CN111472004A - Surface treatment method for improving bioactivity of medical degradable zinc alloy - Google Patents

Surface treatment method for improving bioactivity of medical degradable zinc alloy Download PDF

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CN111472004A
CN111472004A CN202010377090.1A CN202010377090A CN111472004A CN 111472004 A CN111472004 A CN 111472004A CN 202010377090 A CN202010377090 A CN 202010377090A CN 111472004 A CN111472004 A CN 111472004A
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zinc alloy
sample
bioactivity
deionized water
treatment method
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储成林
王婷
张昕
白晶
薛烽
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Southeast University
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Southeast University
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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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F3/00—Brightening metals by chemical means
    • C23F3/04—Heavy metals
    • C23F3/06—Heavy metals with acidic solutions
    • 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
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • 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
    • A61L27/32—Phosphorus-containing materials, e.g. apatite
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
    • 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
    • A61L2420/00—Materials or methods for coatings medical devices
    • A61L2420/02—Methods for coating medical devices
    • 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 invention provides a surface treatment method for improving the bioactivity of a medical degradable zinc alloy, which comprises the following steps: the surface pretreatment, chemical polishing and composite activation treatment can obviously improve the bioactivity of the zinc alloy after the treatment, and mainly reflect that the hydrophilicity of the surface of the material is obviously increased and the surface can be subjected to uniform and compact calcium-phosphorus layer biological deposition. Pure zinc without any treatment is placed in simulated human body fluid SBF, and a calcium-phosphorus layer is difficult to deposit on the surface of the pure zinc; the current density of the treated zinc alloy is reduced, and the resistance modulus of the coating is reduced. The surface treatment method has the advantages of obvious surface treatment effect, simple method, strong operability, low equipment requirement and low cost, and is suitable for large-scale production.

Description

Surface treatment method for improving bioactivity of medical degradable zinc alloy
Technical Field
The invention aims to solve the technical problem of providing the technical field of medical zinc alloy surface modification, and particularly relates to a treatment method for improving the surface bioactivity of a zinc alloy.
Background
Zinc and zinc alloy are taken as a novel medical degradable material, and have better biocompatibility and biodegradability, the bone tissue implantation instrument material can be gradually degraded along with the time extension in the internal service period of a human body, the degraded product is nontoxic and harmless to the human body, and the zinc alloy have better density and elastic modulus and are similar to the bone tissue of the human body, so that the stress shielding effect can not occur. Importantly, the standard electrode potential of zinc is-0.763 v, is greater than-2.363 v of magnesium and is less than-0.440 v of iron, so that the zinc alloy has more moderate degradation rate and better degradation performance compared with iron-based alloy and magnesium-based alloy. However, the untreated zinc alloy has poor biocompatibility and cannot meet the requirements of clinical medical use, so that the improvement of the surface bioactivity of the zinc alloy is an urgent problem to be solved in the field.
The surface modification is mainly to improve the performances of the zinc alloy such as bioactivity and the like by changing the surface components and the state of the zinc alloy. The better biological activity is embodied as follows: the better the hydrophilicity of the surface of a general material is, the more favorable the adhesion and proliferation of cells on the surface of the material are; secondly, the deposition of calcium and phosphorus layers of the sample in simulated body fluid is also widely used for evaluating the biological activity of the biological material. For untreated zinc alloys, the main action in SBF is to perform material corrosion, rather than deposition of a calcium-phosphorous layer. The zinc alloy after surface treatment is placed in simulated human body fluid SBF, the bionic deposition of a calcium-phosphorus layer can be started in a short time, and calcium-phosphorus layers such as hydroxyapatite and the like are main components of human bones, have good biocompatibility and bone conductivity, can promote the growth of bone tissues, and are ideal substitute and repair materials for the human bones. However, at present, the related research for promoting the medical zinc alloy surface to generate the beneficial effect of calcium-phosphorus layer bionic deposition by a surface modification means is less, so the patent provides a treatment method for improving the bioactivity of the medical zinc alloy.
Disclosure of Invention
The technical problem is as follows: aiming at the defects in the prior art, the invention aims to provide a treatment method for improving the surface bioactivity of medical degradable zinc alloy, and solves the problem of poor bioactivity of the current zinc alloy as a medical degradable biological material.
