CN101463496A - Method for preparing porous ceramic membrane on zirconium base block amorphous alloy surface - Google Patents
Method for preparing porous ceramic membrane on zirconium base block amorphous alloy surface Download PDFInfo
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- CN101463496A CN101463496A CNA2009100605465A CN200910060546A CN101463496A CN 101463496 A CN101463496 A CN 101463496A CN A2009100605465 A CNA2009100605465 A CN A2009100605465A CN 200910060546 A CN200910060546 A CN 200910060546A CN 101463496 A CN101463496 A CN 101463496A
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- amorphous alloy
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- ceramic membrane
- arc oxidation
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Abstract
A method for preparing a porous ceramic membrane on the surface of a zirconium-based block amorphous alloy belongs to the method for coating bioactive materials on the surface of inert metal materials. The method solves the problems that the ceramic membrane which is rich in calcium and phosphorus can not be directly obtained by using the existing method; and the prepared ceramic membrane and a matrix are weak combined. The method comprises the steps that (1). Electrolyte preparation: calvital, disodium ethylene diamine tetraacetate, sodium silicate and sodium phosphate are blended and prepared into the electrolyte; (2). Micro-arc oxidation: the block amorphous alloy is taken as the anode and the stainless steel is taken as the cathode; the asymmetry alternating-current pulse source is used for micro-arc oxidation; the cooling water is fed in and blended in the oxidation process. The method has simple technique and lower cost. The prepared membrane is formed by rough porous Zro<2> and is in favor of the growth of biological tissue, tightly combines with the matrix to increase the wearing property of implantation materials; wherein, the membrane contains Ca and P, which is in favor of the membrane to form bone-line phosphorite and expands the application of the block amorphous alloy in the biomedicine field.
Description
Technical field
The invention belongs to the method that applies biological active materials at the inert metal material surface, particularly a kind of method at zirconium-based bulk amorphous alloy surface preparation porous ceramic film.
Background technology
Biomedical metal material is the most traditional, most basic biomaterial, accounts for the share of biomaterial market more than 1/3, is mainly used in joint prosthesis, artificial bone, the interventional therapy of Stomatological Department, cardiovascular systems.At present, Chang Yong biomedical metal material mainly contains medical stainless steel (316L), cobalt base alloy, titanium or titanium alloy, niti-shaped memorial alloy and precious metal (as gold, platinum, palladium etc.).But these material ubiquity Young's modulus height, specific tenacity is low, or problem such as biocompatibility difference.The block metal glass that fast development is in recent years got up (Bulk Metallic Glasses-BMGs) brought new dawn for the high-performance biomedical metal material.
Block metal glass is the novel metastable material of a class that grows up the end of the eighties in last century.Because its special structure makes it have excellent mechanics and chemical property.As the Zr base metal glass have high strength (～2GPa), high-fatigue strength (～800MPa), higher hardness (HRC〉50) and high tenacity (KIC～55MPa.m
1/2).Because the structural homogeneity of amorphous material intrinsic, amorphous material has the corrosion resistance nature more excellent than crystalline material usually, is stainless 100-1000 times of 316L as the corrosion resistance of Zr base metal glass in acid-base salt solution.In addition, block metal glass also have lower Young's modulus (50～80GPa) and very high elastic limit (can reach more than 2%), more approach natural bone than biomedical metal material commonly used at present, therefore have better mechanical compatibility.Therefore the Zr bast block metal glass has broad application prospects at aspects such as joint prosthesis, artificial bones.In addition, the Zr bast block metal glass has in the supercooling liquid phase region of broad, thus in supercooling liquid phase region, can carry out superplastic forming for the precise form of the medical part of complexity provides may.
