CN105087980A - Method for preparing hemostatic clips through surface-passivated degradable magnesium alloy - Google Patents
Method for preparing hemostatic clips through surface-passivated degradable magnesium alloy Download PDFInfo
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Abstract
Disclosed is a method for preparing hemostatic clips through surface-passivated degradable magnesium alloy. The magnesium alloy is composed of alloy elements including, by mass, 3% of Zn, 0.5-1.0% of Zr, 0.0-1.0% of Sr, 0.0-1.0% of Ca, 0.0-1.0% of Ag and the balance Mg. The preparation method includes the steps that ingots obtained through casting are squeezed into profile materials at the temperature of 250-400 DEG C, machined into the hemostatic clips, then subjected to aging treatment and finally subjected to surface passivating treatment. The method for preparing the hemostatic clips through the surface-passivated degradable magnesium alloy has the advantages that the hemostatic clips prepared through the method have proper obdurability and can meet the requirements for mechanical properties of materials by a broken end of a closed vessel; the degrading speed of the hemostatic clips made of the surface-passivated magnesium alloy is controllable, it is guaranteed that the hemostatic clips keep effective within two weeks in clinical use and can be completely corroded and degraded 1-2 months later after performing function.
Description
Technical field
The present invention relates to the preparation of laparoscopic surgery hemostatic clamp for blood vessel, particularly a kind of method adopting the degradable magnesium alloy of surface passivation to prepare hemostatic clamp.
Background technology
Hemostatic clamp be a kind of be mainly used in laparoscopic surgery to close cut the medicine equipment of blood vessel, and because of its good sealing effect with use easily, to be widely used by micro-wound surgical operation.Mainly contain metal clip and high score sub-folder clinically.Wherein, metal hemostatic clamp mainly silver brain clip, tantalum folder and titanium folder.Early stage at laparoscopic surgery, the silver hemostatic clamp of general employing.But it resides in human body for a long time can produce larger toxicity, few absolutely use at present.In recent years, the most widely used titanium alloy hemostatic clamp clinically, main manufacturer is Johnson Co..Domestic also have part medical apparatus corporation, Ltd to produce, but be have problem for the safety performance of titanium folder at clinicing aspect always.
klein, RDdeng research show, after Laparoscopic Cholecystectomy, titanium folder forever retains the interference that postoperative body image can be brought to check, and experimentation on animals shows, and after implantation titanium presss from both sides for some time, bad pathology occurs for the tissue of animal.Because titanium folder is a kind of implant forever retained in body, and easily produce interference to the postoperative imaging examination of human body, the accuracy of impact diagnosis, foreign matter is forever retained in body also can be with and is served potential hazard.
For this reason, have developed biodegradable polymer hemostatic clamp abroad, progressively can degrade in certain hour after surgery, overcome the undesirable action of titanium alloy hemostatic clamp.The degradable hemostasis of clinical application accompanies two kinds, and a kind of ABSOLOK ligation nail clip being Johnson Co. and manufacturing, is made up of PPDO.Final degraded product is CO
2and H
2o.This kind of Absorbable clips can at about 180 days by the degradable absorption of human body after implant into body.Another kind is the Lapro-Clip absorbable ligature clamp that Tai Ke company of the U.S. manufactures, and is made up of inside and outside double-layer structure, and the material of outer folder is polyglycolic acid, and the material of internal layer folder is poly-glycol carbonic acid.The product lactic acid of polyglycolic acid degraded, oxyacetic acid are all the intermediate products of organism metabolism, and poly-glycolic acid is also to be degraded to harmless small molecules, and the final degraded product of curb pins is CO
2and H
2o.The Absorbable clips of domestic Hangzhou Sheng Shi company research and development, on the basis of Lapro-Clip Absorbable clips, the skin of folder adopts polyglycolic acid, and the material of internal layer folder is PPDO.Have outside excellent biological degradability, also with physical and mechanical properties and the thermal characteristics of excellence, but it cannot ensure mechanical integrity within the clinical cycle, and cost is higher.Therefore, needing one badly can be absorbed by organism degrades, can keep again the hemostatic clamp of mechanical integrity.
Magnesium alloy is biodegradable as one, and there is good biocompatibility material implantedly prepared laparoscopic surgery hemostatic clamp by trial.But the present invention prepares the magnesium alloy materials of hemostatic clamp and Treatment technique for processing has no report both at home and abroad.
