CN106544563B - A kind of biodegradable Mg-Ca-Mn-Sn magnesium alloy materials and preparation method and application - Google Patents

Abstract

The invention discloses a biodegradable Mg-Ca-Mn-Sn magnesium alloy material and its preparation method and application. The biodegradable Mg-Ca-Mn-Sn magnesium alloy material is prepared from the following components according to the mass percentage Composition: Ca 0.5~3%, Mn 0.1~2%, Sn 1~5%, the rest is Mg and unavoidable impurity elements brought by raw materials. The specific preparation method includes smelting of raw materials, casting molding, homogenizing annealing treatment, and hot extrusion processing. The biodegradable Mg-Ca-Mn-Sn magnesium alloy of the present invention has no toxicity to the human body, good mechanical properties, simple preparation method and low cost, and plate-shaped and rod-shaped materials with different sizes and cross-section requirements can be prepared according to requirements. It is used in the preparation of orthopedic implants such as bone plates and bone nails and medical materials such as cardiovascular stents.

Description

A kind of biodegradable Mg-Ca-Mn-Sn magnesium alloy material and its preparation method and application

technical field

The invention belongs to the technical field of medical implant materials, and relates to a biodegradable Mg-Ca-Mn-Sn magnesium alloy material and a preparation method and application thereof.

Background technique

At present, the traditional medical metal materials commonly used clinically mainly include medical stainless steel, medical titanium alloy, and medical cobalt alloy. The release of toxic elements; the modulus of elasticity of traditional medical metal materials is higher than that of human bones; a secondary operation is required to remove it.

Magnesium alloys as medical metal materials can be traced back more than 100 years ago. However, due to the poor corrosion resistance of magnesium alloys, the degradation rate in the human body is too fast to meet the performance requirements of medical implants, thus limiting the use of magnesium alloys as medical implants. Wide application of implants. But early clinical applications have confirmed the feasibility of magnesium alloys as medical materials.

With the development and maturity of different processing methods and surface treatment technologies, the corrosion resistance and mechanical properties of magnesium alloys have been greatly improved. In recent years, more and more researchers around the world have begun to study magnesium alloys as biomaterials. Many in vivo and in vitro experimental results have also proved that degradable magnesium alloys have many outstanding performances as medical implant materials.

Compared with traditional medical metal materials, biodegradable magnesium alloys, as a research hotspot of a new generation of medical metal materials, have unique degradability and biocompatibility, so they have great potential in the application of degradable medical implants . Magnesium is an indispensable nutritional element in the human body. Its elastic modulus and density are closer to human bone, which can avoid the "stress shielding effect", and has good osteoinductive properties, which can promote bone growth and healing. Moreover, high-strength magnesium alloys have good mechanical properties, which meet the performance requirements of ideal medical implants. After the bone is healed, the magnesium alloy implant does not need to be removed, which avoids the injury and additional economic burden of the second operation on the patient.

Contents of the invention

The object of the present invention is to provide a biodegradable Mg-Ca-Mn-Sn magnesium alloy material which has no toxicity to human body, good mechanical properties, simple preparation method and low cost, and its preparation method and application.

The purpose of the present invention is achieved through the following technical solutions:

A biodegradable Mg-Ca-Mn-Sn magnesium alloy material is prepared from the following components according to the mass percentage: Ca 0.5-3%, Mn 0.1-2%, Sn 1-5%, the rest is Mg and Unavoidable impurity elements introduced by raw materials.

A preparation method of the above-mentioned biodegradable Mg-Ca-Mn-Sn magnesium alloy material, comprising the following steps:

(1) Using high-purity magnesium ingots, high-purity calcium particles, Mg-10%Mn intermediate alloys and high-purity tin particles as raw materials, the alloy raw materials are configured according to the above mass percentages, and graphite crucibles are used for melting and high-purity argon gas is continuously introduced as protection. gas;

(2) When the graphite crucible is preheated to 450-550°C, evenly sprinkle the covering agent on the bottom of the crucible, add a small piece of high-purity magnesium ingot, raise the temperature to 700-740°C and keep it warm for 10-30min, after the high-purity magnesium ingot is completely melted , remove surface scum, heat up the melt to 760-780°C, add high-purity calcium particles, tin particles and Mg-Mn master alloy in sequence, stir 3-5 times, and let stand for 10-20 minutes;

(3) After all the metal is melted, the temperature of the metal solution is lowered to 735-745°C, and the refining agent is added and stirred continuously. After stirring for 3-5 minutes, the metal solution is subjected to static refining for 20-40 minutes;

(4) When the metal solution is cooled to 690-710°C, it is then poured into a metal mold with a preheating temperature of 340-360°C, and the as-cast biodegradable Mg-Ca-Mn-Sn magnesium is obtained after the ingot is cooled alloy ingot.

