CN104120320B - A kind of degradable magnesium-rare earth biomaterial for medical purpose and preparation method - Google Patents
A kind of degradable magnesium-rare earth biomaterial for medical purpose and preparation method Download PDFInfo
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Abstract
The present invention provides a kind of degradable magnesium-rare earth biomaterial for medical purpose, take magnesium as base alloy, relation adds rare earth, zinc and zr element and makes according to a certain ratio, does is described degradable magnesium-rare earth chemistry composition by mass percentage: Y0.5-2.0wt.%, Dy0.1-0.5wt.%, Zn0.8-1.2wt.%, Zr? 0.35-0.55wt.%, all the other are Mg and inevitable impurity element. Providing the preparation method of described degradable magnesium-rare earth biomaterial for medical purpose simultaneously, comprise the following steps: (1) alloy melting, (2) alloy extrudes, (3) alloy thermal treatment. The present invention has the following advantages: 1, have good mechanical property and processing characteristics, it is possible to meet the needs of medical embedded material; 2, there is good corrosion resistance nature, can realize degrading completely, suitable corrosion speed can be ensured again; 3, the toxicity of alloy element has strict restriction. The present invention is mainly used in medical metal material aspect.
Description
Technical field
The present invention relates to technical field of magnesium alloy material, it is specifically related to a kind of degradable magnesium-rare earth biomaterial for medical purpose and its preparation method.
Background technology
In the current social of intense industrialization, magnesium alloy is subject to people pays close attention to due to features such as its weight are light, specific tenacity height, resource reserve are abundant, and its range of application expands to the field of functional materials such as the energy, biology by structure unit and power system. In medical metal material, magnesium alloy is mechanical property access expansion bone not only, and shows outstanding biocompatibility in human body implantation experiment. In neutral environment and chloride environment, the corrosion of magnesium planting body forms the nontoxic oxide compound of solubility after decomposing, and freshman bone tissue is had and stimulate growth promoting effects effect. But, pure magnesium, magnesium is aluminium base and the conventional mg-based material system erosion rate such as magnesium zinc-base is too fast, poor mechanical integrity, do not have enough time healings, and is not suitable as medical material and uses. Therefore adopt rare earth element as alloying composition, to improve its intensity and corrosion resisting property, thus advance the development of Medical magnesium alloy material.
Summary of the invention
For above-mentioned prior art, technical problem to be solved by this invention is to provide a kind of intensity height, plasticity is good, processing characteristics is excellent, the degradable magnesium-rare earth biomaterial for medical purpose of degradable, nontoxicity. Provide the preparation method of this degradable magnesium-rare earth biomaterial for medical purpose simultaneously.
In order to solve the problems of the technologies described above, the present invention provides a kind of degradable magnesium-rare earth biomaterial for medical purpose, take magnesium as base alloy, relation adds rare earth, zinc and zr element and makes according to a certain ratio, described degradable magnesium-rare earth chemistry composition is by mass percentage: Y0.5-2.0wt.%, Dy0.1-0.5wt.%, Zn0.8-1.2wt.%, Zr0.35-0.55wt.%, all the other are Mg and inevitable impurity element.
Further improvement of the present invention is, rare earth element total content is no more than the 2.5wt% of described degradable magnesium-rare earth total mass, and wherein Y is 0.5-2.0wt.%, Dy is 0.1-0.5wt.%.
Further improvement of the present invention is, described impurity element comprises Fe, Cu, Si, Ni, and the mass percent of each component is: Fe��0.005wt.%, Cu��0.0005wt.%, Si��0.005wt.%, Ni��0.0005wt.%.
Further improvement of the present invention is, described rare earth and zr element all adopt the mode of master alloy to add, described master alloy is magnesium-rare earth intermediate alloy, magnesium-zirconium master alloy, the mass percent of the described each component of magnesium-rare earth intermediate alloy is: magnesium 80wt%, rare earth 20wt%, and the mass percent of described magnesium-each component of zirconium master alloy is: magnesium 70wt%, zirconium 30wt%.