Summary of the invention
The object of the invention is for above-mentioned existing problems, a kind of method adopting the degradable magnesium alloy of surface passivation to prepare hemostatic clamp is provided, the magnesium alloy hemostatic clamp prepared with this material has the biocompatibility of enough vessel sealing holding forces and suitable degradation rate and excellence, meets the clinical demand of laparoscopic surgery hemostasis completely.
Technical scheme of the present invention:
A kind of method adopting the degradable magnesium alloy of surface passivation to prepare hemostatic clamp, described degradable magnesium alloy material, be made up of Mg, Zn, Zr and Addition ofelements, Addition ofelements is the one, two or three in Sr, Ca and Ag, the mass percent of each component is: Zn is 3%, Zr be 0.5-0.8, Sr be 0-1.0%, Ca be 0-1.0%, Ag be 0.0-1.0%, Mg is surplus, and preparation process is as follows:
1) be that the Mg of 99.99wt%, analytically pure Zn, Mg-Zr master alloy and magnesium and Addition ofelements master alloy add in plumbago crucible by purity, be evacuated to 1 × 10
-2pa, passes into argon shield, is heated to 710-780 DEG C and is incubated 10-20 minute, then starts cooling after fully stirring 2-10min with the speed of 2-10r/s, and temperature pours into crystallizer after being down to 650-700 DEG C, obtains the billet that diameter is 50-60mm;
2) above-mentioned billet is placed in air furnace, at 300-350 DEG C, is incubated 20-50h carries out homogenizing annealing, then be warming up to 400-520 DEG C insulation 1-5h carry out solution treatment, finally quench in 30-50 DEG C of warm water;
3) hot extrusion at 300-400 DEG C of temperature of the billet after above-mentioned ageing treatment is obtained magnesium alloy profiles;
4) thickness is become by above-mentioned magnesium alloy profiles Linear cut to be the hemostatic clamp of 1-2mm, finally ageing treatment 20-60h at 150-200 DEG C of temperature;
5) be dipped in hydrofluoric acid aqueous solution by above-mentioned hemostatic clamp and carry out surface passivating treatment, hydrofluoric acid concentration is 10-25wt%, temperature is 20-70 DEG C, soak time is 1-10h, obtains the degradable magnesium alloy hemostatic clamp of surface passivation.
Described step 1) in, in Mg-Zr master alloy, the mass percent of Zr is 30%, and in the master alloy composition of magnesium and Addition ofelements, the mass percent of Addition ofelements is 30%.
Advantage of the present invention and beneficial effect are:
This magnesium alloy hemostatic clamp, after ageing treatment and surface passivating treatment, has suitable combination of strength and toughness, can meet the requirement of closed ends of vessels to material mechanical performance; Particularly by after hydrofluoric acid Passivation Treatment, the MgF that Mg alloy surface is formed
2nano-particle layer can improve the biocompatibility of magnesium alloy greatly, can reduce again the degradation rate of operation initial stage magnesium alloy, ensures the validity that hemostatic clamp is on active service, and after functionating corrosion degradation completely in 1-2 month.
Accompanying drawing explanation
Fig. 1 is the degradable magnesium alloy hemostatic clamp sample of surface passivation prepared by embodiment 1.
Fig. 2 is the pattern of the degradable magnesium alloy hemostatic clamp surface passivation layer of surface passivation prepared by embodiment 1.
Embodiment
Embodiment 1:
A kind of method adopting the degradable magnesium alloy of surface passivation to prepare hemostatic clamp, described degradable magnesium alloy material, be made up of Mg, Zn, Zr, Sr, the mass percent of each component is: Zn is 3%, Zr is 0.8%, Sr is 0.3%, Mg is surplus, and preparation process is as follows:
1) be that the Mg of 99.99wt%, analytically pure Zn, Mg-Zr master alloy and Mg-Sr master alloy add in plumbago crucible by purity, wherein in Mg-Zr master alloy, the mass percent of Zr is 30%, in Mg-Sr master alloy composition, the mass percent of Sr is 30%, is evacuated to 1 × 10
-2pa, passes into argon shield, is heated to 780 DEG C and is incubated 20 minutes, then starts cooling after fully stirring 10min with the speed of 8r/s, and temperature pours into crystallizer after being down to 650 DEG C, obtains the billet that diameter is 60mm;
2) above-mentioned billet is placed in air furnace, is incubated after 6h carries out homogenizing annealing at 350 DEG C of temperature, then be warming up to 500 DEG C of insulation 1h and carry out solution treatment, finally quench in 30-50 DEG C of warm water;
3) by the hot extrusion at 350 DEG C of temperature of the billet after above-mentioned ageing treatment, adopt mould 4 hole, extrusion ratio is 48, the tensile yield strength of As-extruded alloy is 290MPa, tensile strength is 365MPa, elongation is 17.5%, obtain magnesium alloy profiles;
4) thickness is become by above-mentioned magnesium alloy profiles Linear cut to be the hemostatic clamp of 1mm, finally ageing treatment 40h at 170 DEG C of temperature in a vacuum furnace;
5) be dipped in hydrofluoric acid aqueous solution by above-mentioned hemostatic clamp and carry out surface passivating treatment, hydrofluoric acid concentration is 20wt%, temperature is 37 DEG C, soak time is 3h, obtains the degradable magnesium alloy hemostatic clamp of surface passivation.