Further, the as-cast biodegradable Mg-Ca-Mn-Sn magnesium alloy ingot is subjected to homogenization annealing treatment at 350-450°C for 6-24 hours to obtain homogenized biodegradable Mg-Ca-Mn-Sn magnesium alloy.

Further, the Mg-Ca-Mn-Sn magnesium alloy after homogenization annealing is subjected to conventional hot extrusion by using dies with different sizes and forming sections to obtain rod-like or lath-like extruded states with different extrusion ratios. For magnesium alloy, the extrusion temperature is 250-400°C, and the extrusion speed is 0.5-8mm/s.

Compared with prior art, the advantages and beneficial effects that the present invention has are as follows:

(1) The Mg-Ca-Mn-Sn magnesium alloy in the present invention is designed with the addition of non-toxic trace alloy elements to ensure that no toxic elements will be produced after the magnesium alloy degrades in the human body, and the addition of alloy elements can improve the magnesium alloy As a medical implant material, the mechanical properties and corrosion resistance can ensure the role of magnesium alloy as an implant.

(2) The biodegradable magnesium alloy in the present invention selects Mg, Ca, Sn and Mg-10%Mn master alloy as raw materials, wherein Mg, Ca, Mn and Sn are indispensable nutritional elements for the human body. Automatic degradation in the human body, the released non-toxic alloy elements will be absorbed by the human body, avoiding the biological safety problems caused by alloy elements. At the same time, Ca can improve the creep resistance of magnesium alloys; Mn has the effect of refining grains; Sn is beneficial to the growth and development of the body, can promote wound healing, and participates in affecting the function of hemoglobin. At the same time, Sn added to magnesium The grains in the alloy can be refined to improve the mechanical properties and corrosion resistance of the magnesium alloy.

(3) The preparation method of the biodegradable Mg-Ca-Mn-Sn magnesium alloy of the present invention is simple and low in cost, and plate-shaped and rod-shaped materials with different sizes and cross-section requirements can be prepared according to requirements, and can be used as bone plates, bone Preparation of orthopedic implants such as nails and medical materials such as cardiovascular stents.

Detailed ways

The technical solution of the present invention will be further described below in conjunction with the examples, but it is not limited thereto. Any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention should be covered by the present invention within the scope of protection.

Example 1:

The biodegradable Mg-Ca-Mn-Sn magnesium alloy material in this example is prepared from the following components according to the mass percentage: Ca 0.5%, Mn 1%, Sn 2%, the rest is Mg and the Unavoidable impurity elements. Concrete preparation steps are as follows:

(1) Using high-purity magnesium ingots, high-purity calcium particles, Mg-10%Mn intermediate alloys and high-purity tin particles as raw materials, the alloy raw materials are configured according to the above mass percentages, and graphite crucibles are used for melting and high-purity argon gas is continuously introduced as protection. gas;

(2) When the graphite crucible is preheated to 500°C, sprinkle an appropriate amount of RJ-2 covering agent evenly on the bottom of the crucible to avoid burning. Then add a small piece of high-purity magnesium ingot, raise the temperature to 720±20°C and keep it warm for 20 minutes. After the high-purity magnesium ingot is completely melted, remove the surface scum, and heat the melt to 780°C to add high-purity calcium particles, tin particles and Mg-Mn master alloy in turn. , stirred 4 times, and stood still for 15 minutes;

(3) After all the metals are melted, cool down the metal solution to 740±5°C, add an appropriate amount of RJ-5 refining agent and keep stirring to avoid burning. After stirring for 5 minutes, the metal solution should be refined for 30 minutes;

(4) When the metal solution is cooled to 700±10°C, it is poured into a metal mold with a preheating temperature of 350°C, and the as-cast biodegradable Mg-Ca-Mn-Sn magnesium alloy is obtained after the ingot is cooled. ingot. The casting process is uniform and slow, and flowing argon is continuously delivered on the surface of the molten metal for protection.

