity to 150 ℃; to a vacuum degree of less than 3×10 -5 Pa, introducing 30sccm argon, setting the current of the ion beam to be 0.2A and the bias voltage to be-150V, and etching the substrate for 30min; then changing the argon flow to 200sccm, the magnetron sputtering power to 2000W, the electric arc target current to 70A, and cleaning the target for 20min; then argon is introduced with the flow of 200sccm, the flow of methane is 25sccm, the power of an Al target is adjusted to 3300W, the current of a Ti target is adjusted to 60A, the bias voltage is adjusted to-200V, and a Ti-Al-C coating is deposited for 60min, wherein the thickness of the coating is about 4 mu m. Then the medical cutter with deposited Ti-Al-C coating is placed in a tube furnace, the vacuum degree is 2 multiplied by 10 -3 Pa, heating to 700 ℃ at a heating rate of 10 ℃/min, and preserving heat for 1.5h to obtain Ti 2 AlC MAX phase coating
In this example, the preparation method of the Ti-Al-C coating deposited on the surface of the medical cutter is exactly the same as that of example 1, except that: vacuum annealing heat treatment is adopted, the annealing temperature is 700 ℃, and the heat preservation time is 1.5h.
FIG. 2b shows Ti after the vacuum annealing treatment of the present example 2 The surface morphology of the AlC coating, the corrugated morphology of the surface is typical of MAX phase morphology, and large Ti-rich particles generated by electric arc can be obviously observed.
FIG. 3b shows Ti after the vacuum annealing treatment of the present example 2 The AlC coating has a contact angle with water of 126.12 DEG, and is a hydrophobic coating.
Comparative example 2
In the embodiment, the substrate is a 304 stainless steel medical cutter, and the preparation method of the substrate surface coating is as follows:
placing the polished, cleaned and dried 304 stainless steel electrode cutter on a rotatable base frame, and vacuumizing the cavity to 2×10 -3 Pa, heating the cavity to 150 ℃; to a vacuum degree of less than 3×10 -5 Pa，Introducing 30sccm argon, etching the substrate for 30min, wherein the current of the ion beam is 0.2A and the bias voltage is-150V; then changing the argon flow to 200sccm, the magnetron sputtering power to 2000W, the electric arc target current to 70A, and cleaning the target for 20min; then argon is introduced with the flow of 200sccm, the flow of methane is 25sccm, the power of an Al target is adjusted to 3300W, the current of a Ti target is adjusted to 60A, the bias voltage is adjusted to-200V, and a Ti-Al-C coating is deposited for 60min, wherein the thickness of the coating is about 4 mu m.
In this embodiment, after the Ti-Al-C coating deposited on the surface of the medical tool, no treatment was performed, and the contact angle of the obtained coating with water was 98.66 °.
Comparative example 3:
this example is a comparative example of example 1 described above.
In this example, the preparation method of the Ti-Al-C coating deposited on the surface of the medical cutter is exactly the same as that of example 1, except that: the temperature of the high-temperature steam heat treatment is 300 ℃, the heat preservation time is 30 hours, and the contact angle between the coating and water after the high-temperature steam treatment is 81.14 degrees.
Comparative example 4:
this example is a comparative example of example 2 described above.
In this example, the preparation method of the V-Al-C coating deposited on the surface of the medical cutter is exactly the same as that of example 2, except that: the temperature of the high-temperature steam treatment is 1000 ℃, the heat preservation time is 0.5h, and the contact angle between the coating and water after the high-temperature steam treatment is 89.54 degrees.
The above comparative example 1 and examples 1 and 1 were examined by XRD as shown in fig. 5. It can be seen that the phase composition and phase structure of the high-temperature steam heat treatment and the vacuum heat treatment have no obvious change, and are Ti with better crystallinity 2 AlC coating, it shows that the high temperature steam heat treatment does not change the phase structure of the coating, and still has excellent conductivity and high temperature stability of MAX phase coating.
The results of combining the surface morphology and XRD of all examples found that: the phase composition of the coating after high-temperature steam heat treatment is not obviously different from that of vacuum annealing treatment, but the former is decomposed to a certain extent due to large particles generated on the surface of the coating by arc molten dropsThe whole large particles are decomposed into tortoiseshells, so that the roughness of the surface of the coating is improved; on the other hand, the surface of the coating is oxidized by high-temperature steam heat treatment to generate Al 2 O 3 Isooxides, improve the hydrophilicity of the coating, but these oxides are less abundant and cannot be detected by XRD. Compared with the MAX phase prepared by the traditional vacuum annealing, the method greatly improves the wettability of the MAX phase coating and simultaneously still maintains good conductivity and corrosion resistance.
