CN108577922A - A kind of degradable kirsite laparoscope hemostatic clamp and preparation method thereof - Google Patents

Abstract

A degradable zinc alloy laparoscopic hemostatic clip and a preparation method thereof are made of zinc alloy, and the composition of the zinc alloy is that alloy element Mg is added to a pure zinc matrix. The advantages of the present invention are: the stress concentration after the metal hemostatic clip is closed is effectively improved by introducing a circular arc structure, adding lock buckles, anti-slip tooth lines, and limit protrusions, and at the same time, the clamping performance of the hemostatic clip is effectively improved, and the operation time is reduced. The risk of hemostatic clip slippage; Zinc is an essential element for the human body, and the hemostatic clip made of zinc alloy has good biocompatibility and absorbability, and its suitable in vivo degradation characteristics significantly increase the service time of the hemostatic clip; the hemostatic clip The structure is simple, the preparation process is simple, and the preparation cost is effectively reduced; the hemostatic clip designed and prepared by the present invention fully meets the requirements of clinical use.

Description

A kind of degradable zinc alloy laparoscopic hemostatic clip and preparation method thereof

technical field

The invention belongs to the field of biomedical materials, and relates to a degradable zinc alloy laparoscopic hemostatic clip and a preparation method thereof.

Background technique

Laparoscopic surgery is performed outside the body with the help of surgical instruments and display imaging. Due to limited operating space, hemostatic clips are usually used to close blood vessels to stop bleeding. Clinically commonly used hemostatic clips are non-degradable metal titanium clips and degradable polymer clips. Titanium clips can be used to close blood vessels of various sizes, but titanium and titanium alloys have good corrosion resistance and an X-ray absorption coefficient much higher than that of human tissues, and keeping them in the human body will distort the diagnosis of regional tissues and induce relevant clinical allergic reactions . Although biodegradable polymer clips can be degraded, their strength is lower than that of metal clips, their size is larger, and their degradation is uncontrollable, so the scope of application is greatly limited. Therefore, there are certain deficiencies in these two kinds of commonly used hemostatic clips.

In order to meet the mechanical properties required for implantation and solve the non-degradable problem of traditional metal clips, researchers have carried out related research on degradable metal hemostatic clips. At present, it is more common in the preparation of magnesium alloy hemostatic clips. Researchers have used the good biodegradability and mechanical properties of magnesium alloys to invent pure magnesium hemostatic clips and magnesium-based composite hemostatic clips. However, the processing technology is cumbersome, the cycle is long, and the finished product is precise. and production efficiency to be improved. Although some researchers have formulated a simple preparation process, there are still difficulties in popularizing and using it. For example, "A Absorbable Magnesium Alloy Laparoscopic Hemostatic Clip and Its Preparation Method", Patent No.: 201510808275.2. The biodegradability and physical and mechanical properties of magnesium-based alloys are improved by adding a certain proportion of alloying elements. The casting-extrusion-punching-heat treatment process is used to simplify the preparation process and overcome the disadvantage that the magnesium alloy is difficult to plastically deform, and improve the plasticity and toughness of the hemostatic clip. The V-shaped hemostatic clip is designed so that the whole hemostatic clip has a "V"-shaped structure with arc angles. The design of the arc angle structure avoids the phenomenon of fracture during the clamping process of the magnesium-based hemostatic clip. However, there are two hidden dangers in the clinical use of this magnesium alloy hemostatic clip: one is that the postoperative hemostatic clip may move or slip during the residual period of the patient's body, which not only has the risk of bleeding from the wound, but also may be caused by the hemostatic clip. Second, the corrosion potential of magnesium alloy is low, and the corrosion speed is too fast in the physiological environment rich in Cl-. If the magnesium alloy hemostatic clip corrodes too quickly during its use, it will lose its mechanical integrity and there is a risk of blood vessel rupture. The existence of these two hidden dangers in clinical use limits the development of degradable magnesium alloy hemostatic clips.

In order to solve the problems of the above-mentioned hemostatic clips and promote the development of degradable metal hemostatic clips, the present invention uses zinc alloys with good biocompatibility, mechanical properties and in vivo degradation characteristics as raw materials, and designs and develops a Structure of a novel degradable hemostatic clip for laparoscopic surgery. The invention can effectively solve the drawbacks of the existing hemostatic clips, simplify the surgical clipping process, and improve the clipping effect, thereby helping to reduce surgical risks and costs.

