CN110280462B - Composite coating nickel-titanium alloy material with super-hydrophobic and oleophobic properties and preparation method thereof - Google Patents

Composite coating nickel-titanium alloy material with super-hydrophobic and oleophobic properties and preparation method thereof Download PDF

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CN110280462B
CN110280462B CN201910573486.0A CN201910573486A CN110280462B CN 110280462 B CN110280462 B CN 110280462B CN 201910573486 A CN201910573486 A CN 201910573486A CN 110280462 B CN110280462 B CN 110280462B
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titanium alloy
nickel
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张伟星
王瑞兰
宛新建
杨莹
黎金臻
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Shanghai First Peoples Hospital
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Abstract

The invention relates to a composite coating nickel-titanium alloy material with super-hydrophobic and oleophobic properties and a preparation method thereof. The invention uses mixed acid solution and H on the surface of the nickel-titanium alloy material in sequence2SO3The solution is etched twice, then linear low-density polyethylene and ZnO nanoparticles are sprayed, finally stearic acid is used for surface low-surface-energy modification, contact angle test results show that the surface of the modified nickel-titanium alloy material has excellent super-hydrophobic and super-oleophobic properties, and adhesion experiment results show that the adhesion capacity of smooth muscle cells on the surface of the modified nickel-titanium alloy material is weak, and the bacterial colonization capacity is very weak. Therefore, the nickel-titanium alloy material with the composite coating has unique advantages in the aspect of preparing implantable medical instruments, and can effectively inhibit intimal hyperplasia of blood vessels, prevent restenosis of the blood vessels and inhibit colonization and growth of pathogenic bacteria.

Description

Composite coating nickel-titanium alloy material with super-hydrophobic and oleophobic properties and preparation method thereof
Technical Field
The invention relates to the field of super-amphiphobic materials and medical instruments, in particular to a composite coating nickel-titanium alloy material with super-hydrophobic and oleophobic properties and a preparation method thereof.
Background
Nickel titanium alloys are widely used in the field of medical devices based on their unique superelasticity and shape memory effects. The nickel-titanium alloy intravascular stent is widely applied clinically, but the nickel-titanium alloy intravascular stent cannot be absorbed by organisms and cannot be degraded after being implanted into blood vessels, so that the nickel-titanium alloy intravascular stent is easy to cause excessive hyperplasia of intima of the blood vessels when being used as a foreign body in human bodies for a long time, and causes the problems of restenosis, chronic inflammation, late and very late thrombosis and the like in the middle and later stages of the blood vessels. It is important to improve the surface properties of nitinol alloys to avoid the above complications.
Surfaces with contact angles greater than 150 ° for both water and oil are referred to as superhydrophobic/oleophobic surfaces. Superhydrophobic/oleophobic is a particular phenomenon of solid surfaces, primarily related to the roughness and chemical composition of the surface. The super-hydrophobic/oleophobic surface has excellent characteristics of self-cleaning, corrosion resistance, low friction, drag reduction, adhesion resistance and the like, and has potential application values in the industrial field and the medical field, such as developed antifouling paint boats, snow-resistant agents for antennas and windows, self-cleaning windshields, antifouling building coatings, waterproof and antifouling textiles, and vascular implants with super-hydrophobic and oleophobic composite nano coatings disclosed in patent document CN 106806038A.
Patent document CN109732195A discloses a titanium alloy superhydrophobic-superhydrophilic surface, and a preparation method and an application thereof, and specifically, a plurality of subarrays are distributed on the titanium alloy surface, a plurality of superhydrophobic regions and a plurality of superhydrophilic regions in each subarray are alternately arranged in a wedge shape or a triangular shape, and a superhydrophilic collecting region is distributed between each subarray. The super-hydrophobic surface has excellent super-hydrophobic performance, the liquid drop adhesion is very small, and the liquid drop is very easy to roll off; the super hydrophilic area can adsorb liquid drops, the liquid drops at the top end of the wedge-shaped or triangular super hydrophilic area can automatically and rapidly move towards the bottom of the wedge-shaped or triangular area under the driving of the pressure of the Prasiian generated by the wedge-shaped or triangular area, and the super hydrophobic areas alternately arranged with the wedge-shaped or triangular super hydrophilic area can repel the directional transportation of the liquid drops, so that condensed liquid drops are continuously collected in the hydrophilic collection area under the mutual synergistic action, the self-driven water collection with high concentration degree is realized, the dropping of the liquid drops is accelerated, and the condensation heat transfer efficiency is accelerated.