Fig. 1 is the degradable magnesium alloy hemostatic clamp sample of the surface passivation of preparation.
Fig. 2 is the pattern of the degradable magnesium alloy hemostatic clamp surface passivation layer of the surface passivation of preparation, and its surface is in weak golden, and hydrofluoric acid treatment layer thickness is 0.5 μm, is combined well with matrix.
Embodiment 2:
A kind of method adopting the degradable magnesium alloy of surface passivation to prepare hemostatic clamp, described degradable magnesium alloy material is made up of Mg, Zn, Zr, Ca and Ag, the mass percent of each component is: Zn is 3%, Zr is 0.7%, Ca is 0.3%, Ag is 0.3%, Mg is surplus, and preparation process is as follows:
1) be that the Mg of 99.99wt%, analytically pure Zn, Mg-Zr master alloy, Mg-Ca master alloy and Mg-Ag master alloy add in plumbago crucible by purity, wherein in Mg-Zr master alloy, the mass percent of Zr is 30%, in Mg-Ca master alloy composition, the mass percent of Ca is 30%, in Mg-Ag master alloy, the mass percent of Ag is 30%, is evacuated to 1 × 10
-2pa, passes into argon shield, is heated to 780 DEG C and is incubated 20 minutes, then starts cooling after fully stirring 10min with the speed of 8r/s, and temperature pours into crystallizer after being down to 650 DEG C, obtains the billet that diameter is 60mm;
2) above-mentioned billet is placed in air furnace, is incubated after 48h carries out homogenizing annealing at 300 DEG C of temperature, then be warming up to 400 DEG C of insulation 1h and carry out solution treatment, finally quench in 30-50 DEG C of warm water;
3) by the hot extrusion at 350 DEG C of temperature of the billet after above-mentioned ageing treatment, adopt mould 4 hole, extrusion ratio is 48, the tensile yield strength of As-extruded alloy is 288MPa, tensile strength is 370MPa, elongation is 15.6%, obtain magnesium alloy profiles;
4) thickness is become by above-mentioned magnesium alloy profiles Linear cut to be the hemostatic clamp of 2mm, finally ageing treatment 20h at 170 DEG C of temperature in a vacuum furnace;
5) be dipped in hydrofluoric acid aqueous solution by above-mentioned hemostatic clamp and carry out surface passivating treatment, hydrofluoric acid concentration is 20wt%, temperature is 37 DEG C, soak time is 2h, obtains the degradable magnesium alloy hemostatic clamp of surface passivation.
Obtained hemostatic clamp surface is in weak golden, and hydrofluoric acid treatment layer thickness is about 0.5 μm, is combined well with matrix.
