CN113774329A - Multi-stage structure membrane for biomedical use - Google Patents
Multi-stage structure membrane for biomedical use Download PDFInfo
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- CN113774329A CN113774329A CN202111127188.2A CN202111127188A CN113774329A CN 113774329 A CN113774329 A CN 113774329A CN 202111127188 A CN202111127188 A CN 202111127188A CN 113774329 A CN113774329 A CN 113774329A
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- 239000012528 membrane Substances 0.000 title claims abstract description 12
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 239000010936 titanium Substances 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 16
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 15
- 238000004544 sputter deposition Methods 0.000 claims description 32
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 11
- 230000008021 deposition Effects 0.000 claims description 10
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 239000013077 target material Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000005477 sputtering target Methods 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 14
- 230000007797 corrosion Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 48
- 238000002360 preparation method Methods 0.000 description 13
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 4
- 229910000861 Mg alloy Inorganic materials 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000007545 Vickers hardness test Methods 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910010037 TiAlN Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 210000005260 human cell Anatomy 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Classifications
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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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
-
- 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
-
- 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
The present invention provides a multi-stage structural membrane for biomedical use, comprising: the structure of the titanium alloy substrate is composed of Ti, Zr and Ta, the number of layers is 3-4, and the substrate is titanium alloy. The advantages are that: the three materials are 'parent biological metal', are nontoxic, nonmagnetic and strong in corrosion resistance, are favorable for being used as a biomedical film and belong to a biological functional film.
Description
Technical Field
The invention relates to the technical field of biomedical science, in particular to a multi-stage structure membrane for biomedical science.
Background
The surface corrosion resistance and biocompatibility of the existing medical titanium alloy are relatively poor, and the surface modification technology mainly adopts spraying of a Ti or HA coating, so that the defects of low bonding strength between the titanium alloy and the coating and poor abrasion resistance of a film layer exist;
for example, in a patent with publication number CN1648286 and patent name "TiN-TiAIN series hard nano-structure multilayer film coating" (hereinafter referred to as prior art 1), the prepared film has a single structure, is a hard nano-structure multilayer film coating formed by crossing and overlapping two types of nano-films of TiN-TiAIN, is a diamond-like carbon (DLC) hard film, is mainly used for a cutter or a mechanical part, does not have "biocompatibility", and is not suitable for a film preparation technology for the surface of a biomedical material; in terms of preparation process, different reaction gases and special workpiece rotating mechanisms are required to be applied to respectively prepare TiN and TiAlN nano film coatings on the surface of the material, so that the preparation process is complex;
also, for example, in the patent with publication No. CN102703874B, the patent name "preparation method of depositing tantalum film on magnesium alloy surface by magnetron sputtering" (referred to as prior art 2) and the patent name CN103695854A, the patent name "process for manufacturing corrosion-resistant metal material by coating tantalum or niobium by PVD method" (referred to as prior art 3), the tantalum film layer is a single-layer film, and the structure is simple, so that in practical application, after the single-layer film is peeled off, the magnesium alloy substrate is exposed, and the corrosion rate of the magnesium alloy substrate at the film rupture position is accelerated by the potential difference between the substrate and the film layer; in the prior art 2, if the deposition thickness is too thick, the risk of high film cracking risk exists due to the influence of residual stress in a single film layer; in the prior art 3, before the film is prepared, the surface state of the substrate is not required, and polishing and cleaning processes are not performed, so that the PVD tantalum film or niobium film is simple and low in bonding strength with the substrate, is easy to peel off, is not used in a biomedical direction, and is also old in the traditional preparation process.
Therefore, a material which has good surface corrosion resistance and biocompatibility of the medical titanium alloy, high bonding strength between the titanium alloy and the coating, good film abrasion resistance and suitability for biomedical orthopedic implantation is urgently needed.
Disclosure of Invention
The invention provides a multi-stage structure membrane for biomedical use, and provides a method for preparing a multilayer structure biological-friendly membrane layer by titanium alloy surface physical vapor deposition, so as to at least overcome one technical defect.
In order to achieve the above purpose, the invention provides the following technical scheme:
the present invention in a first aspect protects a multi-stage structural membrane for biomedical use, comprising: the structure of the composite material consists of Ti, Zr and Ta, and the number of layers is 3-4.
Preferably, the transition layer is a Ti, Zr, Ta layer and the service layer (exposed/outermost) is a tantalum coating.
