A kind of biological magnesium alloy and preparation method of LPSO structure of high-volume fractional
Technical field
What the present invention relates to is a kind of biological medical magnesium alloy and preparation method thereof, particularly magnesium alloy of a kind of high-volume fractional LPSO structure for biodegradable embedded material field and preparation method thereof.
Background technology
Magnesium alloy, owing to having the advantages such as good biocompatibility, degradable in vivo, becomes the focus of the biomedical sector researchs such as angiocarpy bracket, orthopaedics fixture.But, the degradation rate of current most magnesium alloy in human body surrounding medium is too fast, and show as inhomogeneous degraded, the biological corrosion performance of the magnesium alloy that the people such as Kirkland have studied 31 kinds of different states in " A survey of bio-corrosion rates of magnesium alloys; Corrosion Science; 2010; 52:287-291 " literary composition in simulation human body surrounding medium, wherein 29 kinds all show as non-uniform corrosion, the easy like this material that causes is implanted the rear support function of forfeiture too early, thereby affects the curative effect of disease.Up to now, be not still applied to clinical biological magnesium-alloy material.In order to prevent due to the magnesium alloy too fast or inhomogeneous degraded of degrading in human body environment, thereby cause implant before disease does not heal completely to occur with regard to having lost the situation of support function, be badly in need of research and development degradation rate slowly and the biological magnesium alloy of even degraded.
Mg-Gd series magnesium alloy, because can make the Cathodic polarization behavior of alloy weaken adding in right amount of Gd element, reduces and slowing down corrosion corrosion current.But Gd is rare earth elements, the Gd of too high amount has potential harm to each organs and systems of human body.The Zn of certain content joins in Mg-Gd alloy and can form long period stacking order (LPSO) structure, the corrosive nature that contains the biological magnesium alloy of Mg-11.3Gd-2.5Zn-0.7Zr of LPSO structure is obviously better than not containing the Mg-10.2Gd-3.3Y-0.6Zr magnesium alloy (reference: X. B. Zhang of LPSO structure, Y. J. Wu, Y. J. Xue, Z.Z Wang, L Yang. Biocorrosion behavior and cytotoxicity of a Mg-Gd-Zn-Zr alloy with long period stacking ordered structure[J]. Materials Letters, 2012, 86:42 ~ 45).Also studies have reported that the corrosive nature of the Mg-Zn-Y alloy that contains LPSO structure, but the LSPO structure in this alloy has been accelerated the corrosion of matrix, and be spot corrosion (reference: J.S. Zhang, J.D. Xu, W.L. Cheng, C.J. Chen, J.J. Kang. Corrosion behavior of Mg-Y-Zn alloy with long period stacking ordered structures[J]. Journal of Materials Science and Technology, 2012,28 (12): 1157-1162).These show that Corrosion Behaviors of Magnesium Alloys (degraded) behavior that contains LPSO structure is not only relevant, also relevant with alloying constituent with distribution with LPSO structural content.
Chinese invention patent application number: 201310105667.3, publication number: CN 103184379 A, open day: on July 3rd, 2013, a kind of biodegradable Mg-Gd-Zn-Ag-Zr series magnesium alloy containing LPSO structure and no cytotoxicity is disclosed, the weight percentage of this each component of alloy is Gd5 ~ 10%, Zn0.5 ~ 3%, Ag0.1 ~ 1%, Zr0.1 ~ 1%, surplus is Mg.Chinese invention patent application number: 201310105668.8, publication No.: CN 103184380 A, open day: disclose a kind of Mg-Gd-Zn-Sr-Zr series magnesium alloy containing LPSO structure on July 3rd, 2013, the weight percentage of this each component of alloy is Gd 5 ~ 10%, Zn 0.5 ~ 3%, Sr 0.1 ~ 1%, and Zr 0.1 ~ 1%, and surplus is Mg.Above-mentioned two kinds of magnesium alloy all have LPSO structure, can be as the implant material of low degradation rate and uniform corrosion.Its weak point is the content of rare earth elements Gd higher (massfraction is more than or equal to 5%), and as bio-medical material, long-term safety is indefinite, and the volume fraction of LPSO structure is little, and anti-localized degradation is limited in one's ability.In addition, contain expensive Ag in Mg-Gd-Zn-Ag-Zr series magnesium alloy, cost is higher; And in Mg-Gd-Zn-Sr-Zr series magnesium alloy, contain Sr element, no matter Sr simple substance or Mg-Sr master alloy, its starting material are comparatively harsh to preservation condition, need under vacuum or protective atmosphere, preserve, thereby increased cost.In addition, selection of heat-treatment processes is improper also can be caused in Mg-Gd-Zn-Zr magnesium alloy without LPSO structure (reference: J.F. Nie, X. Gao, S.M. Zhu. Enhanced age hardening response and creep resistance of Mg – Gd alloys containing Zn[J]. Scripta Materialia, 2005,53:1049 ~ 1053).
