CN110916747B

CN110916747B - Absorbable zinc-copper alloy ligation clamp for solution treatment and preparation method thereof

Info

Publication number: CN110916747B
Application number: CN201911098672.XA
Authority: CN
Inventors: 张海军; 周超; 崔晓珊; 赵彦伟; 冯相兿; 宋彩霞; 张军伟
Original assignee: Shandong Rientech Medical Technology Co ltd
Current assignee: Shandong Rientech Medical Technology Co ltd
Priority date: 2019-11-12
Filing date: 2019-11-12
Publication date: 2022-07-26
Anticipated expiration: 2039-11-12
Also published as: CN110916747A

Abstract

The invention relates to an absorbable zinc-copper alloy ligating clip subjected to solution treatment and a preparation method thereof. The ligature clamp 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 ligature clamp 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; after the alloy is subjected to solution treatment, the second phase is reduced or disappears, so that microelectrode corrosion can be prevented, the corrosion uniformity of products is improved, and the mechanical property of the material is enhanced. The ligation clamp is simple in structure and simple in preparation process, can meet clinical requirements, and reduces long-term risks.

Description

Absorbable zinc-copper alloy ligation clamp for solution treatment and preparation method thereof

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 a special design of an arc-shaped belt lock catch, and can be accurately sent to an operation part through a special clip applier, and the tissue to be ligated is 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. The 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 generate inflammation, pain and other diseases in a long-term body; 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 from an 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, and the initial degradation product has an anti-inflammatory effect, and meanwhile, the degradation characteristic of the zinc-based alloy 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 zinc-magnesium 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, which can prevent the corrosion of microelectrodes, improve the uniformity of product corrosion and enhance the mechanical properties 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%; 0.3-1 wt% of copper element.

The absorbable zinc-copper alloy ligature clamp for 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 intermittent small particles, the middle parts of the circular bulges are denser (figure 2), 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 are 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 (5) 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 solution treatment, the heating temperature is 115-410 ℃, and the time is 6-10 h. According to the alloy phase diagram, different copper contents are obtained, and the solution treatment temperature and time are shown in a diagram 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 hooking barbs; 5 is a circular unit; and 6 is a corresponding depression 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 99.7wt% -99 wt%; 0.3-1 wt% of copper element. Solution treatment may not be performed.

Example 2

The ligature clamp can be made of pure zinc and is subjected to solid solution treatment to enhance the mechanical property of the material.

Claims

1. A preparation method of an absorbable zinc-copper alloy ligature clamp subjected to solution treatment, which is characterized by comprising the following steps of,

(1) feeding pure zinc and pure copper according to a certain mass ratio, wherein the mass fraction of zinc is 99.7-99 wt%; the mass fraction of copper is 0.3-1 wt%, and the copper is smelted in vacuum or inert gas, the smelting temperature is 500-600 ℃;

(2) casting the smelting material in the step (1) into a zinc-copper alloy cast ingot, and carrying out large-deformation machining treatment;

(3) performing forming treatment on the alloy obtained in the step (2) to obtain a shape of a zinc-copper alloy ligation clip;

(4) performing solid solution treatment on the ligating clip obtained in the step (3), wherein according to different contents of copper in the alloy, the treatment method comprises the steps of keeping the temperature of Zn-0.3Cu at 120 ℃ for 10 hours, keeping the temperature of Zn-0.8Cu at 225 ℃ for 8 hours, keeping the temperature of Zn-1Cu at 261 ℃ for 6 hours, and rapidly cooling and quenching after the heat preservation treatment to obtain a single-phase supersaturated solid solution zinc-copper alloy ligating clip;

(5) and (5) putting the zinc-copper alloy ligation clip obtained in the step (4) into absolute ethyl alcohol to clean the surface of the zinc-copper alloy ligation clip, taking out the zinc-copper alloy ligation clip after the surface is smooth and clean, and drying to obtain the degradable zinc-copper alloy ligation clip.

2. The method for preparing the absorbable zinc-copper alloy ligature clamp through solution treatment according to claim 1, characterized in that: the ligating clip structure is U-shaped, and the main body is divided into 3 parts, namely an upper clamping surface, a lower clamping surface and a clip; 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 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 parts of the circular bulges are denser, the target tissue is expanded and extruded, and the friction force is increased; the lower clamping surface has a recess of 0.2-0.5mm, which is matched with the upper clamping surface; the clip is provided with a barb and is of a bent structure, and the upper structure and the lower structure are matched.

3. The method for preparing the absorbable zinc-copper alloy ligature clamp by solution treatment according to claim 1, characterized in that: the rapid cooling quenching process is high-pressure gas cooling quenching.