Patent document CN107755228A, discloses a method for preparing a superhydrophobic and oleophobic surface on an aluminum alloy substrate surface, said method comprising the steps of: a) using acetone and ethanol to remove oil on the surface of the alloy aluminum and primarily cleaning; b) polishing the surface into a micron-sized rough surface by using coarse sand paper; c) further cleaning the surface of the alloy aluminum by using acetone and ethanol, and then boiling the alloy aluminum by using deionized water; d) ultrasonic cleaning the substrate in methanol and acetone for 1-5 min, and boiling in boiling water for 20-40min to roughen the surface; e) and (4) surface sizing. This patent enables a metal surface to achieve a wash-free, self-cleaning surface.
However, at present, a composite coating nickel-titanium alloy material which has good super-hydrophobic and oleophobic properties, super-lubrication, effective reduction of intimal hyperplasia and good antibacterial effect is not available.
Disclosure of Invention
The invention aims to provide a composite coating nickel-titanium alloy material with super-hydrophobic and oleophobic properties aiming at the defects in the prior art.
The invention further aims to provide a preparation method of the composite coating nickel-titanium alloy material with the super-hydrophobic and oleophobic properties.
The invention also aims to provide application of the composite coating nickel-titanium alloy material with super-hydrophobic and oleophobic properties.
In order to achieve the first purpose, the invention adopts the technical scheme that:
a composite coating nickel-titanium alloy material with super-hydrophobic and oleophobic properties is prepared by the following method:
a) removing oil from the surface of nickel-titanium alloy material, adding into mixed acid solution containing 0.2-0.4M HBr, 1.8-2.2M hydrochloric acid, and 2.5-3.5M acetic acid, placing in dark for 3-4 hr, taking out, and adding into 0.5-1MH2SO3Treating in the solution for 10-30min, cleaning with deionized water, and blow-drying to obtain a pretreated nickel-titanium alloy material;
b) dispersing LLDPE and ZnO nanoparticles in 3-4 times of absolute ethanol solution, wherein the mass ratio of the LLDPE to the ZnO nanoparticles is 1 (3-4), ultrasonically dispersing for 1-2h, then spraying on the surface of the pretreated nickel-titanium alloy material, then placing at 40-50 ℃ for 1-2h, and keeping at 300-360 ℃ for 80-100min to obtain an LLDPE-ZnO nickel-titanium alloy plate;
c) dispersing stearic acid powder in 2-3 times of absolute ethyl alcohol solution, ultrasonically dispersing for 5-10min, then placing the LLDPE-ZnO nickel-titanium alloy plate in the stearic acid solution, and soaking for 1-2h to prepare the LLDPE-ZnO-SA nickel-titanium alloy plate, namely the composite coating nickel-titanium alloy material.
Preferably, in the step b), the mass ratio of the LLDPE to the ZnO nanoparticles is 1 (3-4).
Preferably, in the step b), the mass ratio of the total mass of the LLDPE and the ZnO nanoparticles to the absolute ethyl alcohol is 1 (3-4).
Preferably, in the step c), the mass ratio of the stearic acid powder to the absolute ethyl alcohol is 1 (2-3).
Preferably, in the step a), the oil removal on the surface of the nickel-titanium alloy material comprises the following specific steps: soaking the nickel-titanium alloy material in acetone to remove oil, taking out, ultrasonically cleaning with absolute ethyl alcohol, ultrasonically cleaning with deionized water, and finally drying with high-pressure nitrogen.
In order to achieve the second object, the invention adopts the technical scheme that:
a preparation method of a composite coating nickel-titanium alloy material with super-hydrophobic and oleophobic properties comprises the following steps:
a) removing oil from the surface of nickel-titanium alloy material, adding into mixed acid solution containing 0.2-0.4M HBr, 1.8-2.2M hydrochloric acid, and 2.5-3.5M acetic acid, placing in dark for 3-4 hr, taking out, and adding into 0.5-1MH2SO3Treating in the solution for 10-30min, cleaning with deionized water, and blow-drying to obtain a pretreated nickel-titanium alloy material;
b) dispersing LLDPE and ZnO nanoparticles in 3-4 times of absolute ethanol solution, wherein the mass ratio of the LLDPE to the ZnO nanoparticles is 1 (3-4), ultrasonically dispersing for 1-2h, then spraying on the surface of the pretreated nickel-titanium alloy material, then placing at 40-50 ℃ for 1-2h, and keeping at 300-360 ℃ for 80-100min to obtain an LLDPE-ZnO nickel-titanium alloy plate;
c) dispersing stearic acid powder in 2-3 times of absolute ethyl alcohol solution, ultrasonically dispersing for 5-10min, then placing the LLDPE-ZnO nickel-titanium alloy plate in the stearic acid solution, and soaking for 1-2h to prepare the LLDPE-ZnO-SA nickel-titanium alloy plate, namely the composite coating nickel-titanium alloy material.
Preferably, in the step b), the mass ratio of the LLDPE to the ZnO nanoparticles is 1 (3-4).