Embodiment 3:
A kind of method adopting the degradable magnesium alloy of surface passivation to prepare hemostatic clamp, described degradable magnesium alloy material is made up of Mg, Zn, Zr, Ca, the mass percent of each component is: Zn is 3%, Zr is 0.6%, Ca is 0.3%, Mg is surplus, and preparation process is as follows:
1) be the Mg of 99.99wt% by purity, analytically pure Zn, Mg-Zr master alloy, Mg-Ca master alloy add in plumbago crucible, wherein in Mg-Zr master alloy, the mass percent of Zr is 30%, in Mg-Ca master alloy composition, the mass percent of Ca is 30%, is evacuated to 1 × 10
-2pa, passes into argon shield, is heated to 780 DEG C and is incubated 20 minutes, then starts cooling after fully stirring 10min with the speed of 8r/s, and temperature pours into crystallizer after being down to 650 DEG C, obtains the billet that diameter is 60mm;
2) above-mentioned billet is placed in air furnace, is incubated after 36h carries out homogenizing annealing at 300 DEG C of temperature, then be warming up to 450 DEG C of insulation 3h and carry out solution treatment, finally quench in 30-50 DEG C of warm water;
3) by the hot extrusion at 300 DEG C of temperature of the billet after above-mentioned ageing treatment, adopt mould 4 hole, extrusion ratio is 48, the tensile yield strength of As-extruded alloy is 248MPa, tensile strength is 305MPa, elongation is 25.5%, obtain magnesium alloy profiles;
4) thickness is become by above-mentioned magnesium alloy profiles Linear cut to be the hemostatic clamp of 1mm, finally ageing treatment 24h at 160 DEG C of temperature in a vacuum furnace;
5) be dipped in hydrofluoric acid aqueous solution by above-mentioned hemostatic clamp and carry out surface passivating treatment, hydrofluoric acid concentration is 20wt%, temperature is 37 DEG C, soak time is 2h, obtains the degradable magnesium alloy hemostatic clamp of surface passivation.
Obtained hemostatic clamp surface is in weak golden, and hydrofluoric acid treatment layer thickness is about 0.5 μm, is combined well with matrix.
Embodiment 4:
A kind of method adopting the degradable magnesium alloy of surface passivation to prepare hemostatic clamp, described degradable magnesium alloy material is made up of Mg, Zn, Zr, Ca and Sr, the mass percent of each component is: Zn is 3%, Zr is 0.8%, Ca is 0.3%, Sr is 0.3%, Mg is surplus, and preparation process is as follows:
1) be that the Mg of 99.99wt%, analytically pure Zn, Mg-Zr master alloy, Mg-Ca master alloy and Mg-Sr master alloy add in plumbago crucible by purity, wherein in Mg-Zr master alloy, the mass percent of Zr is 30%, in Mg-Ca master alloy composition, the mass percent of Ca is 30%, in Mg-Sr master alloy, the mass percent of Sr is 30%, is evacuated to 1 × 10
-2pa, passes into argon shield, is heated to 780 DEG C and is incubated 20 minutes, then starts cooling after fully stirring 10min with the speed of 8r/s, and temperature pours into crystallizer after being down to 650 DEG C, obtains the billet that diameter is 60mm;
2) above-mentioned billet is placed in air furnace, is incubated after 48h carries out homogenizing annealing at 350 DEG C of temperature, then be warming up to 500 DEG C of insulation 2h and carry out solution treatment, finally quench in 30-50 DEG C of warm water;
3) by the hot extrusion at 350 DEG C of temperature of the billet after above-mentioned ageing treatment, adopt mould 4 hole, extrusion ratio is 48, the tensile yield strength of As-extruded alloy is 305MPa, tensile strength is 395MPa, elongation is 14.5%, obtain magnesium alloy profiles;
4) thickness is become by above-mentioned magnesium alloy profiles Linear cut to be the hemostatic clamp of 1.5mm, finally ageing treatment 48h at 170 DEG C of temperature in a vacuum furnace;
5) be dipped in hydrofluoric acid aqueous solution by above-mentioned hemostatic clamp and carry out surface passivating treatment, hydrofluoric acid concentration is 20wt%, temperature is 37 DEG C, soak time is 3h, obtains the degradable magnesium alloy hemostatic clamp of surface passivation.
Obtained hemostatic clamp surface is in weak golden, and hydrofluoric acid treatment layer thickness is about 0.5 μm, is combined well with matrix.