Because the developing history of block metal glass is very short, material educational circles and medical circle just began the biocompatibility of this class material is studied in recent years.The people such as doctor Hiromoto of Japan metal institute have at first studied pH value, Cl in phosphate buffer soln in 2000
-1Concentration, dissolved oxygen dividing potential drop and surface finish are to Zr
65Cu
17.5Ni
10Al
7.5The influence of the electrochemical behavior of block metal glass finds that this alloy has the polarization resistance suitable with the medical pure titanium, at very wide pH value, Cl
-1Shown pitting corrosion resistant performance in concentration, the dissolved oxygen dividing potential drop scope.People such as Hiromoto had studied Zr in 2002
65Cu
17.5Ni
10Al
7.5The again passivation behavior of block metal glass in Hanks ' solution finds that amorphous alloy has than the lower limit of congruent crystalline alloy passivation current density again, and the total charge transfer amount is also littler in passivating process again.This means that as embedded material when causing surface passivated membrane destroyed owing to factors such as frictions, the amount of metal ion that amorphous alloy discharges is less than corresponding crystal alloy, thus littler to the disadvantageous effect of surrounding tissue and human body generation.People such as Hiromoto has also studied Zr subsequently
55Al
10Ni
10Cu
25The polarization behavior of block metal glass in Hanks solution, MEM solution (Minimum essential medium) and cell culture medium (MEM+ calf serum), discovery is in the solution that contains amino acid and gene, and the ability of anti-general corrosion of metallic glass and spot corrosion all increases.
Doctor Parsell of doctor Horton of U.S.'s Oak Ridge National Laboratory in 2003 and University of Mississippi medical center has studied chemical property and cell growth and the metabolic activity on metallic glass of BAM-11 (Zr-10Al-5Ti-17.9Cu-14.6Ni) block metal glass in Ringer solution, find that its corrosion resistance nature is a little less than titanium alloy and 316L stainless steel, but scavenger cell and fibroblast show excellent biological compatibility in the surviving rate on this alloy, active all with suitable on medical pure titanium and polyethylene.But its tensile strength and elastic limit are respectively 1700MPa and 2.0～2.2%, and far above existing biomedical metal material, Young's modulus is that 90GPa also is lower than current material.
The people such as Morrison of the upright university of tennessee,USA in 2004 have studied BAM-11 block metal glass (Zr
52.5Cu
17.9Ni
14.6Al
10.0Ti
5.0) at the electrochemical behavior of buffering phosphate solution (PBS), the erosion rate of discovery this alloy in PBS solution and Ti6Al4V alloy, CoCrMo alloy phase are worked as, and be lower than 316L stainless steel.But corrosion-resistant ability is better than the 316L stainless steel is lower than Ti6Al4V alloy and CoCrMo alloy.
By these research overviews as can be seen, the Zr bast block metal glass presents wide application prospect at aspects such as joint prosthesis, femoral head supporter and tooth root planting bodies.But also be nowhere near with respect to the required existing research of clinical application.
Though non-crystaline amorphous metal is than the Young's modulus height of crystal alloy, but gap is still arranged with the bone photo ratio, completely different with the composition of natural bone, though and have excellent biological compatibility between the bone, implant the back bone regeneration around implant and do not have fiber kystis formation, but and be a kind of bone integration of mechanical embedding company property between the bone, but not therefore strong chemical synostosis carries out surface modification to improve its biological activity paid more and more attention to non-crystaline amorphous metal.At present, crystal alloy is carried out in the surface modification, Yan etc. are at Structure and bioactivity of micro-arc oxidized zirconia films (SURFACE ﹠amp; COATINGS TECHNOLOGY; Volume:201; Issue:9-11; Pages:5692-5695; Published:FEB 26 2007) propose in the literary composition the pure zirconium of crystalline state is carried out differential arc oxidation, obtained bonding strength ZrO preferably
2Ceramic membrane, but ceramic membrane does not comprise Ca, P, only is just to have produced the bioactive calcium phosphorus of representative through after soaking in simulated body fluid.Inoue etc. are at Observation of bone-like apatite on Ti-coated Zr
55Al
10Ni
5Cu
30Bulk metallic glass after alkali treatment (INTERMETALLICS; Volume:16; Issue:7; Pages:917-922; Published:JUL 2008) proposed to utilize alkali treatment method in the literary composition the non-crystaline amorphous metal surface modification is obtained osteoid apatite, but the associativity of ceramic membrane and matrix and bad.Up to now also not about utilizing the non-crystaline amorphous metal differential arc oxidization technique to carry out the relevant report of ceramic membrane preparation.