A preparation method for degradable magnesium-rare earth biomaterial for medical purpose, comprises the following steps:
(1) alloy melting: raw material is undertaken by proportioning preparing burden, surface sand-blasting is removed the peel and is preheating to 200 DEG C; Preheating cast iron crucible, to 300 DEG C, leads to into SF6: CO2Volume ratio is the shielding gas of 1:200, adds magnesium ingot; In crucible, metal melts completely and when melt temperature reaches 740 DEG C, adds metallic zinc, magnesium-yttrium master alloy, magnesium-dysprosium master alloy successively; When melt temperature reaches 770 DEG C, add magnesium-zirconium master alloy, continue after stirring to lead to when melt temperature is down to 730 DEG C into argon gas refining 5 minutes, at 730 DEG C, leave standstill 20 minutes; When melt temperature is down to 720 DEG C, alloy liquid is cast in water cooling mold and makes degradable magnesium-rare earth ingot casting blank;
(2) alloy extruding: described ingot casting blank carries out homogeneous thermal treatment 10 hours at 480 DEG C, carries out turnery processing on lathe, obtains smooth surface, without being mingled with, without extrusion billet material that is lofty and depression;
(3) alloy thermal treatment: the described extrusion billet material after cooling is warming up to 200 DEG C of insulations 2 hours, is then warming up to 260 DEG C of insulations 10 hours; Take out described extrusion billet material at room temperature to cool; Described degradable magnesium-rare earth biomaterial for medical purpose chemistry composition is by mass percentage: Y0.5-2.0wt.%, Dy0.1-0.5wt.%, Zn0.8-1.2wt.%, Zr0.35-0.55wt.%, all the other are Mg and inevitable impurity element.
Further improvement of the present invention is, during step (2) alloy of the preparation method of described degradable magnesium-rare earth biomaterial for medical purpose extrudes: described extrusion billet material extrudes at 350 DEG C, mould, ingot-containing tube temperature are 320-340 DEG C, and extrusion speed is set between 2-0.5m/s.
Further improvement of the present invention is, the preparation method of described degradable magnesium-rare earth biomaterial for medical purpose also comprises the following steps:
Prepare magnesium-rare earth yttrium master alloy: by the magnesia amount per-cent of metal be 80wt%, rare earth yttrium quality be the proportion ingredient of 20wt%, MAGNESIUM METAL and rare earth yttrium are put into cast iron or plumbago crucible heat fused and are warming up to 780 DEG C, stir after evenly and leave standstill 20 minutes, then it is cast into magnesium-yttrium intermediate alloy ingot, fusion process leads to into SF6: CO2Volume ratio is the shielding gas of 1:200; According to same processing parameter and proportioning raw materials, prepare magnesium-zirconium master alloy, magnesium-dysprosium master alloy respectively; By metal magnesia amount per-cent be 70wt%, metal zirconium mass percent be 30wt% proportioning and adopt prepare magnesium-zirconium intermediate alloy ingot with the processing parameter that magnesium-yttrium master alloy is the same.
Compared with prior art, using Medical magnesium alloy material as target, the present invention carrys out refining alloy tissue with improving corrosion resistance nature by adding the rare earth element of different content, obtains outstanding mechanical property with this and retains good biocompatibility simultaneously. On the one hand, rare earth element has high poisoning effect concentration, and Y and Dy of high-dissolvability shows outstanding biological friendly. On the other hand, Mg-Y-Zn-Zr base alloy has excellent mechanical property, it is possible to meet the needs of human body medical material. The present invention has the following advantages: 1, have good mechanical property and processing characteristics, it is possible to meet the needs of medical embedded material; 2, there is good corrosion resistance nature, can realize degrading completely, suitable corrosion speed can be ensured again; 3, the toxicity of alloy element has strict restriction.
Accompanying drawing explanation
Fig. 1 is the metallograph of the present invention: (a) as cast condition (b) homogenization treatment state (c) extrudes state (d) and extrude state;
Fig. 2 is the degradable magnesium-rare earth adopting the present invention: after Mg-1.5Y-0.4Dy-1.0Zn-0.4Zr vat liquor, the L-929 cell cultures form photo of 3 days: (a) 100% vat liquor (b) 50% vat liquor (c) 10% vat liquor (d) positive controls 0.64% phenol;
Fig. 3 is the degradable magnesium-rare earth of the present invention: Mg-1.5Y-0.4Dy-1.0Zn-0.4Zr energy spectrum analysis data after 240 hours of 37 DEG C of successive soakings in SBF simulated body fluid;
Fig. 4 is the room-temperature mechanical property table of the embodiment of the present invention 1, embodiment 2, embodiment 3 and embodiment 4;
Fig. 5 is SBF simulated body fluid successive soaking test mass loss cartogram (unit: gram, specimen finish 15mm, length 20mm) of the embodiment of the present invention 1, embodiment 2, embodiment 3 and embodiment 4.
Embodiment
Illustrate below in conjunction with accompanying drawing and embodiment the present invention is further described.