Example 2:

The difference between this example and Example 1 is that the as-cast biodegradable Mg-Ca-Mn-Sn magnesium alloy ingot is subjected to homogenization annealing at 400°C for 12 hours to obtain a homogenized biodegradable Mg-Ca- Mn-Sn magnesium alloy.

Example 3:

The difference between this embodiment and embodiment 2 is that dies with different sizes and forming sections are selected, and the homogenized annealed Mg-Ca-Mn-Sn magnesium alloy is subjected to conventional hot extrusion to obtain the desired extrusion ratio. Rod or lath extruded magnesium alloy, the extrusion temperature is 300°C, and the extrusion speed is 5mm/s.

Example 4:

The difference between this example and Example 1, 2 or 3 is that the biodegradable Mg-Ca-Mn-Sn magnesium alloy material is prepared from the following components according to the mass percentage: Ca 1%, Mn 1.5%, Sn 3% , and the rest are Mg and unavoidable impurity elements brought in by the raw materials.

Example 5:

The difference between this example and Example 1, 2 or 3 is that the biodegradable Mg-Ca-Mn-Sn magnesium alloy material is prepared from the following components according to the mass percentage: Ca 1.25%, Mn 0.8%, Sn 1% , and the rest are Mg and unavoidable impurity elements brought in by the raw materials.

Embodiment 6:

The difference between this example and Example 1, 2 or 3 is that the biodegradable Mg-Ca-Mn-Sn magnesium alloy material is prepared from the following components according to the mass percentage: Ca 2%, Mn 0.5%, Sn 2% , and the rest are Mg and unavoidable impurity elements brought in by the raw materials.

Claims (2)

1. a kind of preparation method of biodegradable Mg-Ca-Mn-Sn magnesium alloy materials, it is characterised in that the method is in argon gas It carries out, includes the following steps as under conditions of protective gas：

(1) using high-purity magnesium ingot, high-purity calcium grain, Mg-10%Mn intermediate alloys and high purity tin grain as raw material, graphite is used during melting Crucible is simultaneously continually fed into high-purity argon gas as protective gas；

(2) when graphite crucible being preheating to 450~550 DEG C, coverture is equably sprinkled in the bottom of crucible, it is high-purity to add in fritter Magnesium ingot is warming up to 700~740 DEG C and keeps the temperature 10~30min, after high-purity magnesium ingot is completely melt, removes surface scum, melt liter Temperature sequentially adds high-purity calcium grain, tin grain and Mg-Mn intermediate alloys to 760~780 DEG C, stirs 3~5 times, stands 10~20min；

(3) after whole metal moltens, metallic solution is cooled to 735~745 DEG C, adds in refining agent and is stirred continuously, and stirring 3~ After 5min, metallic solution carries out the standing refining of 20~40min；

(4) it when metallic solution is cooled to 690~710 DEG C, is then poured into the metal pattern that preheating temperature is 340~360 DEG C, As cast condition biodegradable Mg-Ca-Mn-Sn magnesium alloy ingots are obtained after ingot casting cooling；

(5) as cast condition biodegradable Mg-Ca-Mn-Sn magnesium alloy ingots carry out to 6 at 350~450 DEG C~homogenization for 24 hours Annealing obtains homogenization state biodegradable Mg-Ca-Mn-Sn magnesium alloys；

(6) homogenization state biodegradable Mg-Ca-Mn-Sn magnesium alloys are subjected to conventional hot extrusion, different extrusion ratios needed for acquisition Rodlike or lath-shaped extruded Magnesium Alloy, extrusion temperature be 250~400 DEG C, extrusion speed be 0.5~8mm/s；

The biodegradable Mg-Ca-Mn-Sn magnesium alloy materials are prepared from the following components according to mass percent： Ca1.25%, Mn0.8%, Sn1%, remaining is Mg and the inevitable impurity element brought by raw material.

2. biodegradable Mg-Ca-Mn-Sn magnesium alloy materials described in claim 1 can be used as the preparation of medical implant material.