Therefore, exploitation has the LPSO structure of high-volume fractional and nontoxic biological magnesium alloy materials and the technology of preparing thereof of even slow degradation, can promote biological magnesium alloy clinical application.
Summary of the invention
The object of the invention is to have the too fast and inhomogeneous problem of degrading of degradation rate for current biological magnesium alloy, a kind of biological magnesium alloy materials of Mg-Gd-Zn-Zr with high-volume fractional LPSO structure and preparation method thereof is provided.This material no cytotoxicity has degradation rate slowly in simulation human body environment, and evenly degraded, can pass through external degradation performance test, and degradation behavior in predictor, is expected to be applied to biomedical sector.
The present invention realizes by following technique means:
A biological magnesium alloy for the LPSO structure of high-volume fractional, is comprised of Gd, Zn, Zr and Mg, and wherein, the weight percentage of each component is respectively: Gd:3.6~4.9%, and Zn:0.6~0.9%, Zr:0.3~0.6%, surplus is Mg; In described alloy, the volume fraction of LPSO structure is greater than 30%.
The weight percentage of aforesaid each component is: Gd:4.2~4.8%, and Zn:0.7~0.8%, Zr:0.4~0.5%, surplus is Mg; In described alloy, the volume fraction of LPSO structure is greater than 30%.
The weight percentage of aforesaid each component is: Gd:4.8%, and Zn:0.8%, Zr:0.5%, surplus is Mg; In described alloy, the volume fraction of LPSO structure is greater than 30%.
The weight percentage of aforesaid each component is: Gd:4.2%, and Zn:0.7%, Zr:0.6%, surplus is Mg; In described alloy, the volume fraction of LPSO structure is greater than 30%.
The weight percentage of aforesaid each component is: Gd:3.6%, and Zn:0.6%, Zr:0.4%, surplus is Mg; In described alloy, the volume fraction of LPSO structure is greater than 30%.
A preparation method with the biological magnesium alloy of high-volume fractional LPSO structure, comprises the following steps successively:
(1) melting:
Purity is greater than to pure zinc and the Mg-Zr master alloy that 99.95% high purity magnesium, Mg-Gd master alloy, purity are greater than 99.99%, by proportioning, successively put into the crucible with shielding gas and carry out melting, in the time of 720 ℃, pour into preheating temperature and be in the steel die of 150 ~ 200 ℃ and form Mg-Gd-Zn-Zr magnesium alloy ingot;
(2) cooling:
The Mg-Gd-Zn-Zr magnesium alloy ingot that step (1) is obtained, puts into water and is cooled to room temperature;
(3) thermal treatment:
The ingot casting of described step (2) is put into the resistance furnace with protective atmosphere, at 340 ℃~460 ℃, be incubated 1~6 hour, obtain the Magnesium Alloy of the LPSO structure of different volumes mark.
In aforesaid step (1) fusion process, the shielding gas of crucible is CO
2and SF
6mixed gas, its throughput ratio is 97:3.
During aforesaid step (1) melting; first high purity magnesium being put into crucible heats; furnace temperature is raised to 300 ℃ and starts to pass into shielding gas; when being raised to 740 ℃, temperature adds Mg-Gd master alloy; after it melts completely, add pure Zn and Mg-Zr master alloy, after starting material melt completely, open automatic stirrer and stir 4-8 minute; then by Temperature Setting, be 720 ℃ after standing 10 minutes, under the protection of shielding gas, be cast in steel die.