A second aspect of the present invention protects a method for producing the multi-stage structural membrane of the first aspect, comprising: respectively installing a plurality of targets on different targets in a magnetron sputtering instrument, and then controlling the sputtering sequence of the different targets according to the specific structure layer of the multi-stage structure film so as to control the deposition thickness of each film layer in a single modulation period and finally obtain the required multi-stage structure film;
wherein, one target material corresponds to one target, and the substrate used in the magnetron sputtering instrument is titanium alloy.
Preferably, the target material is a titanium target, a zirconium target, a tantalum target, and the tantalum target is the outermost layer of the multi-stage structure film.
Preferably, the method of the second aspect of the present invention comprises the following specific steps:
s1, respectively installing a titanium target, a zirconium target and a tantalum target on three targets in a magnetron sputtering instrument;
s2, after the three targets are placed, the vacuum degree of the vacuum chamber is pumped to 4 multiplied by 10-4～6×10-4Pa, filling argon, adjusting sputtering pressure to 1 × 10-1～4×10-1Pa; adjusting the argon gas flow meter valve to stabilize the working pressure of the vacuum chamber at 3 × 10-1～6×10-1Pa；
S3, setting the substrate table rotation speed to be 5-15 rpm, setting the flow limiting valve parameters to be 40-60 degrees, setting the direct current bias power supply to be negative bias voltage of-250V to-350V, pre-sputtering for 10min to 15min at 100w, completing sputtering cleaning, and pulling the baffle plate open, wherein the substrate heating temperature is 200-300 ℃;
and S4, cooling the product obtained in the step S3 to room temperature, taking out, ultrasonically cleaning in absolute ethyl alcohol for 5-10 min again, and air-drying to obtain the multi-stage structural film.
Preferably, in step S3, before the pre-sputtering, the target base distance is set to 50-90 mm, and then the sputtering target baffle and the substrate baffle are opened for the pre-sputtering.
Preferably, in step S3, the current applied to the target is 0.1 to 0.8A, the sputtering power is 60 to 100w, and the sputtering time is 120 to 240min during the target sputtering.
Preferably, in step S3, the sputtering sequence and sputtering time of different targets are controlled according to the structure of the multi-stage structure film and the requirement of the deposition thickness of each film layer.
The invention relates to a multi-stage structure membrane for biological medical use, which has the advantages that:
1. the film layer of the multi-level structure film prepared by the method is a titanium, zirconium and tantalum film layer, and the service layer (exposed layer/outermost layer) is a tantalum coating, and is mainly applied to the surface of the biomedical titanium alloy TC4 for modified deposition; the three materials are 'parent biological metal', are nontoxic, nonmagnetic and strong in corrosion resistance, are favorable for being used as a biomedical film and belong to a biological functional film;
2. in the multilayer structure film, the specific material thickness of the film layers and the like can be designed according to specific requirements, the material and the sequence of each film layer can control the deposition condition of each film layer in a single modulation period by controlling the sputtering sequence of the target material, the modulation layer can be composed of 3-4 film layers, and the three film layers of Ti, Zr and Ta can be randomly arranged and combined, for example: Ti-Zr-Ta film, Zr-Ti-Ta film, Ta-Ti-Zr-Ta film, etc., which have stronger practicability;
3. according to the structural film designed by the invention, the thickness of the modulation period is moderate, each metal film in the modulation layer is made of corrosion-resistant metal, after the surface film fails, the second film still can provide strong corrosion resistance, the tissue matrix is in direct contact with the environment, and the occurrence of ion release risk in matrix alloy is reduced;
4. in the preparation method, 3 target positions are arranged in a magnetron sputtering instrument to simultaneously put three metal targets of Ti, Zr and Ta, so that the preparation efficiency is improved;
5. the thickness of each layer in the multi-level structure film is controlled within 1um, so that the risk of rubbing failure caused by residual stress when the deposition thickness of a single-layer film is increased is reduced; in addition, the base alloy needs to be polished and cleaned before use, so that the bonding strength between the film and the base alloy can be increased, and the film has high wear resistance in actual service.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention. In the drawings:
FIG. 1 is a comparison of the structure of a multi-stage structural film prepared according to example one of the present invention and a matrix of a comparative alloy TC 4;
FIG. 2 is a comparison of the multi-stage structure film prepared by the second embodiment of the present invention and the matrix structure of the comparative alloy TC 4;
FIG. 3 is a comparison of the multi-stage structure film prepared by the third embodiment of the present invention and the matrix structure of the comparative alloy TC 4.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
The mechanism of the invention is as follows: in the surface modification technology, magnetron sputtering can realize two typical characteristics of substrate heating and high-speed preparation. Three targets can be sputtered and deposited simultaneously during sputtering, the film preparation efficiency is high, and in the sputtering material, titanium, zirconium and tantalum have excellent corrosion resistance, good surface mechanical property and good biocompatibility. The tantalum film layer is used as an exposed layer, the service performance of the tantalum film layer is optimal, the bonding strength between the film layers can be increased through the rest transition layers, the risk of matrix ion precipitation after the exposed layer is stripped is reduced, the thickness of the film layer can be increased, and the cost of the film layer can be reduced.