Preferably, in the step b), the mass ratio of the total mass of the LLDPE and the ZnO nanoparticles to the absolute ethyl alcohol is 1 (3-4).
Preferably, in the step c), the mass ratio of the stearic acid powder to the absolute ethyl alcohol is 1 (2-3).
In order to achieve the third object, the invention adopts the technical scheme that:
the application of the composite coating nickel-titanium alloy material in the preparation of medical appliances.
Preferably, the medical device is a vascular implant.
The invention has the advantages that:
1. the invention uses mixed acid solution and H on the surface of the nickel-titanium alloy material in sequence2SO3The solution is etched twice, then linear low-density polyethylene and ZnO nano particles are sprayed, finally stearic acid is used for surface low-surface-energy modification, and contact angle test results show that the surface of the modified nickel-titanium alloy material has excellent super-hydrophobic and super-oleophobic characteristics;
2. the adhesion experiment result shows that the adhesion capability of the smooth muscle cells on the surface of the modified nickel-titanium alloy material is very weak, so that the vascular intimal hyperplasia can be effectively inhibited, and the occurrence of restenosis can be prevented;
3. the adhesion experiment result shows that the modified nickel-titanium alloy material has very weak bacteria colonization capacity on the surface, and the nickel-titanium alloy material has excellent antibacterial capacity.
Detailed Description
The following provides a detailed description of specific embodiments of the present invention.
Example 1 preparation of composite coating nickel-titanium alloy material with super-hydrophobic and oleophobic property of the invention
1 materials of the experiment
1.1 medical nickel-titanium memory alloy plate
The medical nickel-titanium memory alloy plate is purchased from Shenzhen Xinghuan new material Limited, the nickel content is 55.8 wt%, and the size is 5mm × 10 mm.
1.2 cells
Smooth muscle cells were purchased from shanghai cell institute of chinese academy of sciences;
coli strains were purchased from seiko (guangzhou) biotechnology limited.
1.3 reagents
Acetone, absolute ethanol, hydrobromic acid, hydrochloric acid, acetic acid, available from Shanghai Merck reagent, Inc.;
linear Low Density Polyethylene (LLDPE) is available from dow, usa;
ZnO nanoparticles were purchased from Sigma.
1.4 instruments and devices
Ultrasonic oscillation cleaning machine, model: KQ 2200E;
video optical contact angle gauge (OCA 20), available from Dataphysics corporation;
a constant temperature carbon dioxide cell incubator was purchased from Thermo;
a desktop refrigerated centrifuge was purchased from Eppendorf;
the high temperature electric furnace is Shanghai Vaccinium uliginosum MF-12-12A.
2 method of experiment
2.1 pretreatment of the Nitinol sheet
Soaking the nickel-titanium alloy plate with acetone to remove oil, taking out, ultrasonically cleaning with absolute ethyl alcohol, ultrasonically cleaning with deionized water, and blow-drying the cleaned nickel-titanium alloy plate with high-pressure nitrogen. Placing into a clean sealed container containing hydrobromic acid containing 0.3M HBr, 2M hydrochloric acid, and 3M acetic acid, placing in dark for 3.5 hr, taking out, and placing into a container containing 0.8M H2SO3Placing the solution in a clean sealed container for 20min, taking out, ultrasonically cleaning with deionized water, and blow-drying with high-pressure nitrogen.
2.2 preparation of LLDPE-ZnO nickel-titanium alloy plate
Dispersing LLDPE and ZnO nanoparticles in 3.5 times of absolute ethanol solution, wherein the mass ratio of the linear LLDPE to the ZnO nanoparticles is 1:3.5, ultrasonically dispersing for 1.5h, pouring into a spray gun, spraying on the surface of a pretreated nickel-titanium alloy plate, wherein the spraying pressure is 0.5Mpa and the distance is 20cm, then placing in a high-temperature electric furnace, keeping the temperature at 45 ℃ for 1.5h, and keeping the temperature at 320 ℃ for 90min to obtain the LLDPE-ZnO nickel-titanium alloy plate with the LLDPE and ZnO on the surface.
2.3 preparation of LLDPE-ZnO-SA nickel-titanium alloy plate
Dispersing stearic acid powder in 2.5 times of absolute ethyl alcohol solution, ultrasonically dispersing for 8min, then placing the LLDPE-ZnO nickel-titanium alloy plate in the stearic acid solution, and soaking for 1.5h to prepare the LLDPE-ZnO-SA nickel-titanium alloy plate.
2.4 contact Angle test
And (3) dripping a water drop or glycerol on five different positions on the surface of the sample, measuring the contact angle by using a video optical contact angle measuring instrument, and taking the average value as a test result.