Contents of the invention

The purpose of the present invention is to provide a degradable zinc alloy laparoscopic hemostatic clip and its preparation method in view of the above-mentioned technical analysis and existing problems. The hemostatic clip can effectively solve the problem that the existing metal hemostatic clip is easy to slip off. The clip has good clamping performance, and at the same time greatly prolongs the effective service time of the hemostatic clip, avoids its premature failure, has long-term hemostasis safety, and effectively reduces the postoperative risk.

Technical scheme of the present invention:

A degradable zinc alloy laparoscopic hemostatic clip is made of zinc alloy. The composition of the zinc alloy is that an alloy element Mg is added to a pure zinc matrix, and the weight percentage content of the alloy element is 1-6% of Mg. The cross-sectional shape of the hemostatic clip is rectangular, with a length of 1.0-1.2mm and a width of 0.6-1.0mm. 1.0~1.2mm, the outer radius of the arc is 1.8~2.0mm, the upper clamping arm and the lower clamping arm are both arc-shaped structures and the arcs match each other, and the opening angle between the upper and lower clamping arms is about 30°～60° , the upper jig arm is provided with the barb at the end of the upper jig arm and the positioning protrusion of the upper jig arm which is convenient for clamping by the clamp applicator, and the lower jig arm is provided with the end of the lower jig arm which matches the barb at the end of the upper jig arm The upper hook groove, the barb at the end of the upper clamp arm and the hook groove at the end of the lower clamp arm realize the male and female lock through the clamping of the upper clamp arm and the lower clamp arm. The lower clamp arm is provided with a limit protrusion and its end It is an arc-shaped structure; the inside of the upper and lower clamp arms are additionally equipped with anti-slip teeth on the inside of the clamp arm that fit each other to prevent blood vessels from slipping.

A method for preparing the degradable zinc alloy laparoscopic hemostatic clip, which is prepared by using degradable zinc and zinc alloy materials, including smelting of zinc alloy, extrusion molding of zinc alloy plate, punching and forming of zinc alloy hemostatic clip, and annealing treatment With cleaning, the steps are as follows:

1) Homogenize and anneal a zinc alloy ingot with a section size of Φ60-100mm at a temperature of 300-400°C for 12-24 hours, and then extrude it into a zinc-based alloy with a section width of 30-50mm and a height of 0.8-1.5mm on an extrusion machine Plate, extrusion temperature is 200~300℃, extrusion speed is 0.5mm/s~3.5mm/s;

2) Perform aging treatment on the above-mentioned extruded sheet, the aging temperature is 170-180° C., and the time is 24 hours;

3) punching the above-mentioned aged zinc alloy plate into the shape and size of the hemostatic clip through a punching die, and the punching temperature is room temperature;

4) Perform annealing treatment on the formed zinc alloy hemostatic clip, the annealing temperature is 250-300°C, the annealing time is 1-2h, take it out and cool to room temperature;

5) Put the annealed zinc alloy hemostatic clip into absolute ethanol to clean it until its surface is smooth, then take it out and dry it to prepare a degradable zinc-based alloy hemostatic clip.

The preparation method of the zinc alloy ingot is: using zinc ingots and magnesium ingots with a purity ≥ 99.95% as raw materials, in a vacuum melting furnace with an argon protective atmosphere or in _SF6 with a volume percentage of 0.4%. Melting is carried out under a mixed protective atmosphere of ₆ + N ₂ , the melting temperature is 470-500°C, stirring is carried out by means of mechanical stirring, and the temperature is kept for 5 minutes after stirring, and then cast into a zinc alloy casting of Φ60-100mm in the temperature range of 465-475°C Ingot; the composition of the zinc alloy is Zn-Mg, wherein the weight percentage of Mg is 1-6% of Mg, and the balance is Zn.