Example one
Comprises the following steps:
firstly, immersing a titanium alloy substrate in acetone, deionized water and absolute ethyl alcohol respectively, ultrasonically cleaning for 10min, and air-drying; wearing powder-free disposable rubber gloves by hands, clamping a sample on a sample rack in a vacuum chamber of equipment, and cleaning the sample and the surface of the sample rack by using an electric blower again; the sizes of the target materials are phi 76.2 x 5mm, a high-purity titanium target with the purity of 99.995 percent, a high-purity zirconium target with the purity of 99.9 percent and a high-purity tantalum target with the purity of 99.95 percent are respectively arranged on three magnetron sputtering targets, and a target baffle is pushed to block the sputtering targets; and locking the door bolt opening of the vacuum bin to ensure the sealing of the vacuum bin.
And secondly, opening a cooling water system and opening a main power supply of the equipment. Opening the mechanical pump and the backing valve until the vacuum of the backing valve is 5 Pa; closing the front-stage valve, opening the bypass valve and the ionization gauge until the vacuum of the chamber is 5 Pa; closing the by-pass valve, opening the pre-stage valve of molecular pump, molecular pump and main valve, and vacuumizing to 4X 10-4Pa; argon is filled into the vacuum chamber, and the sputtering pressure is adjusted to 1 multiplied by 10-1Pa. The substrate heating temperature was 200 ℃ and the substrate stage rotation speed was set at 5 rpm. Opening a stop valve, setting parameters of a flow limiting valve, adjusting the parameters to 40 degrees, and then adjusting the opening and closing of an argon flowmeter to stabilize the air pressure of the vacuum chamber at 6 x 10-1Pa. Turning on a bias power supply, adjusting bias voltage for cleaning for 10 min; the direct current bias power supply is negative bias voltage of-250V and is loaded to the sample stage for auxiliary deposition; setting the target base distance to be 50mm, and opening a sputtering target baffle and a substrate baffle; the current loaded on the target by the direct current constant current power supply is 0.1A; when sputtering a tantalum target, the sputtering power is 60 w. And (5) pre-sputtering for 5min under the sputtering power of 100w to finish the sputtering cleaning. And pulling the baffle open, and carrying out co-sputtering for 240min according to the deposition thickness requirement of each film layer.
And thirdly, after sputtering for a certain time, closing the target baffle, the power source, the flow controller, the stop valve, the main power supply and the cooling water. After the sample is cooled to room temperature, the sample is ultrasonically cleaned again in absolute ethyl alcohol for 5min and air-dried, and a Ta-Ti-Zr-Ta four-layer multi-stage film sample is prepared, as shown in FIG. 1, the total thickness of the film layer is 1.1 μm in the embodiment.
The second embodiment and the third embodiment are designed, and the differences between the second embodiment and the third embodiment and the first embodiment are that the following parameters shown in table 1 are different in the preparation process (wherein, the structural diagrams of the products obtained in the second embodiment and the third embodiment are respectively shown in fig. 2 and fig. 3), and the following table 1 is specifically shown:
TABLE 1 comparison of parameters for one to three examples of a process for producing tantalum metal coatings
The products obtained in the three examples were subjected to the following relative performance tests:
firstly, according to GB/T10125-:
table 2: test standards of the first, second and third embodiments of the invention and salt spray test results
As can be seen from Table 2, the multi-level structural film sample prepared by the method disclosed by the invention is more excellent in corrosion resistance, and the weight loss after 1440 hours is 54.0628g/m2The corrosion resistance in sodium chloride solution was improved by 87.13% compared to the base TC4 alloy.
And II, performing Vickers hardness test on a multistage structural film sample by GB/T4340.1-2009 part 1 of a metal material Vickers hardness test: test methods the results of the surface microhardness property measurements are shown in table 3 below:
table 3: test standards of the first, second and third embodiments of the invention and salt spray test results
From the above table 3, at the position of 100gf force, the loading and pressure holding time is set to 10s, and 30 points are measured for each sample, the surface hardness of the multi-stage structural film sample of the embodiment is remarkably enhanced, the hardness is 408HV, and the hardness is improved by 30.8% compared with the alloy TC4 matrix.
