CN103239761A - Silicon-nitride-coated medical magnesium alloy material and preparation method thereof - Google Patents
Silicon-nitride-coated medical magnesium alloy material and preparation method thereof Download PDFInfo
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- CN103239761A CN103239761A CN2013101860284A CN201310186028A CN103239761A CN 103239761 A CN103239761 A CN 103239761A CN 2013101860284 A CN2013101860284 A CN 2013101860284A CN 201310186028 A CN201310186028 A CN 201310186028A CN 103239761 A CN103239761 A CN 103239761A
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Abstract
The invention relates to a silicon-nitride-coated medical magnesium alloy material which is composed of a magnesium alloy substrate and a silicon nitride coating attached to the surface of the magnesium alloy substrate. The preparation method comprises the following steps:1) sanding a magnesium alloy test sample, polishing, deoiling, and carrying out grit blasting to remove surface scales, increase the surface roughness and enhance the bonding firmness between the magnesium alloy substrate and the coating; and 2) preparing a silicon nitride ceramic coating on the surface of the magnesium alloy test sample by a radio-frequency plasma reinforced chemical vapor deposition process or particle beam deposition process. The silicon nitride ceramic coating prepared on the magnesium alloy surface is compact, has high bonding strength with the substrate, and enhances the corrosion resistance of the magnesium alloy; the corrosion resistance and degradation time of the coating can be adjusted by changing the SiH4 ratio and deposition time; and in the process of preparing the magnesium alloy coating, no harmful substance is used, and thus, the invention has the advantages of simple technique, controllable coating and the like, and does not need the preformed film treatment on the sample.
Description
Technical field
The invention belongs to biomedical materials field, particularly a kind of silicon nitride coating medical magnesium alloy material and preparation method.
Background technology
The medical metal material of clinical practice at present mainly contains several big classes such as rustless steel, cobalt-base alloys, titanium alloy.But its elastic modelling quantity in use can produce " stress shielding " far above people's bone, thereby and harmful ion stripping phenomenon often cause serious inflammatory reaction and cause that tissue injury causes graft failure.Particularly implant alloy can not be absorbed in vivo, degrade, and must take out by second operation after injury of the bone healing, has increased patient's economy and psychological burden and sensual misery greatly.Therefore, in operation on bone injury, replace the conventional medical metal material more and more to come into one's own with degradation material, become international research forward position and the focus of current technical field of biological material.
Biological medical degradable macromolecular material such as PLLA, PGA have been used for clinical, but because its elastic modelling quantity is less, can only be used for the not position of load, and catabolite is acidity and easily causes aseptic inflammation, thereby have limited its extensive use.
Magnesium or magnesium alloy are a kind of metal materials of environment degradable in vivo, compare with above-mentioned metal implant material such as titanium alloy, rustless steel, and its advantage mainly shows: 1) density of magnesium is 1.74g/cm
3, and with the Compact bone density (1.80g/cm of people's bone
3) very approaching, its mechanical performance is more near natural bone, and its moderate elastic modelling quantity is the relieve stresses occlusion effect effectively, and union of fracture, implantation body stable had important function; 2) magnesium is the element of needed by human, biologically active, mediation ossification, biocompatibility.About more than 20 grams of magnesium total amount in human body can promote formation, the catalysis of bone and cell or activate body 300 plurality of enzymes system, the metabolism of participation energy i (in vivo), and play a crucial role in conveying, storage and the utilization of energy in life process; 3) the standard equilibrium potential of magnesium is-2.34V, is lower than other alloys, is higher chemistry and electro-chemical activity are shown, and has its inherent advantage as degradation material; 4, aboundresources is cheap.
In sum, magnesium or magnesium alloy have the advantages such as minimal side effect of good medical science safety, mechanical property, controlled etching performance and catabolite, are expected to develop into Biodegradable material of new generation.But, be full of Cl at human body
-Corrosive environment in, magnesium and magnesium alloy can be because degradation rate comparatively fast and in advance lose efficacy.Usually interim implant devices requires 3 months to 1 year active time, can extrapolate magnesium and magnesium alloy should control in 0.1mm/a as the embedded material degradation rate, but discover that the degradation rate of pure magnesium in simulated body fluid is 0.2-1.0mm/a, in zoopery, also find pure magnesium corrosion rate too fast, produce a large amount of hydrogen, thereby cause the material premature failure, limited its clinical practice.