2.5 cell adhesion experiments
Smooth muscle cells were trypsinized and finally harvested by centrifugation at 1500rpm for 5 minutes to prepare a cell suspension. Cell suspension of smooth muscle cells at final 1X 105The density of/ml was seeded on the surface of a modified or unmodified nitinol plate in a cell culture plate. Adding 5% CO at 37 deg.C2Incubating in an incubator, and calculating the adhesion amount of the cells after 5 hours.
2.6 bacterial adhesion test
Sterilizing the nickel-titanium alloy plate with or without modification at high temperature and high pressure, placing into cell culture plate, adding 1ml fresh E.coli bacterial suspension into each culture plate, and making the concentration be 1 × 106CFU/ml, repeat 3 plate. Placing the mixture into an incubator for static culture at an aerobic temperature of 37 ℃, slightly taking out the mixture by using sterile forceps after culturing for 6h, slightly washing the mixture by using PBS (phosphate buffer solution) for 3 times, removing floating bacteria which are not adhered to the surface, ultrasonically eluting the bacteria on the surface for 25min, diluting the mixture in a multiple ratio, coating a plate, placing the mixture into the incubator for culture for 24h, calculating the number of bacterial colonies, and further calculating the adhesion amount of E.coli.
2.7 data processing
Average + -SD for data measurement
Figure BDA0002111464340000052
Indicated, groups of t-tests were used and analyzed using SPSS10.0 software.
3 results of the experiment
3.1 Nickel-titanium alloy plate surface hydrophobic and oleophobic Properties
The water and glycerol contact angle measurements of the surface of the modified and unmodified nitinol plates are shown in table 1. The LLDPE-ZnO-SA nickel-titanium alloy plate has super-hydrophobic and super-oleophobic surface properties.
TABLE 1 contact angles of water and glycerol on the surface of a nickel-titanium alloy plate
Figure BDA0002111464340000051
Note: p <0.01 compared to the nitinol plate set.
3.2 anti-intimal hyperplasia ability of the Nickel-titanium alloy sheet surface
The amount of smooth muscle cell adhesion on the surface of the modified and unmodified nitinol plates is shown in table 2. The LLDPE-ZnO-SA nickel-titanium alloy plate has excellent effect of resisting the adhesion and growth of smooth muscle cells, so that the vascular intimal hyperplasia can be effectively inhibited, and the occurrence of vascular restenosis is avoided.
TABLE 2 amount of smooth muscle cells adhering to the surface of the nitinol sheet
Figure BDA0002111464340000061
Note: p <0.05 compared to the nitinol sheet set.
3.3 antibacterial Properties
The adhesion amount of e.coli after the e.coli was inoculated on the modified and unmodified nitinol plates and cultured for 6h is shown in table 3. It can be seen that the LLDPE-ZnO-SA nickel-titanium alloy plate has excellent anti-infection function.
TABLE 3E. adhesion of Ni-Ti alloy sheet to surface
Figure BDA0002111464340000062
Note: p <0.01 compared to the nitinol plate set.
Example 2 preparation of composite coating nickel-titanium alloy material with super-hydrophobic and oleophobic property of the invention
1. Pretreatment of nickel-titanium alloy sheet
Soaking the nickel-titanium alloy plate in acetone to remove oil, taking out, ultrasonically cleaning with absolute ethyl alcohol, ultrasonically cleaning with deionized water, and blow-drying with high-pressure nitrogen. Placing into a clean sealed container containing hydrobromic acid containing 0.3M HBr, 1.8M hydrochloric acid, and 2.5M acetic acid, placing in dark for 3 hr, taking out, and placing into a container containing 1M H2SO3Placing the solution in a clean sealed container for 10min, taking out, ultrasonically cleaning with deionized water, and blow-drying with high-pressure nitrogen.
2. Preparation of LLDPE-ZnO nickel-titanium alloy plate
Dispersing LLDPE and ZnO nanoparticles in 4 times of absolute ethanol solution, wherein the mass ratio of the LLDPE to the ZnO nanoparticles is 1:3, ultrasonically dispersing for 2h, pouring into a spray gun, spraying on the surface of the pretreated nickel-titanium alloy plate, wherein the spraying pressure is 0.5Mpa and the distance is 20cm, then placing the nickel-titanium alloy plate in a high-temperature electric furnace, keeping the temperature at 50 ℃ for 1h and keeping the temperature at 300 ℃ for 100min to obtain the LLDPE-ZnO nickel-titanium alloy plate with the LLDPE and the ZnO on the surface.
3. Preparation of LLDPE-ZnO-SA nickel-titanium alloy plate
Dispersing stearic acid powder in 3 times of absolute ethyl alcohol solution, ultrasonically dispersing for 5min, then placing the LLDPE-ZnO nickel-titanium alloy plate in the stearic acid solution, and soaking for 2h to prepare the LLDPE-ZnO-SA nickel-titanium alloy plate.