The degradable magnesium-rare earth biomaterial for medical purpose of the present invention, take magnesium as base alloy, relation adds rare earth, zinc and zr element and makes according to a certain ratio, described degradable magnesium-rare earth chemistry composition is by mass percentage: Y0.5-2.0wt.%, Dy0.1-0.5wt.%, Zn0.8-1.2wt.%, Zr0.35-0.55wt.%, all the other are Mg and inevitable impurity element. Described impurity element comprises Fe, Cu, Si, Ni, and the mass percent of each component is: Fe��0.005wt.%, Cu��0.0005wt.%, Si��0.005wt.%, Ni��0.0005wt.%. Rare earth element total content is no more than the 2.5wt% of described degradable magnesium-rare earth total mass, and wherein Y is 0.5-2.0wt.%, Dy is 0.1-0.5wt.%. In order to obtain specific metallographic structure and mechanical property, rare earth and zr element all adopt the mode of master alloy to add, and adopt suitable preparation technology according to this mode. Described master alloy is magnesium-rare earth intermediate alloy, magnesium-zirconium master alloy, the mass percent of the described each component of magnesium-rare earth intermediate alloy is: magnesium 80wt%, rare earth 20wt%, and the mass percent of described magnesium-each component of zirconium master alloy is: magnesium 70wt%, zirconium 30wt%. Due to solid solution and the refining effect of rare earth element, degradable magnesium-rare earth intensity and biodegradability obtain obvious improvement. By vitro cytotoxicity evaluation experimental, prove that it has basic biological safety and biocompatibility. The degradable magnesium-rare earth intensity height of the present invention, plasticity is good, processing characteristics is excellent, degradable, nontoxicity, be a kind of can as the lightweight magnesium alloy structured material of degradable medical biological base material.
The preparation method of the degradable magnesium-rare earth biomaterial for medical purpose of the present invention is as follows:
The preparation method of the degradable magnesium-rare earth biomaterial for medical purpose of the present invention, comprises the following steps:
(1) alloy melting: raw material is undertaken by proportioning preparing burden, surface sand-blasting is removed the peel and is preheating to 200 DEG C; Preheating cast iron crucible, to 300 DEG C, leads to into SF6: CO2Volume ratio is the shielding gas of 1:200, adds magnesium ingot; In crucible, metal melts completely and when melt temperature reaches 740 DEG C, adds metallic zinc, magnesium-yttrium master alloy, magnesium-dysprosium master alloy successively; When melt temperature reaches 770 DEG C, add magnesium-zirconium master alloy, continue after stirring to lead to when melt temperature is down to 730 DEG C into argon gas refining 5 minutes, at 730 DEG C, leave standstill 20 minutes; When melt temperature is down to 720 DEG C, alloy liquid is cast in water cooling mold and makes degradable magnesium-rare earth ingot casting blank;
(2) alloy extruding: described ingot casting blank carries out homogeneous thermal treatment 10 hours at 480 DEG C, carries out turnery processing on lathe, obtains smooth surface, without being mingled with, without extrusion billet material that is lofty and depression; Described extrusion billet material extrudes at 350 DEG C, and mould, ingot-containing tube temperature are 320-340 DEG C, and extrusion speed is set between 2-0.5m/s;
(3) alloy thermal treatment: the described extrusion billet material after cooling is warming up to 200 DEG C of insulations 2 hours, is then warming up to 260 DEG C of insulations 10 hours; Take out described extrusion billet material at room temperature to cool; Described degradable magnesium-rare earth biomaterial for medical purpose chemistry composition is by mass percentage: Y0.5-2.0wt.%, Dy0.1-0.5wt.%, Zn0.8-1.2wt.%, Zr0.35-0.55wt.%, all the other are Mg and inevitable impurity element.
The preparation method of the degradable magnesium-rare earth biomaterial for medical purpose of the present invention also comprises the following steps:
Prepare magnesium-rare earth yttrium master alloy: by the magnesia amount per-cent of metal be 80wt%, rare earth yttrium quality be the proportion ingredient of 20wt%, MAGNESIUM METAL and rare earth yttrium are put into cast iron or plumbago crucible heat fused and are warming up to 780 DEG C, stir after evenly and leave standstill 20 minutes, then it is cast into magnesium-yttrium intermediate alloy ingot, fusion process leads to into SF6: CO2Volume ratio is the shielding gas of 1:200; According to same processing parameter and proportioning raw materials, prepare magnesium-zirconium master alloy, magnesium-dysprosium master alloy respectively; By metal magnesia amount per-cent be 70wt%, metal zirconium mass percent be 30wt% proportioning and adopt prepare magnesium-zirconium intermediate alloy ingot with the processing parameter that magnesium-yttrium master alloy is the same.
Embodiment 1:Mg-0.5Y-0.1Dy-0.8Zn-0.4Zr degradable magnesium-rare earth
The preparation method of Mg-0.5Y-0.1Dy-0.8Zn-0.4Zr degradable magnesium-rare earth is as follows:
1, magnesium-rare earth yttrium, magnesium-zirconium master alloy is prepared. By the magnesia amount per-cent of metal be 80wt%, rare earth yttrium quality be the proportion ingredient of 20wt%, MAGNESIUM METAL and rare earth yttrium are put into cast iron or plumbago crucible heat fused and are warming up to 780 DEG C, stir after evenly and leave standstill 20 minutes, be then cast into magnesium-yttrium intermediate alloy ingot. Fusion process leads to into SF6: CO2Volume ratio is the shielding gas of 1:200. According to same processing parameter and proportioning raw materials, prepare magnesium-yttrium, magnesium-zirconium, magnesium-dysprosium master alloy respectively. By the magnesia amount of metal be 70wt%, zirconium quality be the proportioning of 30wt% and adopt above-mentioned technique to prepare magnesium-zirconium intermediate alloy ingot.
