CN102146562B - Silicate coating-containing absorbable medical magnesium-based metal and preparation method and application thereof - Google Patents
Silicate coating-containing absorbable medical magnesium-based metal and preparation method and application thereof Download PDFInfo
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- CN102146562B CN102146562B CN2010101084059A CN201010108405A CN102146562B CN 102146562 B CN102146562 B CN 102146562B CN 2010101084059 A CN2010101084059 A CN 2010101084059A CN 201010108405 A CN201010108405 A CN 201010108405A CN 102146562 B CN102146562 B CN 102146562B
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Abstract
The invention relates to a silicate coating-containing absorbable medical magnesium-based metal, a preparation method and application thereof. The magnesium-based metal belongs to the field of biomedical appliances and is particularly suitable for the field of medical appliances used for bone trauma surgery, reparative and reconstructive surgery, and coining and cosmetology. The magnesium-based metal consists of a magnesium-based metal substrate and a silicate coating formed on the surface of the substrate, wherein the silicate coating consists of magnesium silicate (Mg2SiO4) and magnesium oxide. In an alkaline environment, a protective coating is prepared on the surface of the magnesium-based metal by a low temperature chemical deposition method. The method is simple and feasible and has low requirement on equipment; and the thickness of the coating can be controlled to be between several hundred nanometers and 5 mu m. The protective coating is uniform and dense, has high corrosion resistance, simultaneously has high biological activity and metal appearance, and can control the degradation rate of the magnesium-based metal and the dissolution rate of magnesium ions so as to control the biological activity and the absorption rate of magnesium-based metal implanted devices in organisms. The magnesium-based metal can be used for preparing intra-osteal fixing devices.
Description
Technical field
The present invention relates to a kind of absorbable medical magnesium-base metal that contains silicate coating, belong to the biologic medical instrument field, be mainly used in bone wound surgery, reconstruction surgery, shaping and beauty and use medical instruments field.
Background technology
Magnesium-base metal is one of the lightest structural metallic materials, and density and people's bone density are very near (1.75g/cm
3), having high specific strength, Young's modulus is about 45GPa, and mechanical property and people's osseous tissue have good matching.Magnesium-base metal is active strong, and is very active under the body fluid environment, is prone to corrode in the environment in vivo, thereby realizes degraded in vivo.Magnesium-base metal is as the degradable embedded material, and it is too fast to implant the back degradation speed, particularly at the implantation initial stage, causes local environment pH value too high, and wound is difficult for healing, produces inflammatory reaction etc.Simultaneously, because it is too fast to degrade, its degraded product hydrogen fails in time to be absorbed and form bubble and assemble at tissue local by body, and process for treating surface is the efficient ways that control can absorb magnesium-base metal degradation in vivo speed.
Summary of the invention
The absorbable medical magnesium-base metal that the purpose of this invention is to provide a kind of excellent performance with silicate coating; Through contain the bioactive coating of silicate in the magnesium-base metal surface preparation; Can improve the corrosion resistance nature of magnesium-base metal, improve its biology performance.This modified coating is applied to the magnesium-base metal medicine equipment, can solves problems such as absorbable medical magnesium-base metal degradation speed is fast, surface bioactive is low, promote the organization healing of device implant site.
Technical scheme of the present invention is:
A kind of absorbable medical magnesium-base metal that contains silicate coating is made up of magnesium-base metal matrix and the silicate coating that on matrix surface, forms, and silicate coating is by Magnesium Silicate q-agent (Mg2SiO
4) and Natural manganese dioxide (MgO) form, its thickness between 100 nanometers to 5 micron, coating mesosilicic acid magnesium (Mg2SiO
4) content is 25～50wt%, all the other are Natural manganese dioxide.
The said preparation method who contains the absorbable medical magnesium-base metal of silicate coating:
(1) pre-treatment of magnesium-base metal matrix
With the magnesium-base metal surface degreasing with after carrying out surface activation process, for use.
The art breading liquefaction of said surface activation process is learned composition and is filled a prescription as follows:
Glacial acetic acid min. 99.5 100-400ml;
Zero(ppm) water 100-300ml;
Nitric acid 1-30ml;
Oxalic acid 0.1-10g;
Treatment temp is room temperature (20-27 a ℃), and the treatment time is 10-30 second.