The technical scheme is as follows: the surface treatment method for improving the bioactivity of the medical degradable zinc alloy comprises the following steps:
step 1, surface pretreatment
Sequentially polishing the surface of a zinc alloy sample to be treated from coarse to fine by using sand paper until the surface is smooth, sequentially cleaning the surface in an ultrasonic cleaning machine by using deionized water and absolute ethyl alcohol, and drying the surface for later use after cleaning;
step 2, chemical polishing
Placing the zinc alloy sample subjected to surface pretreatment in a container containing chemical polishing solution, placing the whole container in a water bath kettle for water bath, taking out the zinc alloy sample after treatment, cleaning the surface of the zinc alloy sample with deionized water, and drying for later use;
step 3, composite activation treatment
Putting the zinc alloy sample subjected to the step 2) into a container containing a hydrogen peroxide solution, putting the whole container into a water bath kettle at the temperature of 30-80 ℃, treating for 30-90min, taking out the zinc alloy sample, cleaning the surface of the zinc alloy sample with deionized water, and drying for later use;
and 4, placing the dried zinc alloy sample in a container containing a sodium hydroxide solution, placing the whole container in a water bath kettle at the temperature of 30-60 ℃, treating for 30-120min, taking out the zinc alloy sample, cleaning the surface of the zinc alloy sample with deionized water, and drying.
Pure zinc with the purity of 99.9 wt% is selected as the zinc alloy sample.
The sand paper is 80#, 200#, 400#, 600#, 800# and 1000# in sequence from coarse to fine.
The volume ratio of the chemical polishing solution is 3:70:292 of sulfuric acid, hydrogen peroxide and deionized water.
Wherein the content of the first and second substances,
and (3) carrying out water bath in the water bath kettle in the step 2), wherein the temperature is 30 ℃, and the treatment time is 15 min.
The chemical polishing solution in the step 2) comprises the following components: the sulfuric acid with the mass fraction of 98%, the hydrogen peroxide with the mass fraction of 30% and the deionized water are mixed according to the proportion of 3:70: 292.
And 3) the mass fraction of the hydrogen peroxide solution in the step 3) is 5%.
And 4) the concentration of the sodium hydroxide in the step 4) is 1-5 mol/L.
Has the advantages that:
(1) the treatment method provided by the invention can obviously increase the surface bioactivity of the zinc alloy. The wetting angle of the zinc alloy treated by the method is reduced, and the hydrophilicity is improved. Generally, the better the hydrophilicity of the material is, the more favorable the adhesion and proliferation of the cell on the surface; when the zinc alloy is placed in simulated human body fluid SBF, a uniform and compact calcium-phosphorus layer can be deposited on the surface of the short-term zinc alloy after treatment. For bone tissues, the calcium-phosphorus layer is a good repairing material and is beneficial to the proliferation and growth of bone cells.
(2) The corrosion speed of the zinc alloy treated by the method is accelerated, and the method is mainly used for destroying the integrity of the surface of the zinc alloy, so that the surface of the material loses the protection effect on a matrix, and the corrosion of the zinc alloy is accelerated. According to the fitting of electrochemical test data, the impedance modulus of the processed zinc alloy is reduced, and the current density is increased, so that the method can effectively regulate and control the degradation speed of the medical zinc alloy.
(3) The method for the biological activation treatment of the surface of the medical zinc alloy is simple in preparation process, and all the used equipment are common equipment; the used chemical raw materials are sodium hydroxide, hydrogen peroxide, sulfuric acid and the like, so that the cost is low; the whole operation is simple and convenient, the controllability is good, and the method is suitable for industrial large-scale production and application.
Drawings
FIG. 1 is SEM pictures of comparative example 1, example 1 and example 2,
(A) comparative example 1 morphology after surface pretreatment, (B) morphology of the calcium-phosphorus layer deposited after SBF72h in comparative example 1, (C) morphology of the calcium-phosphorus layer deposited after SBF72h in example 1, (D) morphology of the calcium-phosphorus layer deposited after SBF72h in example 2.
FIG. 2 wetting Angle test for comparative example 1, and example 2,
(a) comparative example 1 wetting angle, (b) is example 1 wetting angle (c) example 2 wetting angle;
FIG. 3 Tafel curves for comparative example 1, and example 2,
FIG. 4 is a graph of Nyqusit, frequency-phase angle, and frequency-modulus for comparative example 1, and example 2.
(a) Nyqusit curves for comparative example 1, examples 1, 2; (b) frequency versus phase angle plots for comparative example 1, examples 1, 2; (c) frequency-modulus plots for comparative example 1, examples 1, 2; (d) electrochemical equivalent circuit diagrams of comparative example 1 and examples 1 and 2.