2, proportioning reasonable offer raw material: according to the loss situation of metallic element each in fusion process is the relationship between quality batching of 4.0wt.% by the magnesia amount per-cent of metal to be 91.6wt.%, metallic zinc mass percent be 0.8wt%, magnesium-yttrium master alloy mass percent to be 3.0wt.%, magnesium-dysprosium master alloy mass percent be 0.6wt.%, magnesium-zirconium master alloy mass percent.
3, alloy melting: the raw material surface sand-blasting prepared is removed the peel and is preheating to 200 DEG C. Preheating cast iron crucible, to 300 DEG C, leads to into SF6: CO2Volume ratio is the shielding gas of 1:200, adds magnesium ingot. In crucible, metal melts completely and when melt temperature reaches 740 DEG C, adds metallic zinc, magnesium-yttrium master alloy, magnesium-dysprosium master alloy successively. When melt temperature reaches 770 DEG C, add magnesium-zirconium master alloy, continue after stirring to lead to when melt temperature is down to 730 DEG C into argon gas refining 5 minutes, at 730 DEG C, leave standstill 20 minutes. When melt temperature is down to 720 DEG C, alloy liquid is cast in water cooling mold and makes degradable magnesium-rare earth ingot casting blank.
4, alloy extruding: ingot casting blank carries out homogeneous thermal treatment 10 hours at 480 DEG C, carries out turnery processing on lathe, obtains smooth surface, without being mingled with, without extrusion billet material that is lofty and depression. For obtaining best performance, extrusion billet material extrudes at 350 DEG C, and mould, ingot-containing tube temperature are 320-340 DEG C, and extrusion speed is set between 2-0.5m/s, finally obtain material requested.
5, alloy thermal treatment: the described extrusion billet material after cooling is warming up to 200 DEG C of insulations 2 hours, is then warming up to 260 DEG C of insulations 10 hours; Take out material at room temperature to cool.
Obtained alloy composition: (mass percent wt%)
The performance of the Mg-0.5Y-0.1Dy-0.8Zn-0.4Zr degradable magnesium-rare earth prepared by above-mentioned processing step is shown in Fig. 4 and Fig. 5.
Embodiment 2:Mg-1.0Y-0.3Dy-1.0Zn-0.4Zr degradable magnesium-rare earth
The preparation method of Mg-1.0Y-0.3Dy-1.0Zn-0.4Zr degradable magnesium-rare earth is as follows:
1, magnesium-rare earth yttrium, magnesium-zirconium master alloy is prepared. By the magnesia amount per-cent of metal be 80wt%, rare earth yttrium mass percent be the proportion ingredient of 20wt%, MAGNESIUM METAL and rare earth yttrium are put into cast iron or plumbago crucible heat fused and are warming up to 780 DEG C, stir after evenly and leave standstill 20 minutes, be then cast into magnesium-yttrium intermediate alloy ingot. Fusion process leads to into SF6: CO2Volume ratio is the shielding gas of 1:200. According to same processing parameter and proportioning raw materials, prepare magnesium-yttrium, magnesium-zirconium, magnesium-dysprosium master alloy respectively. By metal magnesia amount per-cent be 70wt%, zirconium mass percent be the proportioning of 30wt% and adopt above-mentioned technique to prepare magnesium-zirconium intermediate alloy ingot.
2, proportioning reasonable offer raw material: according to the loss situation of metallic element each in fusion process is the relationship between quality batching of 4.0wt.% by the magnesia amount per-cent of metal to be 87.5wt.%, metallic zinc mass percent be 1.0wt%, magnesium-yttrium master alloy mass percent to be 6.0wt.%, magnesium-dysprosium master alloy mass percent be 1.5wt.%, magnesium-zirconium master alloy mass percent.
3, alloy melting: the raw material surface sand-blasting prepared is removed the peel and is preheating to 200 DEG C. Preheating cast iron crucible, to 300 DEG C, leads to into SF6: CO2Volume ratio is the shielding gas of 1:200, adds magnesium ingot. In crucible, metal melts completely and when melt temperature reaches 740 DEG C, adds metallic zinc, magnesium-yttrium master alloy, magnesium-dysprosium master alloy successively. When melt temperature reaches 770 DEG C, add magnesium-zirconium master alloy, continue after stirring to lead to when melt temperature is down to 730 DEG C into argon gas refining 5 minutes, at 730 DEG C, leave standstill 20 minutes. When melt temperature is down to 720 DEG C, alloy liquid is cast in water cooling mold and makes degradable magnesium-rare earth ingot casting blank.