(2) with the magnesium-base metal after (1) processing, use tap water, zero(ppm) water, absolute ethyl alcohol and zero(ppm) water rinsing successively, dry up, for use.
(3) preparation Combined Processing liquid
Combined Processing liquid is the alkaline aqueous solution that contains silicate, and it is formed as follows:
Sodium hydroxide (NaOH) 1-100g/L (being preferably 5-50g/L);
Trisodium phosphate (Na
4P
2O
710H
2O) 1-100g/L (being preferably 30-50g/L);
Water glass (Na
2SiO
39H
2O) 1-100g/L (being preferably 5-20g/L);
Above component is simple, environmental protection.
The best composition as follows:
Sodium hydroxide (NaOH) 40g/L;
Trisodium phosphate (Na
4P
2O
710H
2O) 50g/L;
Water glass (Na
2SiO
39H
2O) 20g/L;
(4) place (3) to go on foot the Combined Processing liquid of preparation the magnesium-base metal after (2) processing, the temperature of Combined Processing liquid is 20-100 ℃, standing and reacting 3-240h.During sample thief, clean 30～60 ℃ of oven dry down successively with tap water, zero(ppm) water, absolute ethyl alcohol.
The said preparation method who contains the absorbable medical magnesium-base metal of silicate coating in Combined Processing liquid process for preparation, adopts the mode of magnetic agitation that solution is mixed.
The present invention contains the absorbable medical magnesium-base metal of silicate coating, can be used for preparing internal fixation device spare.Internal fixation device spare comprises: Steel Plate For Fixation Of Fracture and supporting screw, intramedullary nail, fracture dislocation of spine fixation device, spicule or play screw of fixed action etc. separately.
Among the present invention; Magnesium-base metal comprises pure magnesium or magnesiumalloy, and magnesiumalloy is a kind of of different alloy system such as magnalium series, magnesium manganese series, magnesium zinc series, magnesium zirconium series, magnesium rare earth metal, magnesium lithium series, magnesium calcium series or the three component system or the polynary system magnesiumalloy that are formed by these system combinations.
Characteristics of the present invention are:
1, coating treatment process of the present invention has been avoided the influence of pyroprocessing to magnesium-base metal matrix mechanical property, energy-conserving and environment-protective in alkaline environment, carrying out under the low temperature.
2, the present invention utilizes the excellent biological activity characteristics of magnesium-base metal; Make that promptly there is bone like apatite layer formation the short period to institute's internal fixation device spare that designs in vivo; And, around implant devices, form freshman bone tissue with the prolongation of implanting the time, promote the healing of damaged part.
3, the present invention fully combines to absorb the advantage of magnesium-base metal and surface-treated thereof; Select and optimize surface reforming layer according to the age needs of internal fixation device spare; Reduce the initial stage degradation speed of magnesium-base metal; Make the degraded of the early stage under arms slowly uniform corrosion of medical device, avoid local corrosion phenomenons such as spot corrosion, guarantee that the mechanical property of implant satisfies load bearing requirements; For implant provides bioactivity surface, degradation speed and biological activity before magnesium-base metal implant after the processing is handled all have clear improvement; Can fast and safely degrade at degraded later stage (when being the approaching design of implant age) magnesium-base metal.
4, coating is smooth, has the good metal outward appearance.The color of coating is main with golden yellow, and the difference of science and engineering skill slightly changes everywhere, and color can design according to user's attractive in appearance and performance requirement.
5, safe, practical property is good.Magnesium is the major element that is only second to calcium, sodium and potassium in the human body, and everyone the daily requirement amount of being grown up is greater than 350mg, and it participates in a series of metabolic processes in the body.Can absorb finally be corroded under the physiological environment in vivo degraded and absorbed or metabolism by body of magnesium-base metal Steel Plate For Fixation Of Fracture and screws, its degraded product mainly is the mg ion of needed by human body.Magnesium is the needed by human body major element, and contained other alloying element content is all within the claimed range of bio-medical.Therefore, it is safe adopting the magnesium-base metal medicine equipment that absorbs of the present invention, has very big advantage and application prospect.
