CN110916747A - Absorbable zinc-copper alloy ligation clamp for solution treatment and preparation method thereof - Google Patents
Absorbable zinc-copper alloy ligation clamp for solution treatment and preparation method thereof Download PDFInfo
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- CN110916747A CN110916747A CN201911098672.XA CN201911098672A CN110916747A CN 110916747 A CN110916747 A CN 110916747A CN 201911098672 A CN201911098672 A CN 201911098672A CN 110916747 A CN110916747 A CN 110916747A
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- zinc
- clip
- copper alloy
- copper
- solution treatment
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- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 13
- 239000011701 zinc Substances 0.000 claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 21
- 230000002439 hemostatic effect Effects 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 238000003723 Smelting Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000010587 phase diagram Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000003754 machining Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 206010061218 Inflammation Diseases 0.000 abstract description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 239000007857 degradation product Substances 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 230000004054 inflammatory process Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 230000035755 proliferation Effects 0.000 abstract description 2
- 210000003556 vascular endothelial cell Anatomy 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract 2
- 230000003467 diminishing effect Effects 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 239000011787 zinc oxide Substances 0.000 abstract 1
- 210000001519 tissue Anatomy 0.000 description 6
- 238000002324 minimally invasive surgery Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000001356 surgical procedure Methods 0.000 description 2
- 208000005422 Foreign-Body reaction Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910009369 Zn Mg Inorganic materials 0.000 description 1
- 229910007573 Zn-Mg Inorganic materials 0.000 description 1
- 229910007565 Zn—Cu Inorganic materials 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 210000002808 connective tissue Anatomy 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 210000000626 ureter Anatomy 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods
- A61B17/12—Surgical instruments, devices or methods for ligaturing or otherwise compressing tubular parts of the body, e.g. blood vessels or umbilical cord
- A61B17/122—Clamps or clips, e.g. for the umbilical cord
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods
- A61B2017/00004—(bio)absorbable, (bio)resorbable or resorptive
Landscapes
- Health & Medical Sciences (AREA)
- Surgery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Heart & Thoracic Surgery (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Vascular Medicine (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Reproductive Health (AREA)
- Medical Informatics (AREA)
- Molecular Biology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Surgical Instruments (AREA)
Abstract
The invention relates to an absorbable zinc-copper alloy ligating clip subjected to solution treatment and a preparation method thereof. The ligating clip is prepared from a zinc-copper alloy material, wherein the mass fraction of zinc in the zinc-copper alloy is 99.7-99 wt%, and the mass fraction of copper is 0.3-1 wt%. The zinc-copper alloy has good biocompatibility and degradation performance after solution treatment. The early-stage degradation product of the ligating clip is mainly zinc oxide, has the functions of diminishing inflammation and astringing, and can reduce the complications of appliance use; the copper element can promote the proliferation of vascular endothelial cells and has certain antibacterial effect; the second phase of the alloy is reduced or disappeared after the solution treatment, thereby preventing the corrosion of the microelectrode, improving the corrosion uniformity of the product and enhancing the mechanical property of the material. The ligation clip is simple in structure and simple in preparation process, can meet clinical requirements, and reduces long-term risks.
Description
The technical field is as follows:
the invention belongs to the field of biomedical materials, and particularly relates to an absorbable zinc alloy ligating clip subjected to solution treatment and a preparation method thereof.
Background art:
chinese Disposable ligation clip market research and future prediction report (2017 edition) show: during endoscopic minimally invasive surgery, "incision", "separation", "ligation", and "suturing" are the basic steps in the surgery. The traditional ligation operation generally adopts silk threads to ligate blood vessels, cystic vessels, ureters and other parts, and the operation is complex and takes a long time. Meanwhile, when the part to be ligated is in the deep layer of the tissue, it is more difficult to ligate with the conventional silk thread. For the endoscope minimally invasive surgery, the operation difficulty of the silk ligation is increased due to the limited operation space of the endoscope minimally invasive surgery. The ligation clip adopts the special design of arc-shaped belt lock catches, and the ligation clip can be accurately sent to an operation part through a special clip applier, and the tissues to be ligated are completely locked. The operation is simpler and more convenient, the feedback is sensitive, the time consumption is short, and the ligation effect is more reliable. Currently, ligation clips are indispensable special consumables in endoscopic minimally invasive surgery.
The operation usually adopts the clip of metal material for the centre gripping intracavity tissue prevents that liquid from leaking, plays hemostatic or ligation's effect. Clips made of metal materials, such as stainless steel clips and titanium clips, can not be degraded and absorbed, and can generate foreign body reaction or tissue stimulation to cause inflammation, pain and other diseases in a human body for a long time; and the risk of mechanical damage to the tissue may increase.
Patent CN 103480035 a discloses an absorbable magnesium-based composite hemostatic clamp and a preparation method thereof. The hemostatic clip body is prepared by adopting absorbable magnesium-based composite material. Compared with the prior art, the zinc-based alloy is prepared by zinc-based alloy. The zinc-based alloy has the advantages of good biocompatibility and physical properties, the initial degradation product has the anti-inflammatory effect, and the degradation characteristic can increase the service time of the ligation clip.