Summary of the invention
The invention provides a kind of method at zirconium-based bulk amorphous alloy surface preparation porous ceramic film, solve the ceramic membrane that existing method differential arc oxidation in crystal alloy can not directly obtain being rich in the calcium phosphoric, and in the ceramic membrane and the not firm problem of matrix bond of non-crystaline amorphous metal surface preparation.
A kind of method at zirconium-based bulk amorphous surface preparation high biological activity porous ceramic film of the present invention comprises:
(1) electrolytic solution preparation process: calcium hydroxide, disodium ethylene diamine tetraacetate, water glass and sodium phosphate are mixed and made into electrolytic solution, and the mol ratio of described each component is calcium hydroxide 0.06～0.08mol/L, disodium ethylene diamine tetraacetate 0.10～0.12mol/L, water glass 0.13～0.20mol/L, sodium phosphate 0.02～0.03mol/L;
(2) differential arc oxidation step: with no nickel type zirconium-based bulk amorphous alloy is anode, and stainless steel is that negative electrode places described electrolytic solution, adopts asymmetric alternating-current pulse power supply that block amorphous alloy is carried out differential arc oxidation; Voltage is that 260～400V, frequency are that 100～700Hz, dutycycle are 0.2～0.3, the time is 10～30min; Feed water coolant to electrolytic solution in the differential arc oxidation process, simultaneously electrolytic solution is stirred.
The present invention adopts differential arc oxidization technique to form the good high biological activity porous ceramics rete of one deck bonding force on no nickel type zirconium-based bulk amorphous alloy surface, and technology is simple, cost is lower; Prepared membrane is mainly by the ZrO that is rough porous, has very high bonding strength
2Constitute, help the growth of biological tissue, can improve the adhesion and the cell proliferation of biological tissue and implant; Tight with matrix bond, as to improve implant wearing quality; Wherein contain Ca, P element, and the content of Ca element increases with the rising of oxidation voltage, help film and in body fluid, form osteoid apatite; Thereby expanded the application of block amorphous alloy at biomedical sector.
Description of drawings
Fig. 1 is the X-ray diffractogram of the prepared ceramic membrane of the embodiment of the invention 2,3,4, and X-coordinate is represented two times of diffraction angle, and ordinate zou is represented diffracted intensity;
Fig. 2 (a) is the surface scan electron microscopic pattern of the prepared ceramic membrane of the embodiment of the invention 3;
Fig. 2 (b) is the cross section pattern of the ceramic membrane of Fig. 2 (a), among the figure, and matrix S, ceramic membrane C, resin R;
Fig. 3 is that the embodiment of the invention 4 prepared ceramic membranes pass through the scanning electron microscopy pattern of cell cultures after 1 day.
Embodiment
Below in conjunction with embodiment the present invention is specified:
Embodiment 1
(1) electrolytic solution preparation process: calcium hydroxide, disodium ethylene diamine tetraacetate, water glass and sodium phosphate are mixed and made into electrolytic solution, the mol ratio of described each component is calcium hydroxide 0.06mol/L, disodium ethylene diamine tetraacetate 0.10mol/L, water glass 0.13mol/L, sodium phosphate 0.02mol/L;
(2) differential arc oxidation step: with no nickel type zirconium-based bulk amorphous alloy is anode, and stainless steel is that negative electrode places described electrolytic solution, adopts asymmetric alternating-current pulse power supply that block amorphous alloy is carried out differential arc oxidation; Voltage is that 260V, frequency are that 100Hz, dutycycle are 0.2, the time is 10min; Feed water coolant to electrolytic solution in the differential arc oxidation process, and electrolytic solution is stirred.