6, Young's modulus is low.Traditional metal internal fixation device spare can absorb magnesium-base metal and have density and the Young's modulus more approaching with people's bone relatively.The density of magnesium-base metal is 1.74g/cm
3About, with the Compact bone density (1.75g/cm of people's bone
3) very approaching; The Young's modulus of magnesium-base metal is about 45GPa, near the Young's modulus (about 20GPa) of people's bone.Therefore, magnesium-base metal can be avoided stress-shielding effect as the bone fixture, the good mechanical matching arranged with body bone tissue.
Description of drawings
Fig. 1 is AZ31B Mg alloy surface Magnesium Silicate q-agent (Mg
2SiO
4The surface of)-magnesium oxide coating (a), cross section (b) microscopic appearance.
Fig. 2 is the biological activity device surface coating XPS collection of illustrative plates that adopts the present invention's preparation; Wherein, (a) figure is the XPS figure of element silicon; (b) figure is the XPS figure of oxygen element.
Fig. 3 be adopt the present invention's preparation have a silicate (Mg
2SiO
4The AZ31B magnesiumalloy of)-magnesium oxide coating soaks the macro morphology after 90 days with the AZ31B magnesiumalloy that does not carry out the coating processing in simulated body fluid.
Embodiment
Embodiment 1
With AZ31B (magnesium-aluminium system) magnesiumalloy is research object, and magnesiumalloy is cut into the sample of Φ 10 * 5mm, carries out fine grinding with 1000#, 2000# abrasive paper for metallograph respectively, sull and other impurity of removal Mg alloy surface.After magnesiumalloy carried out oil removing, surface activation process, for use.
The art breading liquefaction of said surface activation process is learned composition and is filled a prescription as follows: consisting of Glacial acetic acid min. 99.5 200ml, and zero(ppm) water 170ml, nitric acid 8ml carries out in the aqueous solution of oxalic acid 0.5g, and treatment temp is a room temperature, and the treatment time is 20 seconds.
The magnesiumalloy that will pass through after the above-mentioned processing is used tap water, zero(ppm) water, absolute ethyl alcohol and zero(ppm) water rinsing successively, dries up, and is for use.
Combined Processing liquid is the alkaline aqueous solution that contains silicate, and it is formed as follows: sodium hydroxide (NaOH) 10g/L, trisodium phosphate (Na
4P
2O
710H
2O) 50g/L, water glass (Na
2SiO
39H
2O) aqueous solution of 5g/L in Combined Processing liquid process for preparation, adopts the mode of magnetic agitation that solution is mixed.After mixing, sample for use is placed treatment solution, temperature is 60 ℃, and the treatment time is 10h.
During sample thief, clean 37 ℃ of oven dry down successively with tap water, zero(ppm) water, absolute ethyl alcohol.
As shown in Figure 1, from Mg alloy surface Magnesium Silicate q-agent (Mg
2SiO
4The microscopic appearance of)-magnesium oxide coating can be found out: the coating even compact is good with matrix bond.The color of protective coating is golden yellow, and its thickness is about 2 μ m, coating mesosilicic acid magnesium (Mg
2SiO
4) content is 26.5wt%, all the other are Natural manganese dioxide.
As shown in Figure 2, use the top coat XPS collection of illustrative plates that the present invention obtains the biologically active device, the XPS figure according to element silicon and oxygen element can explain coating mesosilicic acid magnesium (Mg
2SiO
4) existence.
Embodiment 2
With ZK60 (magnesium-zinc-zirconium) magnesiumalloy is research object, and magnesiumalloy is cut into the sample of Φ 10 * 5mm, carries out fine grinding with 1000#, 2000# abrasive paper for metallograph respectively, removes sull and other impurity of Mg alloy surface.After magnesiumalloy carried out oil removing, surface activation process, for use.
The art breading liquefaction of said surface activation process is learned composition and is filled a prescription as follows: Glacial acetic acid min. 99.5 300ml, and zero(ppm) water 200ml, nitric acid 15ml carries out in the aqueous solution of oxalic acid 3g, and treatment temp is a room temperature, and the treatment time is 30 seconds.
The magnesiumalloy that will pass through after the above-mentioned processing is used tap water, zero(ppm) water, absolute ethyl alcohol and zero(ppm) water rinsing successively, dries up, and is for use.