The invention has the beneficial effects as follows:
(1), by the ratio of appropriate design Gd, Zn and Zr element, make the biological magnesium alloy of as cast condition Mg-Gd-Zn-Zr there is LPSO structure.This structure, with respect to matrix, contains more Gd, and with respect to eutectic phase, contains less Gd.LPSO structure distribution is at grain boundaries, and matrix is surrounded, and becomes the bridge between matrix and second-phase.
(2) LPSO structure contains more Gd with respect to matrix; can in the solution of simulation human body environment, form oxide compound and the oxyhydroxide protective layer of Gd; and the corrosion potential of LPSO structure is between matrix and eutectic phase; the corrosion potential that can effectively weaken between matrix and eutectic phase is poor; thereby significantly improve the degradation rate of alloy in simulation human body environment, and alloy is evenly degraded.Can avoid most magnesium alloy because degradation rate is too fast and localized degradation causes embedded material premature failure, reach the desirable support effect of Biodegradable material, thereby be expected to apply in biomedicine.
(3) the LPSO structural volume mark in the biological magnesium alloy of Mg-Gd-Zn-Zr of the present invention can regulate and control by suitable thermal treatment, and its LPSO volume fraction reaches as high as 50% left and right, and the volume fraction of LPSO structure is higher, and its degradation rate is slower.And heat treatment process parameter selects improper meeting to cause LPSO structure in alloy to disappear, alloy degradation rate in simulated body fluid is accelerated, and it is inhomogeneous to degrade.
(4) alloy element that the present invention chooses on Composition Design is all no cytotoxicities in proposed composition range.
(5) biological magnesium alloy of the present invention have starting material be easy to get, cheap, easily preserve, preparation method is simple, the volume fraction of LPSO structure is easy to the advantages such as control.
(6) the present invention can make body implanting materials such as making angiocarpy bracket, orthopaedics fixture by reprocessing.While using, can realize even degraded, and degradation rate is slower under human body environment, can meets requirement in clinical application and support the requirement of 3-12 month.Therefore, magnesium alloy of the present invention is suitable as body implanting material, as angiocarpy bracket, orthopaedics fixture etc.
Accompanying drawing explanation
Fig. 1 is that in embodiment 1, LPSO structural volume mark is about 10% shape appearance figure;
Fig. 2 is that in embodiment 1, LPSO structural volume mark is about 50% shape appearance figure;
Fig. 3 is that Fig. 2 interalloy washes away the degraded shape appearance figure after degraded product;
Fig. 4 is that the volume fraction of LPSO structure in embodiment 2 is about 45% shape appearance figure;
Fig. 5 is that Fig. 4 interalloy washes away the degraded shape appearance figure after degraded product;
Fig. 6 is that the volume fraction of LPSO structure in embodiment 3 is about 30% shape appearance figure;
Fig. 7 is that Fig. 6 interalloy washes away the degraded shape appearance figure after degraded product;
Fig. 8 is the shape appearance figure that the LPSO structure in embodiment 3 interalloy tissues disappears;
Fig. 9 is that Fig. 8 interalloy washes away the degraded shape appearance figure after degraded product.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The biological magnesium alloy of the LPSO structure of high-volume fractional of the present invention, is comprised of Gd, Zn, Zr and Mg, and wherein, the weight percentage of each component is respectively: Gd:3.6~4.9%, and Zn:0.6~0.9%, Zr:0.3~0.6%, surplus is Mg; In alloy, the volume fraction of LPSO structure is greater than 30%, and can evenly degraded in simulation human body surrounding medium.
Preferably, the weight percentage of each component is: Gd:4.2~4.8%, and Zn:0.7~0.8%, Zr:0.4~0.5%, surplus is Mg; In described alloy, the volume fraction of LPSO structure is greater than 30%, and can evenly degraded in simulation human body surrounding medium.
Preferably, the weight percentage of each component is: Gd:4.8%, and Zn:0.8%, Zr:0.5%, surplus is Mg; In described alloy, the volume fraction of LPSO structure is greater than 30%, and can evenly degraded in simulation human body surrounding medium.
Preferably, the weight percentage of each component is: Gd:4.2%, and Zn:0.7%, Zr:0.6%, surplus is Mg; In described alloy, the volume fraction of LPSO structure is greater than 30%, and can evenly degraded in simulation human body surrounding medium.