According to the same method as the example 1, the contact angles of water and glycerol on the surface of the LLDPE-ZnO-SA nickel-titanium alloy plate are respectively 163.6 +/-1.9 degrees and 162.7 +/-2.0 degrees; the adhesion amount of smooth muscle cells on the surface of the LLDPE-ZnO-SA nickel-titanium alloy plate after 5 hours of culture is 36.5 +/-3.2 cells/mm2(ii) a Inoculating E.coli, and culturing for 6h to obtain the final product with the adhesion amount of 51.7 + -5.2 cells/mm2。
Example 3 preparation of composite coating nickel-titanium alloy material with super-hydrophobic and oleophobic property (III) of the invention
1. Pretreatment of nickel-titanium alloy sheet
Soaking the nickel-titanium alloy plate with acetone to remove oil, taking out, ultrasonically cleaning with absolute ethyl alcohol, ultrasonically cleaning with deionized water, and blow-drying the cleaned nickel-titanium alloy plate with high-pressure nitrogen. Placing into a clean sealed container containing hydrobromic acid containing 0.2M HBr, 2.2M hydrochloric acid and 2.5M acetic acid, standing in dark for 3.5 hr, taking out, and placing into a container containing 0.5M H2SO3Clean sealed container for solutionAnd standing for 30min, taking out, ultrasonically cleaning with deionized water, and blow-drying with high-pressure nitrogen.
2. Preparation of LLDPE-ZnO nickel-titanium alloy plate
Dispersing LLDPE and ZnO nanoparticles in 3 times of absolute ethanol solution, wherein the mass ratio of the LLDPE to the ZnO nanoparticles is 1:4, ultrasonically dispersing for 1h, pouring into a spray gun, spraying on the surface of the pretreated nickel-titanium alloy plate, wherein the spraying pressure is 0.5Mpa and the distance is 20cm, then placing the nickel-titanium alloy plate in a high-temperature electric furnace, keeping the temperature at 40 ℃ for 1.5h, and keeping the temperature at 360 ℃ for 80min to obtain the LLDPE-ZnO nickel-titanium alloy plate with the LLDPE and the ZnO on the surface.
3. Preparation of LLDPE-ZnO-SA nickel-titanium alloy plate
Dispersing stearic acid powder in 2 times of absolute ethyl alcohol solution, performing ultrasonic dispersion for 10min, then placing the LLDPE-ZnO nickel-titanium alloy plate in the stearic acid solution, and soaking for 1.5h to prepare the LLDPE-ZnO-SA nickel-titanium alloy plate.
According to the same method as the example 1, the contact angles of water and glycerol on the surface of the LLDPE-ZnO-SA nickel-titanium alloy plate are respectively 161.3 +/-2.0 degrees and 162.5 +/-2.1 degrees; the adhesion amount of smooth muscle cells on the surface of the LLDPE-ZnO-SA nickel-titanium alloy plate after 5 hours of culture is 38.0 +/-3.2 cells/mm2(ii) a Inoculating E.coli, and culturing for 6h to obtain the final product with the adhesion amount of 48.8 + -4.9 cells/mm2。
Example 4 preparation of composite coating nickel-titanium alloy material with super-hydrophobic and oleophobic property of the Invention (IV)
1. Pretreatment of nickel-titanium alloy sheet
Soaking the nickel-titanium alloy plate with acetone to remove oil, taking out, ultrasonically cleaning with absolute ethyl alcohol, ultrasonically cleaning with deionized water, and blow-drying the cleaned nickel-titanium alloy plate with high-pressure nitrogen. Placing into a clean sealed container containing hydrobromic acid containing 0.4M HBr, 2M hydrochloric acid, and 3.5M acetic acid, placing in dark for 4 hr, taking out, and placing into a container containing 1M H2SO3Placing the solution in a clean sealed container for 20min, taking out, ultrasonically cleaning with deionized water, and blow-drying with high-pressure nitrogen.
2. Preparation of LLDPE-ZnO nickel-titanium alloy plate
Dispersing LLDPE and ZnO nanoparticles in 3 times of absolute ethanol solution, wherein the mass ratio of the LLDPE to the ZnO nanoparticles is 1:3, ultrasonically dispersing for 1.5h, pouring into a spray gun, spraying on the surface of the pretreated nickel-titanium alloy plate, wherein the spraying pressure is 0.5Mpa and the distance is 20cm, then placing the nickel-titanium alloy plate in a high-temperature electric furnace, keeping the temperature at 40 ℃ for 2h, and keeping the temperature at 360 ℃ for 100min to obtain the LLDPE-ZnO nickel-titanium alloy plate with the LLDPE and the ZnO on the surface.