Patent CN 108577922A discloses a degradable zinc alloy laparoscope hemostatic clamp and a preparation method thereof. Is prepared from Zn-Mg alloy. Compared with the prior art, the copper is adopted as the second element of the alloy, and the main reason is that the copper is a trace element necessary for the growth of connective tissues, nerves and bones and can promote the proliferation of vascular endothelial cells; in addition, the Cu element also has a certain antibacterial effect, which may reduce the risk of infection during surgery. The second phase of the zinc-copper alloy is reduced or disappears after the solution treatment, thereby preventing the corrosion of the microelectrode, improving the uniformity of the corrosion of the product and enhancing the mechanical property of the material.
Disclosure of Invention
An absorbable Zn-Cu alloy ligature clamp treated by solution treatment is prepared from pure Zn (99.99%) and pure Cu (99.99%).
The mass fraction of zinc in the zinc-copper alloy material is 99.7-99 wt%; the copper element accounts for 0.3-1 wt%.
The absorbable zinc-copper alloy ligature clamp subjected to solution treatment is characterized in that: the ligating clip is U-shaped, the main body is divided into 3 parts, an upper clamping surface (figure 1-1), a lower clamping surface (figure 1-2) and a clip (figure 1-3); the upper clamping surface and the lower clamping surface are rectangular in shape, the length is 0.5-1.5mm, and the width is 0.5-1.0 mm. The inner side of the upper clamping surface is provided with a plurality of circular unit bulges (figures 1-5) which are 0.1-0.3mm higher than the basal surface, and the peripheries of the circular bulges are dispersedly distributed with small particles with cursive property, the middle parts of the circular bulges are denser (figure 2), so that the target tissue is expanded and squeezed, and the friction force is increased. The lower clamping surface has a 0.2-0.5mm depression (figure 1-6) which is matched with the upper clamping surface, the clip has a barb (figure 1-4) and is in a bent structure, and the upper and lower structures are matched.
The absorbable zinc-copper alloy ligature clamp after the solution treatment can be prepared by adopting a zinc-copper alloy material, and comprises the following steps:
(1) pure zinc (the purity is more than or equal to 99.99%) and copper wire (the purity is more than or equal to 99.99%) are fed according to a certain mass fraction ratio and smelted in vacuum or inert gas at the smelting temperature of 500-600 ℃.
(2) And casting the smelting material into a zinc-copper alloy cast ingot, and carrying out large-deformation machining treatment.
(3) And (3) carrying out forming treatment on the alloy obtained in the step (2) to obtain the shape of the zinc-copper alloy ligation clip.
(4) And (4) heating the formed ligation clip in the step (3) for solution treatment, and rapidly cooling and quenching after treatment to obtain the zinc-copper alloy ligation clip of the single-phase supersaturated solid solution.
(5) And (4) putting the ligation clip obtained in the step (4) into absolute ethyl alcohol, cleaning the surface of the ligation clip to be smooth, taking out the ligation clip and drying the ligation clip to obtain the degradable zinc-copper alloy hemostatic clip.
Solution treatment includes, but is not limited to, heat preservation, pressurization; the quenching is preferably high pressure gas cooling quenching.
And during the solution treatment, the heating temperature is 115-410 ℃, and the time is 6-10 h. According to the phase diagram of the alloy, different copper contents are obtained, and the solution treatment temperature and time are shown in a figure 4:
description of the drawings:
FIG. 1 is a side perspective view of the ligating clip; 1 is an upper clamping surface; 2 is a lower clamping surface; 3 is a clip; 4, clamping and buckling a barb; 5 is a circular unit; and 6 is a corresponding recess of the circular unit.
Fig. 2 is an enlarged view of the circular unit of the ligating clip.
FIG. 3 is a phase diagram of a zinc-copper alloy.
FIG. 4 shows the solution treatment temperature and time.
Example 1:
the ligature clip can be composed of pure zinc (99.99%) and pure copper (99.99%). Wherein the mass fraction of zinc is 99.7-99 wt%; the copper element accounts for 0.3-1 wt%. Solution treatment may not be performed.
Example 2
The ligature clamp can be prepared from pure zinc and is subjected to solution treatment to enhance the mechanical property of the material.
Claims (6)
1. An absorbable zinc-copper alloy ligature clamp subjected to solution treatment is characterized by being made of pure zinc (99.99%) and pure copper (99.99%).
2. The solution treated absorbable zinc-copper alloy ligature clip of claim 1, wherein the material has a zinc mass fraction of 99.7-99 wt%; the copper element accounts for 0.3-1 wt%.