The advantages of the present invention are: the stress concentration after the metal hemostatic clip is closed is effectively improved by introducing a circular arc structure, adding lock buckles and anti-slip tooth lines, and at the same time, the clamping performance of the hemostatic clip is effectively improved, and the risk of postoperative hemostatic clip slippage is reduced. ; Zinc is an essential element for the human body. The hemostatic clip made of zinc alloy has good biocompatibility and absorbability, and its slow in vivo degradation rate significantly prolongs the service time of the hemostatic clip; the structure of the hemostatic clip is simple and the preparation process is It is simple and effectively reduces the preparation cost; the hemostatic clip designed and prepared by the present invention can fully meet the requirements of clinical use.

Description of drawings

Figure 1 is a schematic diagram of the structure of a degradable zinc alloy hemostatic clip.

In the figure: 1. The arc at the top; 2. The upper clamp arm; 3. The lower clamp arm; 4. The barb at the end of the upper clamp arm; 5. The hook groove at the end of the lower clamp arm; 6. The limit protrusion; 7. Anti-slip teeth on the inside of the clamp arm; 8. Positioning protrusions on the upper clamp arm.

Detailed ways

Example:

A kind of degradable zinc alloy laparoscopic hemostatic clip, as shown in Figure 1, is made of zinc alloy, and the composition of described zinc alloy is Zn-1.0Mg, wherein the content of Mg is 1wt%, and purity is 99.99%, surplus It is Zn, with a purity of 99.995%. The hemostatic clip has a rectangular cross-sectional shape with a length of 1.0mm and a width of 0.8mm. The inner radius of the arc is 1.0mm, and the outer radius of the arc is 1.8mm. The upper and lower jaws are arc-shaped and the arcs match each other. The inner arc radius of the upper and lower jaws is 8.0mm. , The opening angle between the lower clamping arms is about 30°, the upper clamping arm is provided with the barb 4 at the end of the upper clamping arm and the positioning protrusion 8 of the upper clamping arm which is convenient for clamping by the clamping pliers, and the end of the upper clamping arm is inverted The opening angle between the hook 4 and the upper jig arm positioning protrusion 8 is 55°, and the lower jig arm 3 is provided with a lower jig end hook groove 5 matching the upper jig end barb 4, and the lower jig arm The opening angle of the hook groove 5 at the end is 40°. The barb 4 at the end of the upper clamp arm and the hook groove 5 at the end of the lower clamp arm realize the yin-yang lock through the clamping of the upper clamp arm 2 and the lower clamp arm 3, and the lower clamp arm A limit protrusion 6 is provided on the arm 3 and its end is arc-shaped, the radius of the arc is 6.0mm, and the distance from the top is 2.3mm. The insides of the upper clamping arm 2 and the lower clamping arm 3 are additionally provided with anti-slip teeth 7 on the inner side of the clamping arms to prevent the blood vessels from slipping.

The preparation method of the above-mentioned degradable zinc alloy laparoscopic hemostatic clip is prepared by using degradable zinc and zinc alloy alloy materials, including smelting of zinc alloy, extrusion molding of zinc alloy sheet, punching and forming of zinc alloy hemostatic clip, annealing treatment and cleaning ,Proceed as follows:

1) Preparation of zinc alloy: the zinc alloy composition is Zn-1.0Mg, wherein the content of Mg is 1wt%, and the balance is Zn; the preparation method of this zinc alloy is: a zinc ingot with a purity of 99.995% and a Magnesium ingots are used as raw materials, stirred and melted in a vacuum melting furnace with an argon protective atmosphere, the melting temperature is 500°C, stirred for 5 minutes, and then cast into a Φ60mm zinc alloy ingot through a copper mold at 470°C after standing for 5 minutes; The zinc alloy ingot is subjected to homogenization annealing treatment, the annealing temperature is 350°C, the annealing time is 24h, and then extruded into a 35×1.25mm zinc alloy sheet through an extrusion machine, the extrusion temperature is 250°C, and the extrusion speed is 1mm/ s;

2) Perform aging treatment on the above-mentioned extruded board, the aging temperature is 170°C, and the time is 24h;

3) Punching the aged Zn-1.0Mg alloy sheet into a hemostatic clip as shown in Figure 1 through a punching die;

4) Anneal the above-mentioned Zn-1.0Mg alloy hemostatic clip, the annealing temperature is 300°C, the annealing time is 2h, take it out and cool to room temperature;

5) Put the annealed Zn-1.0Mg alloy hemostatic clip into absolute ethanol to clean it until its surface is smooth, then take it out and dry it to prepare an absorbable zinc-based alloy laparoscopic hemostatic clip.