The ceramic membrane top layer that obtains is by the ZrO that is rough porous
2Constitute.
Embodiment 2:
(1) electrolytic solution preparation process: calcium hydroxide, disodium ethylene diamine tetraacetate, water glass and sodium phosphate are mixed and made into electrolytic solution, the mol ratio of described each component is calcium hydroxide 0.08mol/L, disodium ethylene diamine tetraacetate 0.10mol/L, water glass 0.13mol/L, sodium phosphate 0.02mol/L;
(2) differential arc oxidation step: with no nickel type zirconium-based bulk amorphous alloy is anode, and stainless steel is that negative electrode places described electrolytic solution, adopts asymmetric alternating-current pulse power supply that block amorphous alloy is carried out differential arc oxidation; Voltage is that 400V, frequency are that 700Hz, dutycycle are 0.3, the time is 15min; Feed water coolant to electrolytic solution in the differential arc oxidation process, and electrolytic solution is stirred.
The ceramic membrane top layer that obtains is by the ZrO that is rough porous
2Constitute.Sample critical load after the oxidation of 400V voltage far surpasses 100N (100N is the maximum load load of test set), illustrates through the bioceramic film after this process to have very high bonding strength.A uppermost X-ray diffraction that curve is the prepared ceramic membrane of present embodiment among Fig. 1, X-coordinate is represented two times of diffraction angle, ordinate zou is represented diffracted intensity.
Embodiment 3:
(1) electrolytic solution preparation process: calcium hydroxide, disodium ethylene diamine tetraacetate, water glass and sodium phosphate are mixed and made into electrolytic solution, the mol ratio of described each component is calcium hydroxide 0.08mol/L, disodium ethylene diamine tetraacetate 0.11mol/L, water glass 0.15mol/L, sodium phosphate 0.03mol/L;
(2) differential arc oxidation step: with no nickel type zirconium-based bulk amorphous alloy is anode, and stainless steel is that negative electrode places described electrolytic solution, adopts asymmetric alternating-current pulse power supply that block amorphous alloy is carried out differential arc oxidation; Voltage is that 350V, frequency are that 700Hz, dutycycle are 0.3, the time is 30min; Feed water coolant to electrolytic solution in the differential arc oxidation process, and electrolytic solution is stirred.
The ceramic membrane top layer that obtains is by the ZrO that is rough porous
2Constitute.ZrO
2The critical load of film and noncrystal substrate surpasses 100N (100N is the maximum load load of test set), illustrates through the bioceramic film after this process to have very high bonding strength.The X-ray diffraction that curve of Fig. 1 intermediary is the prepared ceramic membrane of present embodiment, X-coordinate is represented two times of diffraction angle, ordinate zou is represented diffracted intensity.Fig. 2 (a) is the surface scan electron microscopic pattern of the prepared ceramic membrane of present embodiment; Fig. 2 (b) is the cross section pattern of the prepared ceramic membrane of present embodiment, among the figure, and matrix S, ceramic membrane C, resin R;
Embodiment 4:
(1) electrolytic solution preparation process: calcium hydroxide, disodium ethylene diamine tetraacetate, water glass and sodium phosphate are mixed and made into electrolytic solution, the mol ratio of described each component is calcium hydroxide 0.07mol/L, disodium ethylene diamine tetraacetate 0.12mol/L, water glass 0.20mol/L, sodium phosphate 0.02mol/L;
(2) differential arc oxidation step: with no nickel type zirconium-based bulk amorphous alloy is anode, and stainless steel is that negative electrode places described electrolytic solution, adopts asymmetric alternating-current pulse power supply that block amorphous alloy is carried out differential arc oxidation; Voltage is that 300V, frequency are that 500Hz, dutycycle are 0.3, the time is 20min; Feed water coolant to electrolytic solution in the differential arc oxidation process, and electrolytic solution is stirred.