Preferably, the weight percentage of each component is: Gd:3.6%, and Zn:0.6%, Zr:0.4%, surplus is Mg; In described alloy, the volume fraction of LPSO structure is greater than 30%, and can evenly degraded in simulation human body surrounding medium.
The preparation method with the biological magnesium alloy of high-volume fractional LPSO structure of the present invention, comprises the following steps successively:
(1) melting:
Purity is greater than to pure zinc and the Mg-Zr master alloy that 99.95% high purity magnesium, Mg-Gd master alloy, purity are greater than 99.99%, by proportioning, successively put into the crucible with shielding gas and carry out melting, in the time of 720 ℃, pour into preheating temperature and be in the steel die of 150 ~ 200 ℃ and form Mg-Gd-Zn-Zr magnesium alloy ingot;
(2) cooling:
The Mg-Gd-Zn-Zr magnesium alloy ingot that step (1) is obtained is incubated 1~6 hour at 340~460 ℃, then water-cooled;
(3) thermal treatment:
Ingot casting is put into the resistance furnace with protective atmosphere and heat and be incubated, obtain the Magnesium Alloy of the LPSO structure of different volumes mark.
Provide preparation process and corresponding experiment analysis results that several specific embodiments elaborate biological magnesium alloy of the present invention below.
Embodiment 1
Adopting high purity magnesium (purity of Mg is more than or equal to 99.95%), Mg-Gd master alloy foreign matter contents such as (be less than 0.05%) Fe, Ni, Cu, pure zinc (purity of Zn is more than or equal to 99.99%) and Mg-Zr master alloy foreign matter contents such as (be less than 0.01%) Fe, Ni, Cu, by Mg-4.8Gd-0.8Zn-0.5Zr(massfraction) alloying constituent proportioning carries out melting.During melting, first high purity magnesium is put into crucible and heat, furnace temperature is raised to 300 ℃ and starts to pass into CO
2and SF
6mixed gas is as shielding gas; the throughput ratio of mixed gas is elected 97:3 as; when being raised to 740 ℃, temperature adds Mg-Gd master alloy; after melting completely, it adds pure Zn and Mg-Zr master alloy; after starting material melt completely, open automatic stirrer and stir 4-8 minute, in the present embodiment, stir 5 minutes; then by Temperature Setting, be 720 ℃ after standing 10 minutes, under the protection of shielding gas, be cast to preheating temperature and be in the steel die of 180 ℃.After melt solidifies completely, ingot casting is put into water and be cooled to room temperature.Now, the LPSO structural volume mark of this cast alloy is only about 10%, as shown in Figure 1.Ingot casting is put into the resistance furnace with sulfurous iron ore protective atmosphere and be heated to 400 ℃ of insulations 5 hours; in the Mg-4.8Gd-0.8Zn-0.5Zr tissue of this state, the volume fraction of LPSO structure is significantly increased to 50% left and right; as shown in Figure 2, now the Gd content in eutectic phase, LPSO structure and matrix is respectively 25.0%, 13.1% and 4.7% in tissue.This state alloy structure is soaked after within 5 days, washing away degraded product and shows as even degraded pattern as shown in Figure 3 in simulated body fluid, and degradation rate is 0.47 mm/year.
Embodiment 2
Adopting high purity magnesium (purity of Mg is more than or equal to 99.95%), Mg-Gd master alloy foreign matter contents such as (be less than 0.05%) Fe, Ni, Cu, pure zinc (purity of Zn is more than or equal to 99.99%) and Mg-Zr master alloy foreign matter contents such as (be less than 0.01%) Fe, Ni, Cu, by Mg-4.8Gd-0.8Zn-0.5Zr(massfraction) alloying constituent proportioning carries out melting.During melting, first high purity magnesium is put into crucible and heat, furnace temperature is raised to 300 ℃ and starts to pass into CO
2and SF
6mixed gas is as shielding gas; the throughput ratio of mixed gas is elected 97:3 as; when being raised to 740 ℃, temperature adds Mg-Gd master alloy; after melting completely, it adds pure Zn and Mg-Zr master alloy; after starting material melt completely, open automatic stirrer and stir 4-8 minute, in the present embodiment, stir 5 minutes; then by Temperature Setting, be 720 ℃ after standing 10 minutes, under the protection of shielding gas, be cast to preheating temperature and be in the steel die of 180 ℃.After melt solidifies completely, ingot casting is put into water and be cooled to room temperature.Ingot casting is put into the resistance furnace with sulfurous iron ore protective atmosphere and be heated to 350 ℃ of insulations 5 hours.In the Mg-4.8Gd-0.8Zn-0.5Zr tissue of this state, the volume fraction of LPSO structure is about 45%, as shown in Figure 4, this state alloy is soaked after within 5 days, washing away degraded product and shows as even degraded pattern in simulated body fluid, and as shown in Figure 5, degradation rate is 0.58 mm/year.