Detailed Description
In order to achieve the purpose, the surface treatment method for improving the bioactivity of the medical degradable zinc alloy, provided by the invention, comprises the following steps:
1) surface preparation
Sequentially polishing the surface of a zinc alloy sample to be treated to be smooth by using abrasive paper, sequentially cleaning the surface of the zinc alloy sample in an ultrasonic cleaning machine by using deionized water and absolute ethyl alcohol, and drying the surface of the zinc alloy sample for later use after cleaning.
2) Chemical polishing
And (3) placing the zinc alloy subjected to surface pretreatment into a chemical polishing solution, placing the integral device into a water bath, taking out the sample after treatment, cleaning the surface of the sample with deionized water, and blow-drying for later use.
3) Composite activation treatment
Putting the sample subjected to the step 2) into a hydrogen peroxide solution, putting the integrated device into a water bath kettle at the temperature of 30-80 ℃, treating for 30-90min, taking out the sample, cleaning the surface of the sample with deionized water, and drying for later use; and (3) placing the dried sample in a sodium hydroxide solution, placing the sample in a water bath kettle at the temperature of 30-60 ℃, treating for 30-120min, taking out the sample, cleaning the surface of the sample with deionized water, and drying.
Further, pure zinc with a purity of 99.9% was selected.
Further, the roughness of the sand paper is 80#, 200#, 400#, 600#, 800#, 1000 #.
Further, the water bath temperature in the step 2) is 30 ℃, and the treatment time is 15 min.
Further, the chemical polishing solution used in the step 1) is a mixed solution of sulfuric acid, hydrogen peroxide and deionized water in a volume ratio of 3:70: 292.
Further, the polishing solution in step 2): 98 percent of sulfuric acid by mass fraction, 30 percent of hydrogen peroxide by mass fraction and deionized water.
Further, the mass fraction of the hydrogen peroxide solution in the step 3) is 5%.
Further, the concentration of the sodium hydroxide in the step 3) is 1-5 mol/L.
The invention is further described in detail below with reference to specific embodiments and the accompanying drawings. The following examples are based on pure zinc as the subject of study, example 1 being the best example, comparative example 1 being the control, and example 2 being an example with parameters within this range.
Comparative example 1
And (3) polishing the sample to a smooth pure zinc sample by using coarse-to-fine SiC sand paper (the roughness of the sand paper is 80#, 200#, 400#, 600#, 800#, and 1000 #).
Placing the sample in corrosive solution, wherein the corrosive medium is simulated human body fluid SBF solution (composition: 8.035 g/L NaCl, 0.355 g/L NaHCO) with pH of 7.43、0.225g/LKCl、0.231g/LK2HPO4·3H2O、0.311g/LMgCl2·6H2O、39ml/LHCl、0.292g/LCaCl2、0.292g/LNa2SO4、0.072g/LTris)。
After the SBF soaking for 72 hours, the untreated pure zinc surface is not subjected to deposition of a large amount of calcium-phosphorus layers, more corrosion products are accumulated, and the accumulation of the corrosion products is more dispersed.
The wetting angle of comparative example 1 was 94 deg., and the material exhibited hydrophobicity.
Fitting the AC impedance spectrum of comparative example 1 to obtain an impedance value of 4327. omega. cm2. Polarization curve solving of self-corrosionThe current density was 3.33 × 10-5A/cm2。
Examples 1,
1. The surface of a pure zinc sample is polished to be smooth and free of scratches by SiC sand paper (the roughness of the sand paper is 80#, 200#, 400#, 600#, 800#, and 1000#), and then is cleaned by deionized water and absolute ethyl alcohol in an ultrasonic mode in sequence and is dried for later use.
2. And (3) placing the zinc alloy subjected to surface pretreatment into a solution containing sulfuric acid: hydrogen peroxide: and (3) adding water to a mixed polishing solution of 3:70:292, placing the whole device in a 30 ℃ water bath kettle, treating for 15min, taking out the sample, cleaning the surface of the sample by using deionized water, and drying for later use.
3. And (3) putting the sample subjected to the step (2) into a hydrogen peroxide solution with the concentration of 5%, placing the hydrogen peroxide solution into a water bath kettle at 50 ℃, treating for 60min, cleaning and drying the surface of the sample by using deionized water, placing the sample into a sodium hydroxide solution with the concentration of 1 mol/L, placing the sample into a water bath kettle at 50 ℃, treating for 90min, cleaning and drying the surface of the sample by using the deionized water.
The pure zinc surface after the composite activation treatment has a plurality of holes, and the surface roughness is increased. The surface of the pure zinc after the composite activation treatment is deposited with a uniform calcium-phosphorus layer under the same soaking time, and the calcium-phosphorus layer grows along the surface in a flat way and is uniform and compact.