The ceramic membrane top layer that obtains is by the ZrO that is rough porous
2Constitute.Record ZrO
2Ceramic membrane and bulk amorphous alloy material matrix critical load Lc be 65.5N; Lc increases with the increase of film thickness, matrix and intermembranous bonding strength increase.The nethermost X-ray diffraction that curve is the prepared ceramic membrane of present embodiment of Fig. 1, X-coordinate is represented two times of diffraction angle, ordinate zou is represented diffracted intensity.Fig. 3 is that the prepared ceramic membrane of present embodiment is through the scanning electron microscopy pattern of cell cultures after 1 day.
Claims (1)
1. method at zirconium-based bulk amorphous surface preparation high biological activity porous ceramic film comprises:
(1) electrolytic solution preparation process: calcium hydroxide, disodium ethylene diamine tetraacetate, water glass and sodium phosphate are mixed and made into electrolytic solution, and the mol ratio of described each component is calcium hydroxide 0.06～0.08mol/L, disodium ethylene diamine tetraacetate 0.10～0.12mol/L, water glass 0.13～0.20mol/L, sodium phosphate 0.02～0.03mol/L;
(2) differential arc oxidation step: with no nickel type zirconium-based bulk amorphous alloy is anode, and stainless steel is that negative electrode places described electrolytic solution, adopts asymmetric alternating-current pulse power supply that block amorphous alloy is carried out differential arc oxidation; Voltage is that 260～400V, frequency are that 100～700Hz, dutycycle are 0.2～0.3, the time is 10～30min; Feed water coolant to electrolytic solution in the differential arc oxidation process, simultaneously electrolytic solution is stirred.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102851719A (en) * | 2011-06-29 | 2013-01-02 | 比亚迪股份有限公司 | Zirconia-based amorphous alloy composite material and preparation method thereof |
| CN103603021A (en) * | 2013-11-28 | 2014-02-26 | 山东大学 | Preparation method of homoporous biological ceramic implant material having gradient calcium and phosphor content |
| CN104099654A (en) * | 2014-07-24 | 2014-10-15 | 西安交通大学 | Preparation method for porous calcium silicate bioactive coating |
| CN104745974A (en) * | 2013-12-30 | 2015-07-01 | 比亚迪股份有限公司 | Amorphous alloy product and preparation method thereof |
| CN109930087A (en) * | 2019-05-08 | 2019-06-25 | 常州世竟液态金属有限公司 | A kind of preparation method of zirconium-base amorphous alloy surface nano-structure layer |
-
2009
- 2009-01-16 CN CNA2009100605465A patent/CN101463496A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102851719A (en) * | 2011-06-29 | 2013-01-02 | 比亚迪股份有限公司 | Zirconia-based amorphous alloy composite material and preparation method thereof |
| CN103603021A (en) * | 2013-11-28 | 2014-02-26 | 山东大学 | Preparation method of homoporous biological ceramic implant material having gradient calcium and phosphor content |
| CN103603021B (en) * | 2013-11-28 | 2015-12-30 | 山东大学 | A kind of preparation method of the equal hole bioceramic implant material containing gradient calcium phosphorus |
| CN104745974A (en) * | 2013-12-30 | 2015-07-01 | 比亚迪股份有限公司 | Amorphous alloy product and preparation method thereof |
| CN104099654A (en) * | 2014-07-24 | 2014-10-15 | 西安交通大学 | Preparation method for porous calcium silicate bioactive coating |
| CN109930087A (en) * | 2019-05-08 | 2019-06-25 | 常州世竟液态金属有限公司 | A kind of preparation method of zirconium-base amorphous alloy surface nano-structure layer |
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Open date: 20090624 |