Combined Processing liquid is the alkaline aqueous solution that contains silicate, and it is formed as follows: sodium hydroxide (NaOH) 50g/L, trisodium phosphate (Na
4P
2O
710H
2O) 40g/L, water glass (Na
2SiO
39H
2O) aqueous solution of 10g/L in Combined Processing liquid process for preparation, adopts the mode of magnetic agitation that solution is mixed.After mixing, sample for use is placed treatment solution, temperature is 80 ℃, and the treatment time is 72h.
During sample thief, clean 37 ℃ of oven dry down successively with tap water, zero(ppm) water, absolute ethyl alcohol.
In the present embodiment, the color of protective coating is bronze-colored, and its thickness is about 3 μ m.Protective coating is mainly by Magnesium Silicate q-agent (Mg
2SiO
4) and Natural manganese dioxide (MgO) composition, coating mesosilicic acid magnesium (Mg
2SiO
4) content is 38wt%, all the other are Natural manganese dioxide.
Embodiment 3
With AZ31B (magnesium-aluminium system) magnesiumalloy is research object, and magnesiumalloy is cut into the sample of Φ 10 * 5mm, carries out fine grinding with 1000#, 2000# abrasive paper for metallograph respectively, sull and other impurity of removal Mg alloy surface.After magnesiumalloy carried out oil removing, surface activation process, for use.
The art breading liquefaction of said surface activation process is learned composition and is filled a prescription as follows: Glacial acetic acid min. 99.5 100ml, and zero(ppm) water 300ml, nitric acid 30ml carries out in the aqueous solution of oxalic acid 8g, and treatment temp is a room temperature, and the treatment time is 20 seconds.
The magnesiumalloy that will pass through after the above-mentioned processing is used tap water, zero(ppm) water, absolute ethyl alcohol and zero(ppm) water rinsing successively, dries up, and is for use.
Combined Processing liquid is the alkaline aqueous solution that contains silicate, and it is formed as follows: sodium hydroxide (NaOH) 40g/L, trisodium phosphate (Na
4P
2O
710H
2O) 50g/L, water glass (Na
2SiO
39H
2O) aqueous solution of 20g/L in Combined Processing liquid process for preparation, adopts the mode of magnetic agitation that solution is mixed.After mixing, sample for use is placed treatment solution, temperature is 50 ℃, and the treatment time is 120h.
During sample thief, clean 50 ℃ of oven dry down successively with tap water, zero(ppm) water, absolute ethyl alcohol.
In the present embodiment, the color of protective coating is golden yellow, and its thickness is about 5 μ m.Protective coating is mainly by Magnesium Silicate q-agent (Mg
2SiO
4) and Natural manganese dioxide (MgO) composition, coating mesosilicic acid magnesium (Mg
2SiO
4) content is 46wt%, all the other are Natural manganese dioxide.
Embodiment 4
With Mg-Mn-Zn (Mg-1.2Mn-1.0Zn wt%) alloy is research object, and magnesiumalloy is cut into the sample of Φ 10 * 5mm, carries out fine grinding with 1000#, 2000# abrasive paper for metallograph respectively, removes sull and other impurity of Mg alloy surface.After magnesiumalloy carried out oil removing, surface activation process, for use.
The art breading liquefaction of said surface activation process is learned composition and is filled a prescription as follows: Glacial acetic acid min. 99.5 100ml, and zero(ppm) water 300ml, nitric acid 30ml carries out in the aqueous solution of oxalic acid 8g, and treatment temp is a room temperature, and the treatment time is 20 seconds.
The magnesiumalloy that will pass through after the above-mentioned processing is used tap water, zero(ppm) water, absolute ethyl alcohol and zero(ppm) water rinsing successively, dries up, and is for use.
Combined Processing liquid is the alkaline aqueous solution that contains silicate, and it is formed as follows: sodium hydroxide (NaOH) 5g/L, trisodium phosphate (Na
4P
2O
710H
2O) 30g/L, water glass (Na
2SiO
39H
2O) aqueous solution of 5g/L in Combined Processing liquid process for preparation, adopts the mode of magnetic agitation that solution is mixed.After mixing, sample for use is placed treatment solution, temperature is 60 ℃, and the treatment time is 24h.