The wetting angle of the surface treated is changed into 16.2 degrees, the hydrophilicity of the surface of the treated pure zinc is greatly increased, and the bioactivity is increased.
Compared with the comparative example 1, the pure zinc subjected to the composite activation treatment has a reduced self-corrosion potential and an increased self-corrosion current density. The larger the corrosion resistance current, the more likely the sample is to be corroded.
The AC impedance spectrum of example 1 was fitted to obtain an impedance value of 3110. omega. cm2And the polarization radius of the treated pure zinc is obviously reduced, which shows that the corrosion resistance of the treated pure zinc is reduced and the corrosion speed is accelerated.
Examples 2,
1. The surface of a pure zinc sample is polished to be smooth by SiC sand paper (the roughness of the sand paper is 80#, 200#, 400#, 600#, 800#, and 1000#), and then is cleaned by deionized water and absolute ethyl alcohol in an ultrasonic way in sequence and is dried for standby.
2. And (3) placing the zinc alloy subjected to surface pretreatment into a solution containing sulfuric acid: hydrogen peroxide: and (3) adding water to a mixed polishing solution of 3:70:292, placing the whole device in a 30 ℃ water bath kettle, treating for 15min, taking out the sample, cleaning the surface of the sample by using deionized water, and drying for later use.
3. And (3) putting the sample subjected to the step (2) into a hydrogen peroxide solution with the concentration of 5%, placing the hydrogen peroxide solution into a water bath kettle at the temperature of 30 ℃, treating the hydrogen peroxide solution for 30min, cleaning the surface of the sample by using deionized water, drying the sample, placing the sample into a sodium hydroxide solution with the concentration of 1 mol/L, placing the sample into a water bath kettle at the temperature of 30 ℃, treating the sample for 30min, cleaning the surface of the sample by using the deionized water, and drying the sample.
A uniform and compact calcium-phosphorus layer is deposited on the surface of the pure zinc after the composite activation treatment, and the calcium-phosphorus layer grows along the surface in a flat way.
The wetting angle after the surface treatment is changed to 22.5 degrees, which means that the hydrophilicity of the pure zinc surface is greatly increased and the bioactivity is increased after the surface treatment.
Compared with the comparative example 1, the pure zinc subjected to the composite activation treatment has a reduced self-corrosion potential and an increased self-corrosion current density. The larger the corrosion resistance current, the more likely the sample is to be corroded.
The AC impedance spectrum of example 2 was fitted to obtain an impedance value of 3780. omega. cm2And the polarization radius of the treated pure zinc is obviously reduced, which shows that the corrosion resistance of the treated pure zinc is reduced and the corrosion speed is accelerated.
Examples 3,
1. The surface of a pure zinc sample is polished to be smooth by SiC sand paper (the roughness of the sand paper is 80#, 200#, 400#, 600#, 800#, and 1000#), and then is cleaned by deionized water and absolute ethyl alcohol in an ultrasonic way in sequence and is dried for standby.
2. And (3) placing the zinc alloy subjected to surface pretreatment into a solution containing sulfuric acid: hydrogen peroxide: and (3) adding water to a mixed polishing solution of 3:70:292, placing the whole device in a 30 ℃ water bath kettle, treating for 15min, taking out the sample, cleaning the surface of the sample by using deionized water, and drying for later use.
3. And (3) putting the sample subjected to the step (2) into a hydrogen peroxide solution with the concentration of 5%, placing the hydrogen peroxide solution into a water bath kettle at the temperature of 80 ℃, treating the hydrogen peroxide solution for 90min, cleaning the surface of the sample by using deionized water, drying the sample, placing the sample into a sodium hydroxide solution with the concentration of 1 mol/L, placing the sample into a water bath kettle at the temperature of 60 ℃, treating the sample for 120min, cleaning the surface of the sample by using the deionized water, and drying the sample.
Examples 4,
1. The surface of a pure zinc sample is polished to be smooth by SiC sand paper (the roughness of the sand paper is 80#, 200#, 400#, 600#, 800#, and 1000#), and then is cleaned by deionized water and absolute ethyl alcohol in an ultrasonic way in sequence and is dried for standby.
2. And (3) placing the zinc alloy subjected to surface pretreatment into a solution containing sulfuric acid: hydrogen peroxide: and (3) adding water to a mixed polishing solution of 3:70:292, placing the whole device in a 30 ℃ water bath kettle, treating for 15min, taking out the sample, cleaning the surface of the sample by using deionized water, and drying for later use.