Embodiment 3
Adopting high purity magnesium (purity of Mg is more than or equal to 99.95%), Mg-Gd master alloy foreign matter contents such as (be less than 0.05%) Fe, Ni, Cu, pure zinc (purity of Zn is more than or equal to 99.99%) and Mg-Zr master alloy foreign matter contents such as (be less than 0.01%) Fe, Ni, Cu, by Mg-4.8Gd-0.8Zn-0.5Zr(massfraction) alloying constituent proportioning carries out melting.During melting, first high purity magnesium is put into crucible and heat, furnace temperature is raised to 300 ℃ and starts to pass into CO
2and SF
6mixed gas is as shielding gas; the throughput ratio of mixed gas is elected 97:3 as; when being raised to 740 ℃, temperature adds Mg-Gd master alloy; after melting completely, it adds pure Zn and Mg-Zr master alloy; after starting material melt completely, open automatic stirrer and stir 4-8 minute, in the present embodiment, stir 5 minutes; then by Temperature Setting, be 720 ℃ after standing 10 minutes, under the protection of shielding gas, be cast to preheating temperature and be in the steel die of 180 ℃.After melt solidifies completely, ingot casting is put into water and be cooled to room temperature.Ingot casting is put into the resistance furnace with sulfurous iron ore protective atmosphere to be heated to 450 ℃ and to be incubated respectively 2 hours and 5 hours.In the Mg-4.8Gd-0.8Zn-0.5Zr tissue that is wherein incubated 2 hours, the volume fraction of LPSO structure is about 40%, and this state alloy is soaked after within 5 days, washing away degraded product and shows as even degraded pattern in simulated body fluid, and degradation rate is 0.62 mm/year.In the Mg-4.8Gd-0.8Zn-0.5Zr tissue that is incubated 5 hours, the volume fraction of LPSO structure is about 30%, as shown in Figure 6, this state alloy is soaked after within 5 days, washing away degraded product and shows as even degraded pattern as shown in Figure 7 in simulated body fluid, and degradation rate is 0.67 mm/year.If be heated to 535 ℃ of insulations 10 hours and ingot casting is put into the resistance furnace with protective atmosphere; LPSO structure in tissue disappears as shown in Figure 8; under this state, alloy soaks the degradation rate of 5 days up to 3 mm/year in simulated body fluid, and it is inhomogeneous to degrade, as shown in Figure 9.Therefore, must strictly control thermal treatment process could obtain the LPSO structure of higher volume fraction and degradation rate slowly, the uniform biodegradable magnesium alloy material of degrading, to meet implantation requirement.
Embodiment 4
Adopting high purity magnesium (purity of Mg is more than or equal to 99.95%), Mg-Gd master alloy foreign matter contents such as (be less than 0.05%) Fe, Ni, Cu, pure zinc (purity of Zn is more than or equal to 99.99%) and Mg-Zr master alloy foreign matter contents such as (be less than 0.01%) Fe, Ni, Cu, by Mg-4.2Gd-0.7Zn-0.6Zr massfraction) alloying constituent proportioning carries out melting.During melting, first high purity magnesium is put into crucible and heat, furnace temperature is raised to 300 ℃ and starts to pass into CO
2and SF
6mixed gas is as shielding gas; the throughput ratio of mixed gas is elected 97:3 as; when being raised to 740 ℃, temperature adds Mg-Gd master alloy; after melting completely, it adds pure Zn and Mg-Zr master alloy; after starting material melt completely, open automatic stirrer and stir 4-8 minute, in the present embodiment, stir 5 minutes; then by Temperature Setting, be 720 ℃ after standing 10 minutes, under the protection of shielding gas, be cast to preheating temperature and be in the steel die of 180 ℃.After melt solidifies completely, ingot casting is put into water and be cooled to room temperature.Ingot casting is put into the resistance furnace with sulfurous iron ore protective atmosphere and be heated to 340 ℃ of insulations 6 hours.In the Mg-4.2Gd-0.7Zn-0.6Zr tissue of this state, the volume fraction of LPSO structure is about 45%, this state group is woven in simulated body fluid, to soak after within 5 days, washing away degraded product show as even degraded pattern, and degradation rate is 0.53 mm/year.