In this embodiment, the Mg element in the zinc-based alloy is used as an important alloy element, which can refine the alloy grains, improve the strength and ductility of the zinc alloy, and form a second phase to improve the slow corrosion characteristics of the zinc alloy, and obtain a suitable degradation rate. Both Zn and Mg are one of the main nutritional elements for the human body and have good biocompatibility.

Claims (3)

1. A degradable zinc alloy laparoscopic hemostatic clip is characterized in that: it is made of zinc alloy, and the composition of said zinc alloy is to add alloying element Mg in the pure zinc matrix, and the weight percentage content of alloying element in the alloy is Mg 1 to 6%, the hemostatic clip has a rectangular section shape, 1.0 to 1.2 mm in length, and 0.6 to 1.0 mm in width. It is composed of parts, the length is 8.0-12.0mm, the inner radius of the arc is 1.0-1.2mm, the outer radius of the arc is 1.8-2.0mm, the upper clamping arm (2) and the lower clamping arm (3) are both arc-shaped structures and arc-shaped Match each other, the opening angle between the upper and lower clamping arms is 30°～60°, the upper clamping arm (2) is provided with the barb (4) at the end of the upper clamping arm and the upper clamping arm which is convenient for clamping by the clamp applicator The positioning protrusion (8), the lower clamp arm (3) is provided with the lower clamp arm end hook groove (5) matching the upper clamp arm end barb (4), and the upper clamp arm end barb (4 ) and the hook groove (5) at the end of the lower clamping arm (5) are clamped by the clamping of the upper clamping arm (2) and the lower clamping arm (3) to realize the male-female locking, and the lower clamping arm (3) is provided with a limit protrusion (6 ) and its end is an arc-shaped structure; the inside of the upper clamp arm (2) and the lower clamp arm (3) are additionally equipped with anti-slip teeth (7) on the inner side of the clamp arm that fit each other to prevent blood vessels from sliding. 2. A preparation method of degradable zinc alloy laparoscopic hemostatic clip as claimed in claim 1, characterized in that: it is prepared by using degradable zinc alloy material, including smelting of zinc alloy, extrusion molding of zinc alloy plate, zinc alloy The steps of punching, annealing and cleaning of the hemostatic clip are as follows: 1) Homogenize and anneal a zinc alloy ingot with a section size of Φ60-100mm at a temperature of 300-400°C for 12-24 hours, and then extrude it into a zinc-based alloy with a section width of 30-50mm and a height of 0.8-1.5mm on an extrusion machine Plate, extrusion temperature is 200~300℃, extrusion speed is 0.5mm/s~3.5mm/s; 2) Perform aging treatment on the above-mentioned extruded sheet, the aging temperature is 170-180° C., and the time is 24 hours; 3) punching the Zn-Mg alloy sheet material after the above-mentioned aging into the hemostatic clip described in claim 1 through a punching die; 4) Perform annealing treatment on the formed zinc alloy hemostatic clip, the annealing temperature is 250-300°C, the annealing time is 1-2h, take it out and cool to room temperature; 5) Put the annealed zinc alloy hemostatic clip into absolute ethanol to clean it until its surface is smooth, then take it out and dry it to prepare a degradable zinc-based alloy hemostatic clip. 3. according to the preparation method of the described degradable zinc alloy laparoscopic hemostatic clip of claim 2, it is characterized in that: the preparation method of described zinc alloy ingot is: take the zinc ingot and the magnesium ingot of purity ≥ 99.95% as raw material, in Melting is carried out in a vacuum melting furnace with a protective atmosphere of argon or in a mixed protective atmosphere of SF ₆ +N ₂ with a volume percentage of SF ₆ of 0.4%. The melting temperature is 470-500°C. Stir and keep warm for 5 minutes, and then cast zinc alloy ingots with a diameter of 60 to 100mm in the temperature range of 465 to 475°C; the composition of the zinc alloy is Zn-Mg, and the weight percentage of Mg is Mg 1 to 6%, and the balance is Zn.