3. Preparation of LLDPE-ZnO-SA nickel-titanium alloy plate
Dispersing stearic acid powder in 2 times of absolute ethyl alcohol solution, ultrasonically dispersing for 5min, then placing the LLDPE-ZnO nickel-titanium alloy plate in the stearic acid solution, and soaking for 1h to prepare the LLDPE-ZnO-SA nickel-titanium alloy plate.
According to the same method as the example 1, the contact angles of water and glycerol on the surface of the LLDPE-ZnO-SA nickel-titanium alloy plate are respectively 165.0 +/-1.8 degrees and 164.8 +/-2.0 degrees; the adhesion amount of smooth muscle cells on the surface of the LLDPE-ZnO-SA nickel-titanium alloy plate after 5 hours of culture is 35.4 +/-3.9 cells/mm2(ii) a Inoculating E.coli, culturing for 6h, wherein the adhesion amount of E.coli on the surface of the LLDPE-ZnO-SA nickel-titanium alloy plate is 50.5 +/-5.8 cells/mm2。
Comparative example 1
1. Pretreatment of nickel-titanium alloy sheet
Soaking the nickel-titanium alloy plate with acetone to remove oil, taking out, ultrasonically cleaning with absolute ethyl alcohol, ultrasonically cleaning with deionized water, and blow-drying the cleaned nickel-titanium alloy plate with high-pressure nitrogen. Putting into a clean sealed container containing hydrobromic acid containing 0.3M HBr, 2M hydrochloric acid and 3M acetic acid, placing in a dark place for 3.5h, taking out, ultrasonically cleaning with deionized water, and blow-drying with high-pressure nitrogen.
2. Preparation of LLDPE-ZnO nickel-titanium alloy plate
Dispersing LLDPE and ZnO nanoparticles in 3.5 times of absolute ethanol solution, wherein the mass ratio of the LLDPE to the ZnO nanoparticles is 1:3.5, ultrasonically dispersing for 1.5h, pouring into a spray gun, spraying on the surface of a pretreated nickel-titanium alloy plate, wherein the spraying pressure is 0.5Mpa and the distance is 20cm, then placing the nickel-titanium alloy plate in a high-temperature electric furnace, keeping the temperature at 45 ℃ for 1.5h, and keeping the temperature at 320 ℃ for 90min to obtain the LLDPE-ZnO nickel-titanium alloy plate with the LLDPE and ZnO on the surface.
3. Preparation of LLDPE-ZnO-SA nickel-titanium alloy plate
Dispersing stearic acid powder in 2.5 times of absolute ethyl alcohol solution, ultrasonically dispersing for 8min, then placing the LLDPE-ZnO nickel-titanium alloy plate in the stearic acid solution, and soaking for 1.5h to prepare the LLDPE-ZnO-SA nickel-titanium alloy plate.
According to the same method as the example 1, the contact angles of water and glycerol on the surface of the LLDPE-ZnO-SA nickel-titanium alloy plate are respectively measured to be 110.6 +/-1.8 degrees and 103.5 +/-2.3 degrees; the adhesion amount of smooth muscle cells on the surface of the LLDPE-ZnO-SA nickel-titanium alloy plate after 5 hours of culture is 47.0 +/-2.9 cells/mm2(ii) a Inoculating E.coli, and culturing for 6h to obtain the final product with the adhesion amount of 101.6 +/-6.3 cells/mm on the surface of LLDPE-ZnO-SA nickel-titanium alloy plate2。
Comparative example 2
1. Pretreatment of nickel-titanium alloy sheet
Soaking the nickel-titanium alloy plate with acetone to remove oil, taking out, ultrasonically cleaning with absolute ethyl alcohol, ultrasonically cleaning with deionized water, and blow-drying the cleaned nickel-titanium alloy plate with high-pressure nitrogen. Placing into a clean sealed container containing 2.3M hydrochloric acid and 3M acetic acid, placing in dark for 3.5 hr, taking out, and placing into a container containing 0.8MH2SO3Placing the solution in a clean sealed container for 20min, taking out, ultrasonically cleaning with deionized water, and blow-drying with high-pressure nitrogen.
2. Preparation of LLDPE-ZnO nickel-titanium alloy plate
Dispersing LLDPE and ZnO nanoparticles in 3.5 times of absolute ethanol solution, wherein the mass ratio of the LLDPE to the ZnO nanoparticles is 1:3.5, ultrasonically dispersing for 1.5h, pouring into a spray gun, spraying on the surface of a pretreated nickel-titanium alloy plate, wherein the spraying pressure is 0.5Mpa and the distance is 20cm, then placing the nickel-titanium alloy plate in a high-temperature electric furnace, keeping the temperature at 45 ℃ for 1.5h, and keeping the temperature at 320 ℃ for 90min to obtain the LLDPE-ZnO nickel-titanium alloy plate with the LLDPE and ZnO on the surface.
