CN114395713A - Degradable in-situ authigenic Mg2Ge particle reinforced Zn-based composite material and preparation method thereof - Google Patents

Degradable in-situ authigenic Mg2Ge particle reinforced Zn-based composite material and preparation method thereof Download PDF

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CN114395713A
CN114395713A CN202210053889.4A CN202210053889A CN114395713A CN 114395713 A CN114395713 A CN 114395713A CN 202210053889 A CN202210053889 A CN 202210053889A CN 114395713 A CN114395713 A CN 114395713A
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ingot
pure
composite material
hot rolling
single crystal
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CN114395713B (en
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黄盛斌
童先
林继兴
朱莉
麻健丰
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SCHOOL & HOSPITAL OF STOMATOLOGY WENZHOU MEDICAL UNIVERSITY
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
    • A61L27/427—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of other specific inorganic materials not covered by A61L27/422 or A61L27/425
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/58—Materials at least partially resorbable by the body
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/165—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon of zinc or cadmium or alloys based thereon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The invention provides degradable in-situ authigenic Mg2Ge particle reinforced Zn-based composite material and preparation method thereof, wherein the matrix of the composite material is Zn, and the reinforcing phase of the composite material is Mg2Ge, degradable in situ authigenic Mg as described in this invention2The Ge particle reinforced Zn-based composite material has excellent mechanical property, proper degradation rate and good cell compatibility.

Description

Degradable in-situ authigenic Mg2Ge particle reinforced Zn-based composite material and preparation method thereof
Technical Field
The invention relates to the field of biomedical metal materials, in particular to degradable in-situ authigenic Mg2Ge particlesA particle-reinforced Zn-based composite material and a preparation method thereof.
Background
In medical bone repair and bone replacement implant materials, medical stainless steel, titanium and titanium alloy become metal materials widely applied in clinic due to excellent mechanical property, biocompatibility and corrosion resistance. However, after the bone tissue is healed, the implants such as stainless steel and titanium alloy bone nails and bone plates need to be removed by subsequent operations, which undoubtedly increases the pain and economic burden of the patients.
Meanwhile, the mechanical properties of stainless steel and titanium alloy are not matched with those of bone tissues, particularly the elastic modulus, for example, the elastic modulus of stainless steel is about 200GPa (specifically, the elastic modulus of 316L stainless steel is 210GPa), most of the titanium alloy in clinical application has an elastic modulus greater than 100GPa, and the elastic modulus of bone tissues is about 1-30GPa, so that the implant will bear most of the load during use, which is easy to cause stress shielding, and the bone tissues around the implant will shrink or loosen.
Therefore, compared with the existing biomedical metal material for clinical application, the novel biomedical metal material still needs to have the functions of internal degradation and absorption on the basis of meeting the excellent biocompatibility and mechanical matching capability so as to further meet the clinical requirement, avoid or reduce the stress shielding phenomenon, and simultaneously reduce the pain and economic burden of patients through internal degradation and absorption.
At present, the degradable metal materials mainly comprise three types of iron-based, magnesium-based and zinc-based alloys. Among these degradable metal materials, iron-based alloys have a slow degradation rate, corrosion products are difficult to absorb and discharge in vivo, and are not friendly to nuclear magnetic resonance technology, which restricts clinical application of some iron-based degradable materials. Although clinical applications have demonstrated that magnesium alloys have very good biocompatibility, the use of magnesium alloys as implant materials is limited due to the fact that magnesium alloys corrode and degrade too quickly in the human body and the generation of hydrogen is detrimental to wound healing.
Zinc is an essential nutrient element in the human body, plays a leading role in enzyme synthesis, DNA replication, transcription and expression, and can promote osteointegration and osteoinduction. Nearly half of zinc in human body is located in bone, and zinc has great influence on functions of normal development of bone tissue of human body and the like. In addition, the zinc-based alloy has low melting temperature, low energy consumption in the production process and low pollutant emission in smelting and casting, and meets the requirement of sustainable development of the environment. Therefore, in recent years, pure zinc and its alloy as a novel degradable medical material have become a research hotspot in the field of biological materials. However, studies have shown that: the cast pure zinc has the defects of lower strength and toughness which are not matched with human bones, slower degradation speed which is not matched with the growth speed of bone cells, surface biocompatibility which needs to be improved, and the like, and the defects always plague the further development and application of the zinc and the alloy thereof. At present, the degradation speed and the mechanical property of the zinc alloy are improved mainly by alloying and combining with a deformation process, and the biocompatibility of the zinc alloy is further improved.