4, alloy extruding: ingot casting blank carries out homogeneous thermal treatment 10 hours at 480 DEG C, carries out turnery processing on lathe, obtains smooth surface, without being mingled with, without extrusion billet material that is lofty and depression. For obtaining best performance, extrusion billet material extrudes at 350 DEG C, and mould, ingot-containing tube temperature are 320-340 DEG C, and extrusion speed is set between 2-0.5m/s, finally obtain material requested.
5, alloy thermal treatment: the described extrusion billet material after cooling is warming up to 200 DEG C of insulations 2 hours, is then warming up to 260 DEG C of insulations 10 hours; Take out material at room temperature to cool.
Obtained alloy composition: (mass percent wt%)
| Y | Dy | Zn | Zr | Fe | Cu | Si | Ni | Mg |
| 1.04 | 0.28 | 1.02 | 0.40 | 0.001 | 0.0004 | 0.001 | 0.0003 | Surplus |
The performance of the Mg-1.0Y-0.3Dy-1.0Zn-0.4Zr degradable magnesium-rare earth prepared by above-mentioned processing step is shown in Fig. 4 and Fig. 5.
Embodiment 3:Mg-1.5Y-0.4Dy-1.0Zn-0.4Zr degradable magnesium-rare earth
The preparation method of Mg-1.5Y-0.4Dy-1.0Zn-0.4Zr degradable magnesium-rare earth is as follows:
1, magnesium-rare earth yttrium, magnesium-zirconium master alloy is prepared. By the magnesia amount per-cent of metal be 80wt%, rare earth yttrium mass percent be the proportion ingredient of 20wt%, MAGNESIUM METAL and rare earth yttrium are put into cast iron or plumbago crucible heat fused and are warming up to 780 DEG C, stir after evenly and leave standstill 20 minutes, be then cast into magnesium-yttrium intermediate alloy ingot. Fusion process leads to into SF6: CO2Volume ratio is the shielding gas of 1:200. According to same processing parameter and proportioning raw materials, prepare magnesium-yttrium, magnesium-zirconium, magnesium-dysprosium master alloy respectively. By metal magnesia amount per-cent be 70wt%, zirconium mass percent be the proportioning of 30wt% and adopt above-mentioned technique to prepare magnesium-zirconium intermediate alloy ingot.
2, proportioning reasonable offer raw material: according to the loss situation of metallic element each in fusion process, by the relationship between quality batching of the magnesia amount per-cent 83.5wt.% of metal, metallic zinc mass percent to be 1.0wt%, magnesium-yttrium master alloy mass percent be 9.0wt.%, magnesium-dysprosium master alloy mass percent to be 2.5wt.%, magnesium-zirconium master alloy mass percent be 4.0wt.%.
3, alloy melting: the raw material surface sand-blasting prepared is removed the peel and is preheating to 200 DEG C. Preheating cast iron crucible, to 300 DEG C, leads to into SF6: CO2Volume ratio is the shielding gas of 1:200, adds magnesium ingot. In crucible, metal melts completely and when melt temperature reaches 740 DEG C, adds metallic zinc, magnesium-yttrium master alloy, magnesium-dysprosium master alloy successively. When melt temperature reaches 770 DEG C, add magnesium-zirconium master alloy, continue after stirring to lead to when melt temperature is down to 730 DEG C into argon gas refining 5 minutes, at 730 DEG C, leave standstill 20 minutes. When melt temperature is down to 720 DEG C, alloy liquid is cast in water cooling mold and makes degradable magnesium-rare earth ingot casting blank.
4, alloy extruding: ingot casting blank carries out homogeneous thermal treatment 10 hours at 480 DEG C, carries out turnery processing on lathe, obtains smooth surface, without being mingled with, without extrusion billet material that is lofty and depression. For obtaining best performance, extrusion billet material extrudes at 350 DEG C, and mould, ingot-containing tube temperature are 320-340 DEG C, and extrusion speed is set between 2-0.5m/s, finally obtain material requested.
5, alloy thermal treatment: the described extrusion billet material after cooling is warming up to 200 DEG C of insulations 2 hours, is then warming up to 260 DEG C of insulations 10 hours; Take out material at room temperature to cool.
Obtained alloy composition: (mass percent wt%)
The performance of the Mg-1.5Y-0.4Dy-1.0Zn-0.4Zr degradable magnesium-rare earth prepared by above-mentioned processing step is shown in Fig. 4 and Fig. 5.