3. Preparation of LLDPE-ZnO-SA nickel-titanium alloy plate
Dispersing stearic acid powder in 2.5 times of absolute ethyl alcohol solution, ultrasonically dispersing for 8min, then placing the LLDPE-ZnO nickel-titanium alloy plate in the stearic acid solution, and soaking for 1.5h to prepare the LLDPE-ZnO-SA nickel-titanium alloy plate.
According to the same method as the example 1, the contact angles of water and glycerol on the surface of the LLDPE-ZnO-SA nickel-titanium alloy plate are respectively 123.0 +/-1.8 degrees and 116.7 +/-2.2 degrees; the adhesion amount of smooth muscle cells on the surface of the LLDPE-ZnO-SA nickel-titanium alloy plate after 5 hours of culture is 49.0 +/-4.2 cells/mm2(ii) a Inoculating E.coli, and culturing for 6h to obtain the final product with the adhesion amount of 84.7 +/-7.0 cells/mm on the surface of LLDPE-ZnO-SA nickel-titanium alloy plate2。
Comparative example 3
1. Pretreatment of nickel-titanium alloy sheet
Soaking the nickel-titanium alloy plate with acetone to remove oil, taking out, ultrasonically cleaning with absolute ethyl alcohol, ultrasonically cleaning with deionized water, and blow-drying the cleaned nickel-titanium alloy plate with high-pressure nitrogen. Placing into a clean sealed container containing hydrobromic acid containing 0.4M HBr, 2M hydrochloric acid, and 3.5M acetic acid, placing in dark for 4 hr, taking out, and placing into a container containing 1.1M H2SO3Placing the solution in a clean sealed container for 20min, taking out, ultrasonically cleaning with deionized water, and blow-drying with high-pressure nitrogen.
2. Preparation of LLDPE-ZnO nickel-titanium alloy plate
Dispersing LLDPE and ZnO nanoparticles in 3 times of absolute ethanol solution, wherein the mass ratio of the LLDPE to the ZnO nanoparticles is 1:3, ultrasonically dispersing for 1.5h, pouring into a spray gun, spraying on the surface of the pretreated nickel-titanium alloy plate, wherein the spraying pressure is 0.5Mpa and the distance is 20cm, then placing the nickel-titanium alloy plate in a high-temperature electric furnace, keeping the temperature at 40 ℃ for 2h, and keeping the temperature at 360 ℃ for 100min to obtain the LLDPE-ZnO nickel-titanium alloy plate with the LLDPE and the ZnO on the surface.
3. Preparation of LLDPE-ZnO-SA nickel-titanium alloy plate
Dispersing stearic acid powder in 2 times of absolute ethyl alcohol solution, ultrasonically dispersing for 5min, then placing the LLDPE-ZnO nickel-titanium alloy plate in the stearic acid solution, and soaking for 1h to prepare the LLDPE-ZnO-SA nickel-titanium alloy plate.
According to the same method as the example 1, the contact angles of water and glycerol on the surface of the LLDPE-ZnO-SA nickel-titanium alloy plate are respectively measured to be 102.7 +/-1.8 degrees and 105.8 +/-2.1 degrees; the adhesion amount of the smooth muscle cells on the surface of the LLDPE-ZnO-SA nickel-titanium alloy plate after 5 hours of culture is 51.4 +/-4.3cells/mm2(ii) a Inoculating E.coli, and culturing for 6h to obtain the final product with the adhesion amount of 85.1 + -7.5 cells/mm2。
Comparative example 4
1. Pretreatment of nickel-titanium alloy sheet
Soaking the nickel-titanium alloy plate with acetone to remove oil, taking out, ultrasonically cleaning with absolute ethyl alcohol, ultrasonically cleaning with deionized water, and blow-drying the cleaned nickel-titanium alloy plate with high-pressure nitrogen. Placing into a clean sealed container containing hydrobromic acid containing 0.4M HBr, 2M hydrochloric acid, and 3.5M acetic acid, placing in dark for 4 hr, taking out, and placing into a container containing 1M H2SO3Placing the solution in a clean sealed container for 20min, taking out, ultrasonically cleaning with deionized water, and blow-drying with high-pressure nitrogen.
2. Preparation of LLDPE-ZnO nickel-titanium alloy plate
The preparation method comprises the steps of dispersing polyphenylene sulfide (PPS) and ZnO nanoparticles in 3 times of absolute ethanol solution, wherein the mass ratio of the PPS to the ZnO nanoparticles is 1:3, ultrasonically dispersing for 1.5h, pouring into a spray gun, spraying onto the surface of a pretreated nickel-titanium alloy plate, wherein the spraying pressure is 0.5Mpa and the distance is 20cm, then placing in a high-temperature electric furnace, keeping the temperature at 40 ℃ for 2h, and keeping the temperature at 360 ℃ for 100min to obtain the LLDPE-ZnO nickel-titanium alloy plate with LLDPE and ZnO on the surface.