Among them, Metal Matrix Composites (MMCs) have both the advantages of high toughness of metals and high strength, high hardness, and high thermal stability of ceramic particles, and have attracted extensive attention in the fields of the automotive industry and the aerospace industry. The preparation method plays an important role in the performance and the application of the MMCs. At present, the preparation method of MMCs mainly comprises a plurality of preparation technologies such as Mechanical Alloying (MA), direct metal oxidation (DIMOXTM), self-propagating high-temperature synthesis (SHS), exothermic dispersion (XDTM), direct melt reaction, Mixed Salt Reaction (MSR), in-situ self-generated reaction method and the like. The interface wettability between the reinforcement body and the substrate is the most critical factor in the preparation process of the MMCs at present, and the control of the interface wettability can directly influence the performance and stability of the MMCs during high-temperature preparation and application. Among a plurality of preparation processes, the in-situ autogenous method is a simple and low-cost preparation process, can be shaped nearly cleanly, has huge potential and is a hot point of research in recent decades. The reinforced particles which are thermodynamically stable, fine in size and uniformly distributed can be obtained by an in-situ autogenesis method, no inclusions exist between the particles and the matrix alloy, the interface combination is good, and the problems of wettability and interface reaction between the reinforced phase and the matrix are solved. Therefore, compared with the externally added particles, the reinforcing phase obtained by the method has better wettability with the matrix and more dispersed distribution, and the agglomeration and segregation phenomena are greatly reduced. By this method, the metal matrix composite material reinforced by particles such as carbide, boride, oxide, nitride, silicide, etc. can be obtained.
At present, in the particle-reinforced metal matrix composite material prepared by the in-situ authigenic process, a great deal of reports on degradable iron matrix and magnesium matrix exist, the research and preparation of the in-situ authigenic zinc material are mainly carried out around Zn-Al matrix, and the reports on the Al-free biodegradable zinc matrix composite material are less. In addition, no report on biodegradable in-situ authigenic Mg is found in domestic and foreign documents2Ge particle reinforced Zn-Mg2Preparation of Ge composite material and research of corresponding performance, so that degradable Zn-Mg is proposed2The Ge composite material is used as a degradable biomedical material in the next stage.
Disclosure of Invention
The invention provides degradable in-situ authigenic Mg2Ge particle reinforced Zn-based composite material and a preparation method thereof, so as to provide a novel biomedical metal material with excellent biocompatibility, mechanical matching capability and in-vivo degradability and absorption.
In order to solve the problems, the invention discloses degradable in-situ authigenic Mg2The Ge particle reinforced Zn-based composite material is characterized in that a matrix of the composite material is Zn, and a reinforcing phase of the composite material is Mg2Ge。
The composite material is taken as Zn-XMg2Ge composite material by Mg2Ge particle reinforced Zn Material, resulting Zn-XMg2The Ge composite material has excellent mechanical property, proper degradation rate and good cell compatibility, and is expected to be widely used in a large scale as a degradable biomedical material. Said Zn-XMg2Mg in Ge composites2The Ge reinforcing phase has high melting point, high hardness, high elastic modulus, good corrosion resistance and biocompatibility, and is an ideal reinforcing body of the zinc-based composite material.
Further, the composite material is reinforcedPhase Mg2The content of Ge is 0.5-10 wt.%.
Further, the reinforcing phase Mg2Ge comprises nascent Mg2Ge phase and eutectic Mg2A Ge phase.
Further, the composite material is used as a medical material for bone repair and bone replacement implantation.