Therefore, make magnesium or its alloy real for clinical, must improve its corrosion resistance, be one of method that effectively improves magnesium and corrosion stability of magnesium alloy energy and handle by face coat.Adopting the good silicon nitride material of biocompatibility that magnesium alloy is carried out surface treatment is a kind of effective control mg-based material degradation rate important channel.
Summary of the invention
The objective of the invention is at above-mentioned existing problems, a kind of silicon nitride coating medical magnesium alloy material and preparation method are provided, this material be combined with coating firmly and coating fine and close, have good heat stability and biological stability, degradation cycle can be by coating layer thickness and hydrogen content regulation and control, be suitable as medium-term and long-term embedded material and use, especially meet the clinical needs of Orthopeadic Surgery.
Technical scheme of the present invention:
A kind of silicon nitride coating medical magnesium alloy material is made of magnesium alloy base material and the silicon nitride coating had on its surface.
A kind of described silicon nitride coating medical magnesium alloy material is preparation method, and step is as follows:
1) with after magnesium alloy sample polishing, polishing, the oil removing, carries out blasting treatment to remove surface scale, to increase the firmness that surface roughness and coating and enhancing magnesium alloy substrate engage with coating;
2) adopt radio frequency plasma to strengthen chemical vapour deposition technique or particle beam sedimentation the magnesium alloy sample after above-mentioned processing, in magnesium alloy sample surface preparation silicon nitride ceramics coating.
The technological parameter that described radio frequency plasma strengthens chemical vapour deposition technique is: magnesium alloy sample is put into the inner chamber settling chamber that radio frequency plasma strengthens chemical vapor depsotition equipment, and it is 1 * 10 that system is evacuated to vacuum
-4-1 * 10
-5Pa is with SiH
4And NH
3Or N
2Gaseous mixture is reactant gas source, and depositing temperature is that 150-450 ℃, radio-frequency power are under the condition of 80-400W, and sedimentation time is 10s-60min, and the cooling back makes the silicon nitride ceramics coating at alloy surface.
Described SiH
4And NH
3Or N
2SiH in the gaseous mixture
4Flow be 10-100sccm; SiH
4And NH
3Or N
2Flow-rate ratio l:0.2-1.
The technological parameter of described particle beam sedimentation is: magnesium alloy sample is put into the particle beam depositing device, as target, is 1 * 10 in vacuum with block silicon nitride
-4-1 * 10
-5Under the Pa, with high-temperature heat treatment again behind the argon ion bombardment, argon ion bombardment voltage is 10-100KeV, and the density of argon ion is (1-5) * 10
16Ions/cm
3, heat treatment temperature is 200-450 ℃, heat treatment time is 2-12h.
The present invention has the following advantages and good effect:
1) the silicon nitride ceramics coating densification for preparing at Mg alloy surface is big with substrate combinating strength, has improved the corrosion resistance of magnesium alloy;
2) by changing SiH
4The decay resistance of ratio and sedimentation time adjustable coating and degradation time;
3) use of unharmful substance in the process of preparation magnesium alloy coating has that technology is simple, coating is controlled, need not sample carried out advantage such as prefabricated membrane processing.
Description of drawings
Accompanying drawing is at AZ31 Mg alloy surface silicon nitride coating and the polarization curve of AZ31 magnesium alloy in simulated body fluid of coating not in different ways.
The specific embodiment
Be described further below in conjunction with the present invention of embodiment.