3. The solution treated absorbable zinc-copper alloy ligature clip of claim 1, wherein: the method is characterized in that: the ligating clip is U-shaped, the main body is divided into 3 parts, an upper clamping surface (figure 1-1), a lower clamping surface (figure 1-2) and a clip (figure 1-3); the upper clamping surface and the lower clamping surface are rectangular in shape, the length is 0.5-1.5mm, and the width is 0.5-1.0 mm; the inner side of the upper clamping surface is provided with a plurality of circular unit bulges (figures 1-5) which are 0.1-0.3mm higher than the basal surface, and the peripheries of the circular bulges are dispersedly distributed with intermittent small particles, the middle of the circular bulges is denser (figure 2), so that the target tissue is expanded and extruded and the friction force is increased; the lower clamping surface has a 0.2-0.5mm recess (figure 1-6) which is matched with the upper clamping surface, and the clip has a barb (figure 1-4) and is in a bent structure, and the upper and lower structures are matched.
4. The solution treated absorbable zinc-copper alloy ligature clip of claim 1, wherein: the preparation method can adopt a zinc-copper alloy material for preparation, and comprises the following steps:
pure zinc (the purity is more than or equal to 99.99%) and copper wire (the purity is more than or equal to 99.99%) are fed according to a certain mass fraction ratio and are smelted in vacuum or inert gas at the smelting temperature of 500-600 ℃;
casting the smelting material into a zinc-copper alloy cast ingot, and carrying out large-deformation machining treatment;
carrying out forming treatment on the alloy obtained in the step (2) to obtain a shape of a zinc-copper alloy ligation clip;
heating the formed ligating clip obtained in the step (3) for solution treatment, and rapidly cooling and quenching the treated ligating clip to obtain a zinc-copper alloy ligating clip of single-phase supersaturated solid solution;
and (4) putting the ligation clip obtained in the step (4) into absolute ethyl alcohol, cleaning the surface of the ligation clip to be smooth, taking out the ligation clip and drying the ligation clip to obtain the degradable zinc-copper alloy hemostatic clip.
5. The method according to claim 4, wherein: solution treatment includes, but is not limited to, heat preservation, pressurization; the quenching is preferably high pressure gas cooling quenching.
6. The method according to claim 4, wherein: during solution treatment, the heating temperature is 115-410 ℃, and the time is 6-10 h; according to the phase diagram of the alloy, different copper contents are obtained, and the solution treatment temperature and time are shown in figure 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911098672.XA CN110916747B (en) | 2019-11-12 | 2019-11-12 | Absorbable zinc-copper alloy ligation clamp for solution treatment and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911098672.XA CN110916747B (en) | 2019-11-12 | 2019-11-12 | Absorbable zinc-copper alloy ligation clamp for solution treatment and preparation method thereof |
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| Publication Number | Publication Date |
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| CN110916747A true CN110916747A (en) | 2020-03-27 |
| CN110916747B CN110916747B (en) | 2022-07-26 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020004060A1 (en) * | 1997-07-18 | 2002-01-10 | Bernd Heublein | Metallic implant which is degradable in vivo |
| US20170028107A1 (en) * | 2013-12-26 | 2017-02-02 | Xi'an Advanced Medical Technology Co., Ltd. | Kind of absorbable high strength and toughness corrosion-resistant zinc alloy implant material for human body |
| CN106467942A (en) * | 2015-08-19 | 2017-03-01 | 上海交通大学 | Biodegradable medical pltine and its production and use |
| WO2017084363A1 (en) * | 2015-11-16 | 2017-05-26 | 上海交通大学 | Medical degradable zn-cu-x alloy material and preparation method thereof |
| CN108577922A (en) * | 2018-02-26 | 2018-09-28 | 天津理工大学 | A kind of degradable kirsite laparoscope hemostatic clamp and preparation method thereof |
-
2019
- 2019-11-12 CN CN201911098672.XA patent/CN110916747B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020004060A1 (en) * | 1997-07-18 | 2002-01-10 | Bernd Heublein | Metallic implant which is degradable in vivo |
| US20170028107A1 (en) * | 2013-12-26 | 2017-02-02 | Xi'an Advanced Medical Technology Co., Ltd. | Kind of absorbable high strength and toughness corrosion-resistant zinc alloy implant material for human body |
| CN106467942A (en) * | 2015-08-19 | 2017-03-01 | 上海交通大学 | Biodegradable medical pltine and its production and use |
| WO2017084363A1 (en) * | 2015-11-16 | 2017-05-26 | 上海交通大学 | Medical degradable zn-cu-x alloy material and preparation method thereof |
| CN108577922A (en) * | 2018-02-26 | 2018-09-28 | 天津理工大学 | A kind of degradable kirsite laparoscope hemostatic clamp and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 冯相等: "生物可降解锌基金属材料研究进展", 《材料导报》 * |
| 雷廷权，傅家骐: "《热处理工艺方法300种》", 31 March 1982, 中国农业机械出版社 * |
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| CN110916747B (en) | 2022-07-26 |
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Inventor after: Zhang Haijun Inventor after: Zhou Chao Inventor after: Feng Xiangyi Inventor after: Song Caixia Inventor after: Zhang Junwei Inventor before: Zhang Haijun Inventor before: Zhou Chao Inventor before: Cui Xiaoshan Inventor before: Zhao Yanwei Inventor before: Feng Xiangyi Inventor before: Song Caixia Inventor before: Zhang Junwei |
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