The invention utilizes metal titanium, zirconium and tantalum to provide a multi-level nanostructure modified layer for titanium alloy, develops a novel tantalum film layer material and a preparation technology thereof, utilizes various 'parent biological metals' (namely titanium, zirconium and tantalum) as modulation layer materials aiming at a multi-layer nanostructure film layer, designs a modulation layer structure and constructs a plurality of novel multi-level structure multi-layer film structures which can be combined and arranged; compared with a matrix titanium alloy (TC4), the corrosion resistance of the prepared multi-stage structure film in a sodium chloride salt mist test is improved by 87.13-88.06%, the surface microhardness is improved by 24.4-30.8%, and the two aspects are remarkably improved;
the multi-level structure multi-layer film can achieve the purposes of light weight, functionalization and low cost. The exposed layer is metal tantalum, so that the most excellent biocompatibility, corrosion resistance and wear resistance can be provided, the proliferation of human cells is facilitated, and the corrosion and wear degree in the service process is reduced; the method for preparing the transition layer can effectively enhance the stability of the outermost tantalum film layer;
the preparation method reduces the cost of preparing the tantalum coating on the surface, and has high preparation efficiency due to the improvement of the process technology.
The steps and the like which are not described in detail in the invention can be realized by the conventional technology, and therefore, the detailed description is not repeated.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (8)
1. A multi-stage structural membrane for biomedical use, characterized by: the structure of the titanium alloy substrate is composed of Ti, Zr and Ta, the number of layers is 3-4, and the substrate is titanium alloy.
2. The multi-stage structural membrane for biomedical use according to claim 1, wherein: the transition layer is a Ti, Zr and Ta layer, and the service layer (exposed layer/outermost layer) is a tantalum coating.
3. A method for producing the multi-stage structural membrane for biomedical use according to claim 1 or 2, characterized in that: respectively installing a plurality of targets on different targets in a magnetron sputtering instrument, and then controlling the sputtering sequence of the different targets according to the specific structure layer of the multi-stage structure film so as to control the deposition thickness of each film layer in a single modulation period and finally obtain the required multi-stage structure film;
wherein, one target material corresponds to one target, and the substrate used in the magnetron sputtering instrument is titanium alloy.
4. The method of claim 3, further comprising: the target material is a titanium target, a zirconium target and a tantalum target, and the tantalum target is the outermost layer of the multi-stage structural film.
5. The method of claim 4, further comprising: the method comprises the following steps:
s1, respectively installing a titanium target, a zirconium target and a tantalum target on three targets in a magnetron sputtering instrument;
s2, after the three targets are placed, the vacuum degree of the vacuum chamber is pumped to 4 multiplied by 10-4～6×10-4Pa, filling argon, adjusting sputtering pressure to 1 × 10-1～4×10-1Pa; adjusting the argon gas flow meter valve to stabilize the working pressure of the vacuum chamber at 3×10-1～6×10- 1Pa；
S3, setting the substrate table rotation speed to be 5-15 rpm, setting the flow limiting valve parameters to be 40-60 degrees, setting the direct current bias power supply to be negative bias voltage of-250V to-350V, pre-sputtering for 10min to 15min at 100w, completing sputtering cleaning, and pulling the baffle plate open, wherein the substrate heating temperature is 200-300 ℃;
and S4, cooling the product obtained in the step S3 to room temperature, taking out, ultrasonically cleaning in absolute ethyl alcohol for 5-10 min again, and air-drying to obtain the multi-stage structural film.
6. The method of claim 5, further comprising: in step S3, before pre-sputtering, the target base distance is set to 50 to 90mm, and then the sputtering target baffle and the substrate baffle are opened for pre-sputtering.
7. The method of claim 5, further comprising: in step S3, when the target material is sputtered, the current loaded on the target material is 0.1-0.8A, the sputtering power is 60-100 w, and the sputtering time is 120-240 min.
8. The method of claim 5, further comprising: in step S3, the sputtering sequence and sputtering time of different targets are controlled according to the structure of the multi-level structure film and the requirement of the deposition thickness of each film layer.
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| CN202111127188.2A CN113774329A (en) | 2021-09-26 | 2021-09-26 | Multi-stage structure membrane for biomedical use |
| PCT/CN2022/092850 WO2023045352A1 (en) | 2021-09-26 | 2022-05-13 | Multi-stage structural membrane for biomedical use |
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