3. Preparation of LLDPE-ZnO-SA nickel-titanium alloy plate
Dispersing stearic acid powder in 2 times of absolute ethyl alcohol solution, ultrasonically dispersing for 5min, then placing the LLDPE-ZnO nickel-titanium alloy plate in the stearic acid solution, and soaking for 1h to prepare the LLDPE-ZnO-SA nickel-titanium alloy plate.
According to the same method as the example 1, the contact angles of water and glycerol on the surface of the LLDPE-ZnO-SA nickel-titanium alloy plate are respectively measured to be 136.0 +/-2.1 degrees and 128.4 +/-2.2 degrees; the adhesion amount of smooth muscle cells on the surface of the LLDPE-ZnO-SA nickel-titanium alloy plate after 5 hours of culture is 45.8 +/-4.6 cells/mm2(ii) a Inoculating E.coli, and culturing for 6h to obtain the final product with the adhesion amount of 82.4 + -6.9 cells/mm on the surface of LLDPE-ZnO-SA nickel-titanium alloy plate2。
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.

Claims (4)

1. A composite coating nickel-titanium alloy material with super-hydrophobic and oleophobic properties is characterized by being prepared by the following method:
a) removing oil from the surface of nickel-titanium alloy material, adding into mixed acid solution containing 0.2-0.4M HBr, 1.8-2.2M hydrochloric acid, and 2.5-3.5M acetic acid, placing in dark for 3-4 hr, taking out, and adding into 0.5-1M H2SO3Treating in the solution for 10-30min, cleaning with deionized water, and blow-drying to obtain a pretreated nickel-titanium alloy material;
b) dispersing LLDPE and ZnO nanoparticles into an absolute ethanol solution which is 3-4 times of the total mass of the LLDPE and ZnO nanoparticles, wherein the mass ratio of the LLDPE to the ZnO nanoparticles is 1 (3-4), ultrasonically dispersing for 1-2h, then spraying the solution on the surface of the pretreated nickel-titanium alloy material, and then placing the pretreated nickel-titanium alloy material at 40-50 ℃ for 1-2h and 300-360 ℃ for 80-100min to obtain an LLDPE-ZnO nickel-titanium alloy plate;
c) dispersing stearic acid powder into an absolute ethyl alcohol solution which is 2-3 times of the mass of the stearic acid powder, ultrasonically dispersing for 5-10min, then placing the LLDPE-ZnO nickel-titanium alloy plate into the stearic acid solution, and soaking for 1-2h to prepare the LLDPE-ZnO-SA nickel-titanium alloy plate, namely the composite coating nickel-titanium alloy material.
2. The composite coating nickel titanium alloy material of claim 1, wherein in the step a), the step of removing oil from the surface of the nickel titanium alloy material comprises the following specific steps: soaking the nickel-titanium alloy material in acetone to remove oil, taking out, ultrasonically cleaning with absolute ethyl alcohol, ultrasonically cleaning with deionized water, and finally drying with high-pressure nitrogen.
3. A preparation method of a composite coating nickel-titanium alloy material with super-hydrophobic and oleophobic properties is characterized by comprising the following steps:
a) removing oil from the surface of nickel-titanium alloy material, adding into mixed acid solution containing 0.2-0.4M HBr, 1.8-2.2M hydrochloric acid, and 2.5-3.5M acetic acid, placing in dark for 3-4 hr, taking out, and adding into 0.5-1M H2SO3Treating in the solution for 10-30min, cleaning with deionized water, and blow-drying to obtain a pretreated nickel-titanium alloy material;
b) dispersing LLDPE and ZnO nanoparticles into an absolute ethanol solution which is 3-4 times of the total mass of the LLDPE and ZnO nanoparticles, wherein the mass ratio of the LLDPE to the ZnO nanoparticles is 1 (3-4), ultrasonically dispersing for 1-2h, then spraying the solution on the surface of the pretreated nickel-titanium alloy material, and then placing the pretreated nickel-titanium alloy material at 40-50 ℃ for 1-2h and 300-360 ℃ for 80-100min to obtain an LLDPE-ZnO nickel-titanium alloy plate;
c) dispersing stearic acid powder into an absolute ethyl alcohol solution which is 2-3 times of the mass of the stearic acid powder, ultrasonically dispersing for 5-10min, then placing the LLDPE-ZnO nickel-titanium alloy plate into the stearic acid solution, and soaking for 1-2h to prepare the LLDPE-ZnO-SA nickel-titanium alloy plate, namely the composite coating nickel-titanium alloy material.
4. Use of the composite coated nickel titanium alloy material of claim 1 or 2 in the manufacture of a medical device.
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