Embodiment 5
Adopting high purity magnesium (purity of Mg is more than or equal to 99.95%), Mg-Gd master alloy foreign matter contents such as (be less than 0.05%) Fe, Ni, Cu, pure zinc (purity of Zn is more than or equal to 99.99%) and Mg-Zr master alloy foreign matter contents such as (be less than 0.01%) Fe, Ni, Cu, by Mg-4.2Gd-0.7Zn-0.6Zr(massfraction) alloying constituent proportioning carries out melting.During melting, first high purity magnesium is put into crucible and heat, furnace temperature is raised to 300 ℃ and starts to pass into CO
2and SF
6mixed gas is as shielding gas; the throughput ratio of mixed gas is elected 97:3 as; when being raised to 740 ℃, temperature adds Mg-Gd master alloy; after melting completely, it adds pure Zn and Mg-Zr master alloy; after starting material melt completely, open automatic stirrer and stir 4-8 minute, in the present embodiment, stir 5 minutes; then by Temperature Setting, be 720 ℃ after standing 10 minutes, under the protection of shielding gas, be cast to preheating temperature and be in the steel die of 180 ℃.After melt solidifies completely, ingot casting is put into water and be cooled to room temperature.Ingot casting is put into the resistance furnace with protective atmosphere and be heated to 400 ℃ of insulations 2 hours, in the Mg-4.2Gd-0.7Zn-0.6Zr tissue of this state, the volume fraction of LPSO structure is about 40%.If ingot casting is put into the resistance furnace with protective atmosphere, be heated to 400 ℃ of insulations 5 hours, in tissue, the volume fraction of LPSO structure is about 35%.Under above two states, the degraded pattern of magnesium alloy in simulated body fluid is all uniform.
Embodiment 6
Adopting high purity magnesium (purity of Mg is more than or equal to 99.95%), Mg-Gd master alloy foreign matter contents such as (be less than 0.05%) Fe, Ni, Cu, pure zinc (purity of Zn is more than or equal to 99.99%) and Mg-Zr master alloy foreign matter contents such as (be less than 0.01%) Fe, Ni, Cu, by Mg-3.6Gd-0.6Zn-0.4Zr(massfraction) alloying constituent proportioning carries out melting.During melting, first high purity magnesium is put into crucible and heat, furnace temperature is raised to 300 ℃ and starts to pass into CO
2and SF
6mixed gas is as shielding gas; the throughput ratio of mixed gas is elected 97:3 as; when being raised to 740 ℃, temperature adds Mg-Gd master alloy; after melting completely, it adds pure Zn and Mg-Zr master alloy; after starting material melt completely, open automatic stirrer and stir 4-8 minute, in the present embodiment, stir 5 minutes; then by Temperature Setting, be 720 ℃ after standing 10 minutes, under the protection of shielding gas, be cast to preheating temperature and be in the steel die of 180 ℃.After melt solidifies completely, ingot casting is put into water and be cooled to room temperature.Ingot casting is put into the resistance furnace with protective atmosphere and be heated to 420 ℃ of insulations 2 hours, in the Mg-3.6Gd-0.6Zn-0.4Zr tissue of this state, the volume fraction of LPSO structure is about 35%.If ingot casting is put into the resistance furnace with sulfurous iron ore protective atmosphere, be heated to 420 ℃ of insulations 5 hours, in Mg-3.6Gd-0.6Zn-0.4Zr tissue, the volume fraction of LPSO structure is about 30%.Under above two states, the degraded pattern of magnesium alloy in simulated body fluid is all uniform.
The present invention is not limited to above-described embodiment; every on the basis of technical scheme disclosed by the invention; those skilled in the art is according to disclosed technology contents; do not need performing creative labour just can make some replacements and distortion to some technical characterictics wherein, these replacements and distortion are all in the scope of protection of the invention.