Embodiment 4:Mg-2.0Y-0.5Dy-1.2Zn-0.4Zr degradable magnesium-rare earth
The preparation method of Mg-2.0Y-0.5Dy-1.2Zn-0.4Zr degradable magnesium-rare earth is as follows:
1, magnesium-rare earth yttrium, magnesium-zirconium master alloy is prepared. By the magnesia amount per-cent of metal be 80wt%, rare earth yttrium mass percent be the proportion ingredient of 20wt%, MAGNESIUM METAL and rare earth yttrium are put into cast iron or plumbago crucible heat fused and are warming up to 780 DEG C, stir after evenly and leave standstill 20 minutes, be then cast into magnesium-yttrium intermediate alloy ingot. Fusion process leads to into SF6: CO2Volume ratio is the shielding gas of 1:200. According to same processing parameter and proportioning raw materials, prepare magnesium-yttrium, magnesium-zirconium, magnesium-dysprosium master alloy respectively. By metal magnesia amount per-cent be 70wt%, zirconium mass percent be the proportioning of 30wt% and adopt above-mentioned technique to prepare magnesium-zirconium intermediate alloy ingot.
2, proportioning reasonable offer raw material: according to the loss situation of metallic element each in fusion process is the relationship between quality batching of 4.0wt.% by the magnesia amount per-cent of metal to be 77.8wt.%, metallic zinc mass percent be 1.2wt%, magnesium-yttrium master alloy mass percent to be 13.5wt.%, magnesium-dysprosium master alloy mass percent be 3.5wt.%, magnesium-zirconium master alloy mass percent.
3, alloy melting: the raw material surface sand-blasting prepared is removed the peel and is preheating to 200 DEG C. Preheating cast iron crucible, to 300 DEG C, leads to into SF6: CO2Volume ratio is the shielding gas of 1:200, adds magnesium ingot. In crucible, metal melts completely and when melt temperature reaches 740 DEG C, adds metallic zinc, magnesium-yttrium master alloy, magnesium-dysprosium master alloy successively. When melt temperature reaches 770 DEG C, add magnesium-zirconium master alloy, continue after stirring to lead to when melt temperature is down to 730 DEG C into argon gas refining 5 minutes, at 730 DEG C, leave standstill 20 minutes. When melt temperature is down to 720 DEG C, alloy liquid is cast in water cooling mold and makes degradable magnesium-rare earth ingot casting blank.
4, alloy extruding: ingot casting blank carries out homogeneous thermal treatment 10 hours at 480 DEG C, carries out turnery processing on lathe, obtains smooth surface, without being mingled with, without extrusion billet material that is lofty and depression. For obtaining best performance, extrusion billet material extrudes at 350 DEG C, and mould, ingot-containing tube temperature are 320-340 DEG C, and extrusion speed is set between 2-0.5m/s, finally obtain material requested.
5, alloy thermal treatment: the described extrusion billet material after cooling is warming up to 200 DEG C of insulations 2 hours, is then warming up to 260 DEG C of insulations 10 hours; Take out material at room temperature to cool.
Obtained alloy composition: (mass percent wt%)
The performance of the Mg-2.0Y-0.5Dy-1.2Zn-0.4Zr degradable magnesium-rare earth prepared by above-mentioned processing step is shown in Fig. 4 and Fig. 5.
Fig. 1 is the metallograph of the degradable magnesium-rare earth of the present invention: (a) as cast condition (b) homogenization treatment state (c) extrudes state (being perpendicular to the direction of extrusion) (d) and extrude state (along the direction of extrusion). As can be seen from the figure suitable proportion, the Mg-RE phase of Dispersed precipitate be the major cause that degradable magnesium-rare earth has excellent mechanical property.
Fig. 2 is after adopting the degradable magnesium-rare earth Mg-1.5Y-0.4Dy-1.0Zn-0.4Zr vat liquor of the present invention, the L-929 cell cultures form photo of 3 days: (a) 100% vat liquor (b) 50% vat liquor (c) 10% vat liquor (d) positive controls 0.64% phenol. Compared with the unsound cellular form (rounded do not paste wall) cultivated in 0.64% phenol, the most cells cultivated in the vat liquor of the degradable magnesium-rare earth 100%, 50% and 10% of the present invention are in normal and healthy state (pasting wall in elongated shape), show that the degradable magnesium-rare earth of the present invention is to tissue nontoxicity.
Fig. 3 is the degradable magnesium-rare earth of the present invention: Mg-1.5Y-0.4Dy-1.0Zn-0.4Zr energy spectrum analysis data after 240 hours of 37 DEG C of successive soakings in SBF simulated body fluid. As can be seen from the results, degradable magnesium-rare earth generates degraded product in immersion 240 hours rear surfaces, mainly containing the phosphoric acid salt of Ca and Mg, has good biocompatibility. Ca element that spectroscopy detection goes out and P element are all from SBF simulated body fluid.
Fig. 4 is the room-temperature mechanical property table of the embodiment of the present invention 1, example 2, example 3 and example 4, result shows: the degradable magnesium-rare earth of the present invention has excellent mechanical property, meet the requirement of medical structured material, obtain optimum strengthening effect when content of rare earth is 1.5wt%Y, 0.4wt%Dy.