Embodiment 1:
A kind of silicon nitride coating medical magnesium alloy material is preparation method, and step is as follows:
1) the AZ91D magnesium alloy substrate polished, after the polishing of PG-1 type buffing machine, is cut into the sample of long 10mm, wide 10mm, thick 2mm, ultrasonic cleaning oil removing 10min in acetone soln, ultrasonic cleaning 10min in ethanol again, clean 10min in deionized water for ultrasonic at last, carry out blasting treatment 3min after the drying;
2) above-mentioned magnesium alloy sheet is put into RF-PECVD plasma chemical vapor deposition platform, depositional plane up, system pump down to vacuum is 1 * 10
-5Pa, design temperature are 250 ℃, and frequency 13.56MHz opens heater, treat that settling chamber's temperature stabilization begins deposition in the time of 250 ℃.The radio-frequency power of selecting for use is 200w, makes the flow of silane and ammonia be respectively SiH by quality of regulation effusion meter (MFC)
4And N
2Flow is respectively 50sccm and 10sccm, and behind the deposit 5min, off-response source of the gas, radio frequency source and heater stop deposition, treats sample cooling back taking-up, obtains the silicon nitride coating of even compact.
Polarization curve in the simulated body fluid of this silicon nitride coating and coating not as shown in drawings, show among the figure: the silicon nitride coating that adopts this method, the polarization potential of sample raises, and corrosion resistance strengthens, and proves that silicon nitride coating increases the corrosion proof effectiveness of magnesium alloy substrate.
Embodiment 2:
A kind of silicon nitride coating medical magnesium alloy material is preparation method, and step is as follows:
1) the AZ31 magnesium alloy substrate polished, after the polishing of PG-1 type buffing machine, is cut into the sample of long 10mm, wide 10mm, thick 2mm, ultrasonic cleaning oil removing 10min in acetone, ultrasonic cleaning 10min in ethanol again, clean 10min in deionized water for ultrasonic at last, carry out blasting treatment 3min after the drying;
2) above-mentioned magnesium alloy sheet is put into the inner chamber settling chamber of RF-PECVD equipment, it is 1 * 10 that system is evacuated to vacuum
-4, design temperature is 300 ℃, opens heater, treats that settling chamber's temperature stabilization begins deposition in the time of 300 ℃.The radio-frequency power of selecting for use is 80W, makes the flow of silane and ammonia be respectively 30sccm and 10sccm by quality of regulation effusion meter (MFC).After sedimentation time reached 5min, off-response source of the gas, radio frequency source and heater stopped deposition, treated alloy sheet cooling back taking-up, obtained the silicon nitride coating of even compact.
Polarization curve in the simulated body fluid of this silicon nitride coating and coating not as shown in drawings, show among the figure: the silicon nitride coating that adopts this method, the polarization potential of sample raises, and corrosion resistance strengthens, and proves that silicon nitride coating increases the corrosion proof effectiveness of magnesium alloy substrate.
Embodiment 3:
A kind of silicon nitride coating medical magnesium alloy material is preparation method, and step is as follows:
1) the AZ31 magnesium alloy substrate polished, after the polishing of PG-1 type buffing machine, is cut into the sample of long 10mm, wide 10mm, thick 2mm, ultrasonic cleaning oil removing 10min in acetone, ultrasonic cleaning 10min in ethanol again, clean 10min in deionized water for ultrasonic at last, carry out blasting treatment 3min after the drying;
2) magnesium alloy sample being put into the particle beam depositing device, as target, is 1 * 10 in vacuum with block silicon nitride
-5Under the Pa, with high-temperature heat treatment again behind the argon ion bombardment, argon ion bombardment voltage is at 60KeV, and the density of argon ion is 3 * 10
16Ions/cm
3, the magnesium alloy sample after argon ion bombardment is handled is put into high temperature furnace, be heated to 300 ℃, be incubated 2h, obtain the silicon nitride coating of even compact after the cooling.
Polarization curve in the simulated body fluid of this silicon nitride coating and coating not as shown in drawings, show among the figure: the silicon nitride coating that adopts this method, the polarization potential of sample raises, and corrosion resistance strengthens, and proves that silicon nitride coating increases the corrosion proof effectiveness of magnesium alloy substrate.