3. And (3) putting the sample subjected to the step (2) into a hydrogen peroxide solution with the concentration of 5%, placing the hydrogen peroxide solution into a water bath kettle at the temperature of 30 ℃, treating the hydrogen peroxide solution for 30min, cleaning the surface of the sample by using deionized water, drying the sample, placing the sample into a sodium hydroxide solution with the concentration of 1 mol/L, placing the sample into a water bath kettle at the temperature of 30 ℃, treating the sample for 30min, cleaning the surface of the sample by using the deionized water, and drying the sample.
The data obtained in the above examples were collated to give Table 1
TABLE 1
Figure BDA0002480546530000071
As can be seen from Table 1, after the surface of the pure zinc is subjected to composite activation treatment, the wetting angles of the pure zinc from the surface are reduced, and the hydrophilicity is greatly increased; the pure zinc is placed in SBF, a uniform and compact calcium-phosphorus layer film layer is deposited on the surface of the treated pure zinc in a short time, untreated pure zinc shows that the calcium-phosphorus layer deposition is difficult to carry out under the same condition, and the biocompatibility of the surface of the pure zinc is greatly increased after the pure zinc is treated by the method. Compared with electrochemical data, the impedance value is reduced from the average value, and the corrosion current density is increased according to the polarization curve, which shows that the corrosion degradation speed of the treated pure zinc is accelerated.
Finally, the above examples are only used to illustrate the technical solution and implementation steps of the present invention, and are not limited to pure zinc, and the surface treatment method is also suitable for other medical zinc alloys. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art will appreciate that modifications and similar substitutions can be made thereto without departing from the spirit and scope of the present invention as set forth in the appended claims.

Claims (8)

1. A surface treatment method for improving the bioactivity of medical degradable zinc alloy is characterized by comprising the following steps:
step 1, surface pretreatment
Sequentially polishing the surface of a zinc alloy sample to be treated from coarse to fine by using sand paper until the surface is smooth, sequentially cleaning the surface in an ultrasonic cleaning machine by using deionized water and absolute ethyl alcohol, and drying the surface for later use after cleaning;
step 2, chemical polishing
Placing the zinc alloy sample subjected to surface pretreatment in a container containing chemical polishing solution, placing the whole container in a water bath kettle for water bath, taking out the zinc alloy sample after treatment, cleaning the surface of the zinc alloy sample with deionized water, and drying for later use;
step 3, composite activation treatment
Putting the zinc alloy sample subjected to the step 2) into a container containing a hydrogen peroxide solution, putting the whole container into a water bath kettle at the temperature of 30-80 ℃, treating for 30-90min, taking out the zinc alloy sample, cleaning the surface of the zinc alloy sample with deionized water, and drying for later use;
and 4, placing the dried zinc alloy sample in a container containing a sodium hydroxide solution, placing the whole container in a water bath kettle at the temperature of 30-60 ℃, treating for 30-120min, taking out the zinc alloy sample, cleaning the surface of the zinc alloy sample with deionized water, and drying.
2. The method as claimed in claim 1, wherein the zinc alloy sample is pure zinc with a purity of 99.9 wt%.
3. The treatment method for improving the bioactivity of the surface of zinc alloy according to claim 1, wherein the sand paper has a coarse-to-fine mesh size of 80#, 200#, 400#, 600#, 800#, and 1000 #.
4. The treatment method for improving the bioactivity of the surface of zinc alloy according to claim 1, wherein the chemical polishing solution is a chemical polishing solution prepared from the following components in a volume ratio of 3:70:292 of sulfuric acid, hydrogen peroxide and deionized water.
5. The treatment method for improving the surface bioactivity of zinc alloy according to claim 1, wherein the water bath in the water bath kettle in the step 2) is carried out at 30 ℃ for 15 min.
6. The method as claimed in claim 1, wherein the chemical polishing solution of step 2) comprises: the sulfuric acid with the mass fraction of 98%, the hydrogen peroxide with the mass fraction of 30% and the deionized water, wherein the ratio of the sulfuric acid to the hydrogen peroxide to the deionized water is 3:70: 292.
7. The treatment method for improving the bioactivity of the surface of the zinc alloy according to claim 1, wherein the mass fraction of the hydrogen peroxide solution in the step 3) is 5%.
8. The treatment method for improving the bioactivity of the surface of the zinc alloy as claimed in claim 1, wherein the concentration of the sodium hydroxide in the step 4) is 1-5 mol/L.
CN202010377090.1A 2020-05-07 2020-05-07 Surface treatment method for improving bioactivity of medical degradable zinc alloy Pending CN111472004A (en)

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