Fig. 5 be the embodiment of the present invention 1, example 2, example 3 and example 4 SBF simulated body fluid successive soaking test mass loss cartogram (unit: gram, specimen finish 15mm, length 20mm), result shows: the degradable magnesium-rare earth of the present invention has suitable erosion resistance and degradability, be conducive to tissue to absorb to recover, it is possible to as biological structure materials application in medical use. By the adjustment to degradable magnesium-rare earth middle-weight rare earths component concentration, it may be achieved to the control of biological structure material corrosion speed.
Described degradable magnesium-rare earth has specific rare earth element ratio, and its intensity and biodegradability obtain obvious improvement, has basic biological safety and biocompatibility. Rare earth and zr element all adopt the mode of master alloy to add, and adopt suitable melting preparation technology according to this mode. Degradable magnesium-rare earth have employed its specific thermal treatment process. Therefore adopt rare earth element as the chemical conversion point of described degradable magnesium-rare earth, to improve its intensity and corrosion resisting property, thus advance the development of Medical magnesium alloy material. Research shows: the rare earth element velocity of diffusion of biological vivo degradation is very slow, and the rare earth concentration after human body fluid dilutes obviously reduces, and is obviously weakened by the poisoning effect of human body. In addition, rare earth magnesium alloy material can promote bone growth, is of value to wound and recovers. These results show that magnesium-rare earth is a kind of potential desirable biomaterial.
Therefore, using Medical magnesium alloy material as target, the degradable magnesium-rare earth of the present invention carrys out refinement degradable magnesium-rare earth tissue with improving corrosion resistance nature by adding the rare earth element of different content, obtains outstanding mechanical property with this and retains good biocompatibility simultaneously. On the one hand, rare earth element has high poisoning effect concentration, and Y and Dy of high-dissolvability shows outstanding biological friendly. On the other hand, Mg-Y-Zn-Zr base alloy has excellent mechanical property, it is possible to meet the needs of human body medical material. The degradable magnesium-rare earth of the present invention has the following advantages: 1, have good mechanical property and processing characteristics, it is possible to meet the needs of medical embedded material; 2, there is good corrosion resistance nature, can realize degrading completely, suitable corrosion speed can be ensured again; 3, the toxicity of alloy element has strict restriction.
The useful effect of the present invention is as follows:
1, degradable magnesium-rare earth has good mechanical property, it is possible to meet the performance needs of medical bio base material, and its room temperature tensile intensity, yield strength, unit elongation reach respectively: 190-280MPa, 100-170MPa, 5-15%. Meanwhile, good plasticity also ensures that the degradable magnesium-rare earth of the present invention can carry out precise forming processing, has the ability of preparation biological structure parts.
2, the degradable magnesium-rare earth of the present invention is not containing the alloying element that human body has poisoning effect, safe and reliable. By the degradable magnesium-rare earth 100%, 50% of the present invention and 10% vat liquor appreciation rate relative to the cell after L-929 cell cultures is analyzed, confirm that degradable magnesium-rare earth has basic biological safety and biocompatibility, it is possible to be applied to medical field.
3, degradable magnesium-rare earth has erosion resistance to a certain degree and degradability concurrently, it is possible to as biological structure materials application in medical use. The test of simulated body fluid successive soaking proves that the degradable magnesium-rare earth of the present invention has suitable erosion rate, is conducive to tissue to absorb and recovers. Degradable magnesium-rare earth reacts at 37 DEG C and SBF simulated body fluid, and Surface Creation main component is soluble M g (OH)2With the degraded product of hydroxyapatite HA. Wherein, hydroxyapatite is the main component of bone, therefore has good biocompatibility and uses as embedded material.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations. For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, it is also possible to make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (3)
1. the preparation method of a degradable magnesium-rare earth biomaterial for medical purpose, it is characterised in that, comprise the following steps:
(1) alloy melting: raw material is undertaken by proportioning preparing burden, surface sand-blasting is removed the peel and is preheating to 200 DEG C; Preheating cast iron crucible, to 300 DEG C, leads to into SF6: CO2Volume ratio is the shielding gas of 1:200, adds magnesium ingot; In crucible, metal melts completely and when melt temperature reaches 740 DEG C, adds metallic zinc, magnesium-yttrium master alloy, magnesium-dysprosium master alloy successively; When melt temperature reaches 770 DEG C, add magnesium-zirconium master alloy, continue after stirring to lead to when melt temperature is down to 730 DEG C into argon gas refining 5 minutes, at 730 DEG C, leave standstill 20 minutes; When melt temperature is down to 720 DEG C, alloy liquid is cast in water cooling mold and makes degradable magnesium-rare earth ingot casting blank;
(2) alloy extruding: described ingot casting blank carries out homogeneous thermal treatment 10 hours at 480 DEG C, carries out turnery processing on lathe, obtains smooth surface, without being mingled with, without extrusion billet material that is lofty and depression;
(3) alloy thermal treatment: the described extrusion billet material after cooling is warming up to 200 DEG C of insulations 2 hours, is then warming up to 260 DEG C of insulations 10 hours; Take out described extrusion billet material at room temperature to cool; Described degradable magnesium-rare earth biomaterial for medical purpose chemistry composition is by mass percentage: Y0.5-2.0wt.%, Dy0.1-0.5wt.%, Zn0.8-1.2wt.%, Zr0.35-0.55wt.%, all the other are Mg and inevitable impurity element.