Claims (2)
1. the method adopting the degradable magnesium alloy of surface passivation to prepare hemostatic clamp, described degradable magnesium alloy material, be made up of Mg, Zn, Zr and Addition ofelements, Addition ofelements is the one, two or three in Sr, Ca and Ag, the mass percent of each component is: Zn is 3%, Zr be 0.5-0.8, Sr be 0-1.0%, Ca be 0-1.0%, Ag be 0.0-1.0%, Mg is surplus, it is characterized in that preparation process is as follows:
1) be that the Mg of 99.99wt%, analytically pure Zn, Mg-Zr master alloy and magnesium and Addition ofelements master alloy add in plumbago crucible by purity, be evacuated to 1 × 10
-2pa, passes into argon shield, is heated to 710-780 DEG C and is incubated 10-20 minute, then starts cooling after fully stirring 2-10min with the speed of 2-10r/s, and temperature pours into crystallizer after being down to 650-700 DEG C, obtains the billet that diameter is 50-60mm;
2) above-mentioned billet is placed in air furnace, at 300-350 DEG C, is incubated 20-50h carries out homogenizing annealing, then be warming up to 400-520 DEG C insulation 1-5h carry out solution treatment, finally quench in 30-50 DEG C of warm water;
3) hot extrusion at 300-400 DEG C of temperature of the billet after above-mentioned ageing treatment is obtained magnesium alloy profiles;
4) thickness is become by above-mentioned magnesium alloy profiles Linear cut to be the hemostatic clamp of 1-2mm, finally ageing treatment 20-60h at 150-200 DEG C of temperature;
5) be dipped in hydrofluoric acid aqueous solution by above-mentioned hemostatic clamp and carry out surface passivating treatment, hydrofluoric acid concentration is 10-25wt%, temperature is 20-70 DEG C, soak time is 1-10h, obtains the degradable magnesium alloy hemostatic clamp of surface passivation.
2. adopt the degradable magnesium alloy of surface passivation to prepare the method for hemostatic clamp according to claim 1, it is characterized in that: described step 1) in, in Mg-Zr master alloy, the mass percent of Zr is 30%, and in the master alloy composition of magnesium and Addition ofelements, the mass percent of Addition ofelements is 30%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105455863A (en) * | 2015-12-31 | 2016-04-06 | 山东中保康医疗器具有限公司 | Degradable magnesium alloy mini clamp |
| CN105603282A (en) * | 2015-12-30 | 2016-05-25 | 天津理工大学 | Method for preparing magnesium alloy laparoscope hemostasis clip |
| CN106377803A (en) * | 2016-08-31 | 2017-02-08 | 济南大学 | Mg-Zn-Sr-Ca-Zr medicinal bone nail and preparation method thereof |
| CN107435116A (en) * | 2017-07-10 | 2017-12-05 | 太原理工大学 | A kind of magnesium alloy biological implantation material and preparation method thereof |
| CN107736906A (en) * | 2017-09-18 | 2018-02-27 | 天津理工大学 | A kind of Absorbale magnesium alloy skin closure nail and preparation method thereof |
| CN109280828A (en) * | 2018-12-10 | 2019-01-29 | 南京工程学院 | A kind of high-strength degradable implantation instrument composite material and preparation method |
| CN109295367A (en) * | 2018-12-10 | 2019-02-01 | 南京工程学院 | A kind of high-strength anticorrosion Biological magnesium alloy and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603282A (en) * | 2015-12-30 | 2016-05-25 | 天津理工大学 | Method for preparing magnesium alloy laparoscope hemostasis clip |
| CN105455863A (en) * | 2015-12-31 | 2016-04-06 | 山东中保康医疗器具有限公司 | Degradable magnesium alloy mini clamp |
| CN106377803A (en) * | 2016-08-31 | 2017-02-08 | 济南大学 | Mg-Zn-Sr-Ca-Zr medicinal bone nail and preparation method thereof |
| CN106377803B (en) * | 2016-08-31 | 2019-09-03 | 济南大学 | A kind of medical bone nail of Mg-Zn-Sr-Ca-Zr and preparation method thereof |
| CN107435116A (en) * | 2017-07-10 | 2017-12-05 | 太原理工大学 | A kind of magnesium alloy biological implantation material and preparation method thereof |
| CN107435116B (en) * | 2017-07-10 | 2019-06-11 | 太原理工大学 | A kind of magnesium alloy biological implantation material and preparation method thereof |
| CN107736906A (en) * | 2017-09-18 | 2018-02-27 | 天津理工大学 | A kind of Absorbale magnesium alloy skin closure nail and preparation method thereof |
| CN109280828A (en) * | 2018-12-10 | 2019-01-29 | 南京工程学院 | A kind of high-strength degradable implantation instrument composite material and preparation method |
| CN109295367A (en) * | 2018-12-10 | 2019-02-01 | 南京工程学院 | A kind of high-strength anticorrosion Biological magnesium alloy and preparation method thereof |
| CN109280828B (en) * | 2018-12-10 | 2021-03-02 | 南京工程学院 | High-strength degradable composite material for implanting instrument and preparation method thereof |
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Application publication date: 20151125 |