During sample thief, clean 50 ℃ of oven dry down successively with tap water, zero(ppm) water, absolute ethyl alcohol.
In the present embodiment, the color of protective coating is light yellow, and its thickness is about 1 μ m.Protective coating is mainly by Magnesium Silicate q-agent (Mg
2SiO
4) and Natural manganese dioxide (MgO) composition, coating mesosilicic acid magnesium (Mg
2SiO
4) content is 28wt%, all the other are Natural manganese dioxide.
Embodiment 5
The AZ31B magnesiumalloy is made into Steel Plate For Fixation Of Fracture and nails such as L shaped, T shape, trilobal, Y shape, abnormity, arc, S shape, according to embodiment 1 technology at the surface preparation protective coating.Has a silicate (Mg with prepared then
2SiO
4The implantation instrument of)-magnesium oxide coating soaked in simulated body fluid 90 days, and there is the bone like apatite layer deposition on the surface, proved that this magnesiumalloy implant has excellent biological activity, can induce freshman bone tissue to form.
Embodiment 6
With the ZK60 magnesiumalloy is research object, and magnesiumalloy is cut into the sample of Φ 10 * 5mm, at the surface preparation protective coating, has a Magnesium Silicate q-agent (Mg with prepared according to embodiment 2 technologies then
2SiO
4The sample of)-magnesium oxide coating is not handled sample and in simulated body fluid, was soaked 90 days respectively with carrying out coating, estimates the protective effect of coating.Soak after 90 days, coated samples keeps original size basically, does not carry out the sample generation heavy corrosion (Fig. 3) that coating is handled, and explains that coating has good protective action to matrix.
Embodiment 7
The AZ31B magnesiumalloy is made into the interference screw of Φ 2.4, according to embodiment 1 technology at the surface preparation protective coating.Above-mentioned magnesiumalloy apparatus with coating is implanted from creating in the pig damaged bone model, carried out the torsional test experiment.The interface nail is analyzed its top coat and is destroyed situation after being torqued into, back-outing, and coating still has good metal appearance, explains that coating and matrix alloy have bonding force preferably.
The result shows, the present invention adopts the cryochemistry deposition method on medical magnesium-base metal surface, to prepare protective coating under alkaline environment, and this method is simple, and equipment requirements is low, and coat-thickness can be controlled between the hundreds of nanometer to 5 micron.Protective coating even compact of the present invention; Corrosion resistance is excellent; Have good biological activity and metal appearance simultaneously; The degradation speed of may command magnesium-base metal and the dissolution rate of mg ion, thus control magnesium-base metal implant devices biological activity and absorption rate in vivo can be used for preparing internal fixation device spare.
Claims (7)
1. an absorbable medical magnesium-base metal that contains silicate coating is characterized in that, this magnesium-base metal is made up of magnesium-base metal matrix and the silicate coating that on matrix surface, forms, and silicate coating is by Mg
2SiO
4Form with Natural manganese dioxide, its thickness between 100 nanometers to 5 micron, Mg in the coating
2SiO
4Content is 25～50wt%, and all the other are Natural manganese dioxide.
2. according to the described absorbable medical magnesium-base metal that contains silicate coating of claim 1; It is characterized in that: magnesium-base metal comprises pure magnesium or magnesiumalloy, the alloy system that magnesiumalloy is magnalium series, magnesium manganese series, magnesium zinc series, magnesium zirconium series, magnesium rare earth metal, magnesium lithium series, magnesium calcium series is different a kind of or the three component system or the polynary system magnesiumalloy that are formed by these system combinations.
3. according to the described preparation method who contains the absorbable medical magnesium-base metal of silicate coating of claim 1, it is characterized in that, comprise the steps:
A. with the magnesium-base metal surface degreasing with carry out surface activation process, for use;
B. the magnesium-base metal after a step handles is used tap water, zero(ppm) water, absolute ethyl alcohol and zero(ppm) water rinsing successively, dries up;
C. prepare Combined Processing liquid, it is formed as follows:
Sodium hydroxide 1-100g/L;
Trisodium phosphate 1-100g/L;
Water glass 1-100g/L;
D. the material after a step, b step being handled places the Combined Processing liquid of c step preparation, and the temperature of Combined Processing liquid is 20-100 ℃, standing and reacting 3-240h;
When material takes out, clean 30～60 ℃ of oven dry down successively with tap water, zero(ppm) water and absolute ethyl alcohol.