Claims (5)
1. silicon nitride coating medical magnesium alloy material is characterized in that: be made of magnesium alloy base material and the silicon nitride coating had on its surface.
One kind according to claim 1 silicon nitride coating medical magnesium alloy material be preparation method, it is characterized in that step is as follows:
1) with after magnesium alloy sample polishing, polishing, the oil removing, carries out blasting treatment to remove surface scale, to increase the firmness that surface roughness and coating and enhancing magnesium alloy substrate engage with coating;
2) adopt radio frequency plasma to strengthen chemical vapour deposition technique or particle beam sedimentation the magnesium alloy sample after above-mentioned processing, in magnesium alloy sample surface preparation silicon nitride ceramics coating.
3. be preparation method according to the described silicon nitride coating medical magnesium alloy of claim 2 material, it is characterized in that: the technological parameter that described radio frequency plasma strengthens chemical vapour deposition technique is: magnesium alloy sample is put into the inner chamber settling chamber that radio frequency plasma strengthens chemical vapor depsotition equipment, and it is 1 * 10 that system is evacuated to vacuum
-4-1 * 10
-5Pa is with SiH
4And NH
3Or N
2Gaseous mixture is reactant gas source, and depositing temperature is that 150-450 ℃, radio-frequency power are under the condition of 80-400W, and sedimentation time is 10s-60min, and the cooling back makes the silicon nitride ceramics coating at alloy surface.
4. be preparation method according to the described silicon nitride coating medical magnesium alloy of claim 2 material, it is characterized in that: described SiH
4And NH
3Or N
2SiH in the gaseous mixture
4Flow be 10-100sccm; SiH
4And NH
3Or N
2Flow-rate ratio l:0.2-1.
5. be preparation method according to the described silicon nitride coating medical magnesium alloy of claim 2 material, it is characterized in that: the technological parameter of described particle beam sedimentation is: magnesium alloy sample is put into the particle beam depositing device, as target, be 1 * 10 in vacuum with block silicon nitride
-5Under the Pa, with high-temperature heat treatment again behind the argon ion bombardment, argon ion bombardment voltage is 10-100KeV, and the density of argon ion is (1-5) * 10
16Ions/cm
3, heat treatment temperature is 200-450 ℃, heat treatment time is 2-12h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106620889A (en) * | 2017-02-16 | 2017-05-10 | 鼎科医疗技术（苏州）有限公司 | Medical device implanted in vivo and manufacturing method of medical device |
| CN107604359A (en) * | 2017-09-22 | 2018-01-19 | 安徽霍山龙鑫金属科技有限公司 | A kind of corrosion-resistant magnesium alloy process of surface treatment |
| WO2019007341A1 (en) * | 2017-07-03 | 2019-01-10 | 无锡华润上华科技有限公司 | Method for improving corrosion resistance of silicon nitride, and method for manufacturing semiconductor device |
| CN109999224A (en) * | 2019-04-17 | 2019-07-12 | 中国科学院理化技术研究所 | A kind of antibacterial and biocompatibility bone implant material and its preparation method and application |
| CN111599672A (en) * | 2019-02-21 | 2020-08-28 | 东莞新科技术研究开发有限公司 | Semiconductor side surface roughness improving method |
| CN115702013A (en) * | 2020-04-23 | 2023-02-14 | 辛特科技公司 | Silicon nitride laser cladding method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106620889A (en) * | 2017-02-16 | 2017-05-10 | 鼎科医疗技术（苏州）有限公司 | Medical device implanted in vivo and manufacturing method of medical device |
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| CN111599672A (en) * | 2019-02-21 | 2020-08-28 | 东莞新科技术研究开发有限公司 | Semiconductor side surface roughness improving method |
| CN109999224A (en) * | 2019-04-17 | 2019-07-12 | 中国科学院理化技术研究所 | A kind of antibacterial and biocompatibility bone implant material and its preparation method and application |
| CN115702013A (en) * | 2020-04-23 | 2023-02-14 | 辛特科技公司 | Silicon nitride laser cladding method |
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Application publication date: 20130814 |