Fig. 6 shows a comparison of contact angles for comparative example 1, example 2 and example 3. It can be seen that comparative example 1 has a contact angle greater than 90 °, and is a hydrophobic coating; whereas the contact angles of the examples are all less than 90 deg., a hydrophilic coating. It is particularly pointed out that example 1 has a minimum contact angle of 52.95 °, and the hydrophilicity is significantly improved compared to comparative example 1. And can be seen from the illustrations: the comparative example showed severe tissue adhesion on the medical knife after the surgical environment test, but no such condition on the knife after the high temperature steam heat treatment, and no obvious difference between the knife and the morphology before the test.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
It should be understood that the technical solution of the present application is not limited to the above specific embodiments, and all technical modifications made according to the technical solution of the present application without departing from the spirit of the present application and the scope of the claims are within the scope of the present application.
Claims (11)
1. The preparation method of the conductive hydrophilic MAX phase coating on the surface of the medical cutter is characterized by comprising the following steps of:
providing a medical cutter as a substrate;
adopting a direct current magnetron sputtering composite cathode arc coating technology, taking an M target as an arc target, taking an Al target as a direct current pulse magnetron sputtering target, taking methane and inert gas as working gases, and depositing and forming an M-Al-C amorphous coating on the surface of the substrate; wherein M is selected from any one of Ti, V, cr, zr;
and, at a vacuum level of 1.0X10 -2 And under the condition of Pa or below, heating the reaction cavity to 400-900 ℃ at a heating rate of 5-10 ℃/min, then introducing steam and keeping the pressure of the reaction cavity at 1 atmosphere, and performing high-temperature steam heat treatment on the matrix deposited with the M-Al-C amorphous coating for 0.5-20 hours, so that a conductive hydrophilic MAX phase coating is formed on the surface of the medical cutter.
2. The method of manufacturing according to claim 1, characterized in that: when the M-Al-C amorphous coating is deposited, the substrate bias voltage is-50 to-200V, the inflow rate of methane gas is 15-30 sccm, the inflow rate of inert gas is 150-200 sccm, the deposition temperature is 30-200 ℃, and the deposition time is 0.5-3 h.
3. The method of manufacturing according to claim 1, characterized in that: and when the M-Al-C amorphous coating is deposited, the average sputtering power of the Al target is 2000-3500W.
4. The method of manufacturing according to claim 1, characterized in that: and when the M-Al-C amorphous coating is deposited, the current of the M target is 30-70A.
5. The method of manufacturing according to claim 1, characterized in that: the thickness of the M-Al-C amorphous coating is 2-10 mu M.
6. The method of manufacturing according to claim 1, characterized in that: when the M-Al-C amorphous coating is deposited, the target distance between the substrate and the Al target is 10-15 cm, and the target distance between the substrate and the M target is 15-20 cm.
7. The method of manufacturing according to claim 1, characterized in that: the medical knife is selected from an electrocoagulation knife or a high-frequency surgical knife.
8. The method of manufacturing according to claim 1, characterized in that: the medical cutter is made of any one of titanium, titanium alloy and stainless steel.
9. A conductive hydrophilic MAX-phase coating of a medical tool surface produced by the production method of any one of claims 1 to 8, the conductive hydrophilic MAX-phase coating having a layered structure;
the contact angle between the surface of the conductive hydrophilic MAX phase coating and water is smaller than 60 degrees; the conductivity of the conductive hydrophilic MAX phase coating is 0.1-0.6 mu omega-m; the thickness of the conductive hydrophilic MAX phase coating is 2-10 mu m;
the conductive hydrophilic MAX phase coating is selected from Ti 2 AlC、Ti 3 AlC 2 、Ti 4 AlC 3 、V 2 AlC、Cr 2 AlC、Zr 2 AlC、Zr 3 AlC 2 Any one of the following.
10. Use of the electrically conductive hydrophilic MAX phase coating of a medical tool surface according to claim 9 for modifying an electrocoagulation blade or a high frequency surgical blade.
11. A method of modifying a surface of a medical tool, comprising: a method according to any one of claims 1 to 8 for producing a conductive hydrophilic MAX-phase coating on the surface of a medical tool.
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| CN111519157A (en) * | 2020-06-23 | 2020-08-11 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of Cr-Al-C series MAX phase coating |
| CN113529033A (en) * | 2021-06-11 | 2021-10-22 | 中国科学院宁波材料技术与工程研究所 | Preparation method of protective coating and protective coating prepared by preparation method |
| CN113981392A (en) * | 2021-10-09 | 2022-01-28 | 中国科学院宁波材料技术与工程研究所 | Ti-Al-C MAX phase coating and low-temperature phase forming preparation method thereof |
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| CN113529033A (en) * | 2021-06-11 | 2021-10-22 | 中国科学院宁波材料技术与工程研究所 | Preparation method of protective coating and protective coating prepared by preparation method |
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