4. according to the described preparation method who contains the absorbable medical magnesium-base metal of silicate coating of claim 3, it is characterized in that the art breading liquefaction of surface activation process is learned composition and filled a prescription as follows:
Glacial acetic acid min. 99.5 100-400ml;
Zero(ppm) water 100-300ml;
Nitric acid 1-30ml;
Oxalic acid 0.1-10g;
Treatment temp is a room temperature, and the treatment time is 10-30 second.
5. according to the described preparation method who contains the absorbable medical magnesium-base metal of silicate coating of claim 3, it is characterized in that, in Combined Processing liquid process for preparation, adopt the mode of magnetic agitation that solution is mixed.
6. according to the described application that contains the absorbable medical magnesium-base metal of silicate coating of claim 1, it is characterized in that the absorbable medical magnesium-base metal is used to prepare internal fixation device spare.
7. according to the described application that contains the absorbable medical magnesium-base metal of silicate coating of claim 6; It is characterized in that internal fixation device spare comprises Steel Plate For Fixation Of Fracture and supporting screw, intramedullary nail, fracture dislocation of spine fixation device, spicule or plays the screw of fixed action separately.
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| CN102345151B (en) * | 2011-10-08 | 2013-11-20 | 长安大学 | Method for preparing ZrO2 compound ceramic film on surfaces of magnesium and magnesium alloy through microarc oxidization |
| CN105327397B (en) * | 2015-11-17 | 2018-07-13 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation of the degradable implantation material of the mesoporous calcium silicates coating of medical magnesium alloy surface |
| CN106362220B (en) * | 2016-08-31 | 2019-10-11 | 东北大学 | The modified Mg alloy thin wall pipe in surface and its reverse extrusion mold and preparation method |
| CN113577383B (en) * | 2021-07-21 | 2022-10-14 | 西南交通大学 | Metal-organic/inorganic hybrid coating for promoting bone regeneration and regulating corrosion on degradable metal surface and preparation method thereof |
| CN116565170A (en) * | 2023-05-26 | 2023-08-08 | 广东凯金新能源科技股份有限公司 | Silicon-based anode material, preparation method thereof and secondary battery |
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| CN101560686A (en) * | 2009-04-28 | 2009-10-21 | 先健科技(深圳)有限公司 | Treatment method of magnesium alloy material capable of being absorbed by human body and magnesium alloy composite layer |
| CN101559239A (en) * | 2009-05-27 | 2009-10-21 | 山东大学 | Magnesium base degradable implant material and preparation method thereof |
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| CN101560686A (en) * | 2009-04-28 | 2009-10-21 | 先健科技(深圳)有限公司 | Treatment method of magnesium alloy material capable of being absorbed by human body and magnesium alloy composite layer |
| CN101559239A (en) * | 2009-05-27 | 2009-10-21 | 山东大学 | Magnesium base degradable implant material and preparation method thereof |
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Effective date of registration: 20160115 Address after: 213164 Longmen Road, Wujin hi tech Industrial Development Zone, Jiangsu, China, No. 9, No. Patentee after: TRAUSON MEDICAL INSTRUMENT (CHINA) Co.,Ltd. Address before: 110016 Shenyang, Liaoning Province Cultural Road, No. 72, Shenhe Patentee before: INSTITUTE OF METAL RESEARCH CHINESE ACADEMY OF SCIENCES |
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Effective date of registration: 20190226 Address after: 110016 No. 72, Wenhua Road, Shenhe District, Liaoning, Shenyang Patentee after: INSTITUTE OF METAL RESEARCH CHINESE ACADEMY OF SCIENCES Address before: 213164 No. 9 Longmen Road, Wujin High-tech Industrial Development Zone, Changzhou City, Jiangsu Province Patentee before: TRAUSON MEDICAL INSTRUMENT (CHINA) Co.,Ltd. |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120829 Termination date: 20220210 |