2. the preparation method of degradable magnesium-rare earth biomaterial for medical purpose as claimed in claim 1, it is characterized in that, during step (2) alloy extrudes: described extrusion billet material extrudes at 350 DEG C, and mould, ingot-containing tube temperature are 320-340 DEG C, and extrusion speed is set between 2-0.5m/s.
3. the preparation method of degradable magnesium-rare earth biomaterial for medical purpose as claimed in claim 1 or 2, it is characterised in that, this preparation method also comprises the following steps:
Prepare magnesium-rare earth intermediate alloy: by the magnesia amount per-cent of metal be 80wt%, rare earth quality be the proportion ingredient of 20wt%, MAGNESIUM METAL and rare earth are put into cast iron or plumbago crucible heat fused and are warming up to 780 DEG C, stir after evenly and leave standstill 20 minutes, then it is cast into magnesium-rare earth intermediate alloy ingot, fusion process leads to into SF6: CO2Volume ratio is the shielding gas of 1:200; According to same processing parameter and proportioning raw materials, prepare magnesium-yttrium master alloy, magnesium-dysprosium master alloy respectively; By metal magnesia amount per-cent be 70wt%, metal zirconium mass percent be 30wt% proportioning and adopt the processing parameter the same with magnesium-rare earth intermediate alloy prepare magnesium-zirconium intermediate alloy ingot.
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| CN104846247B (en) * | 2015-05-04 | 2017-05-31 | 河南科技大学 | Addition gadolinium, magnesium alloy biodegradation material of yttrium and preparation method thereof |
| CN105803282B (en) * | 2016-03-22 | 2017-12-08 | 中国兵器科学研究院宁波分院 | A kind of single-phase Multielement rare-earth magnesium alloy biodegradation material and preparation method thereof |
| CN105950931B (en) * | 2016-07-20 | 2018-10-02 | 肖旅 | The high-strength high hard magnesium alloy of controllable reaction and its manufacturing method of component occurs with water |
| CN106319313A (en) * | 2016-10-21 | 2017-01-11 | 郑州大学 | Biomedical degradable Mg-Zn-Y-Nd-Cu alloy and preparation method thereof |
| CN109266889B (en) * | 2018-12-05 | 2020-10-02 | 四川大学 | Composite refining method of zirconium-containing magnesium alloy |
| CN109680195B (en) * | 2019-02-19 | 2020-03-27 | 北京大学 | Mg-RE series magnesium alloy and preparation method and application thereof |
| CN112126836B (en) * | 2019-06-25 | 2022-04-29 | 河南科技大学 | Biodegradable magnesium alloy and preparation method thereof |
| CN110468319B (en) * | 2019-08-13 | 2021-05-18 | 中国兵器科学研究院宁波分院 | Mg-Y-Nd- (La + Ce) -Zr biodegradable magnesium alloy and preparation method thereof |
| CN112813324B (en) * | 2019-11-18 | 2021-09-28 | 西南大学 | Precipitation strengthening type implantable magnesium alloy and preparation process thereof |
| WO2021102922A1 (en) * | 2019-11-29 | 2021-06-03 | 福建坤孚股份有限公司 | Preparation method for high-strength soluble magnesium alloy material |
| WO2022056790A1 (en) * | 2020-09-17 | 2022-03-24 | 深圳镁极净科技有限公司 | Solid metal material quickly soluble in water and preparation method therefor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102762235A (en) * | 2010-03-25 | 2012-10-31 | 百多力股份公司 | Implant made of a biodegradable magnesium alloy |
| CN103498088A (en) * | 2013-10-17 | 2014-01-08 | 中国科学院长春应用化学研究所 | Rare earth magnesium alloy and preparation method thereof |
| CN103889475A (en) * | 2011-08-15 | 2014-06-25 | Meko激光材料加工公司 | Resorbable stents which contain a magnesium alloy |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102762235A (en) * | 2010-03-25 | 2012-10-31 | 百多力股份公司 | Implant made of a biodegradable magnesium alloy |
| CN103889475A (en) * | 2011-08-15 | 2014-06-25 | Meko激光材料加工公司 | Resorbable stents which contain a magnesium alloy |
| CN103498088A (en) * | 2013-10-17 | 2014-01-08 | 中国科学院长春应用化学研究所 | Rare earth magnesium alloy and preparation method thereof |
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