In addition, the application also provides degradable in-situ authigenic Mg2Method for preparing Ge particle reinforced Zn-based composite material, and method for preparing Zn-XMg described above2A Ge composite, the method of preparation comprising the steps of:
s1, preparing materials: pure Zn ingot, single crystal Ge and pure Mg ingot are taken as raw materials, and the reinforcing phase Mg in the composite material is selected2Respectively weighing pure Zn ingots, single crystal Ge and pure Mg ingots according to the content of Ge for later use; wherein the pure Zn ingot has a Zn content of 99.99 wt.% or more, the single crystal Ge has a Ge content of 99.999 wt.% or more, and the pure Mg ingot has a Mg content of 99.95 wt.% or more;
s2, smelting: sequentially adding pure Zn ingots, single crystal Ge and pure Mg ingots into a smelting furnace for smelting, and then pouring to obtain metal ingots;
s3, homogenization treatment: carrying out homogenization treatment on the metal ingot at the temperature of 250-320 ℃ for 4-20 h;
s4, hot rolling: cutting off the top and the bottom of a metal ingot, cutting to obtain a metal plate for hot rolling, adjusting hot rolling process parameters to ensure that the deformation of the metal plate is 60-95%, and hot rolling to obtain the degradable in-situ authigenic Mg2The Ge particles reinforce the Zn-based composite.
Further, in the step S1, the mass ratio of the single crystal Ge to the pure Mg ingot is 48: 73. the proportion of Ge and Mg elements is strictly controlled according to the relative atomic weight, and the reinforcing phase Mg in the composite material can be controlled2And forming Ge.
Further, in the step S2:
firstly, adding the pure Zn ingot weighed in the step S1 into a smelting furnace, and adding the pure Zn ingot into Ar2Heating to 500-600 ℃ under the protection of atmosphere for smelting;
adding single crystal Ge after the pure Zn ingot is completely melted, and raising the temperature to 550-650 ℃ for smelting;
after the single crystal Ge is completely melted, adding a pure Mg ingot, and cooling to 520-620 ℃ for smelting;
and after the pure Mg ingot is completely melted, carrying out slag skimming treatment, reducing the pouring temperature to 500-560 ℃, and finally pouring into a steel die preheated to 150-250 ℃ to obtain the metal ingot.
Further, in the step S3, the ingot is heat-preserved at 250 to 320 ℃ for 4 to 20 hours to perform homogenization treatment, and then the ingot is air-cooled or water-cooled to room temperature.
Further, in the step S4, the hot rolling process is multi-pass hot rolling, the reduction of each pass of hot rolling is 0.2-1 mm, and the metal plate is heated in a heating furnace for 1-5 min immediately after each pass of hot rolling.
Further, in the step S4, the metal plate is finally rolled to a thickness of 4 to 0.5mm by multi-pass hot rolling.
Further, in the step S4, the metal plate is preheated to 230 to 300 ℃ and maintained for 1 to 15min before hot rolling.
Degradable in situ authigenic Mg as described herein2The Ge particle reinforced Zn-based composite material and the preparation method have the following advantages: the composite material has excellent mechanical property, good cell compatibility and biodegradability suitable for bone implant, and is expected to be widely used in large scale as a degradable biomedical material.
Drawings
FIG. 1 shows degradable in situ authigenic Mg according to the present invention2A preparation flow chart of the Ge particle reinforced Zn-based composite material;
FIG. 2 shows as-cast and hot-rolled Zn-3Mg according to the present invention2XRD pattern of Ge composite;
FIG. 3 shows as-cast and hot-rolled Zn-3Mg according to the present invention2Metallographic structure of the Ge composite material;
FIG. 4 shows Zn-3Mg in a hot rolled state according to the present invention2Polarization curves of Ge composites in Hanks' solution.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
The invention provides degradable in-situ authigenic Mg2The Ge particle reinforced Zn-based composite material is characterized in that a matrix of the composite material is Zn, and a reinforcing phase of the composite material is Mg2Ge, a reinforcing phase Mg in said composite2The content of Ge is 0.5-10 wt.%, and the reinforcing phase Mg2Ge comprises nascent Mg2Ge phase and eutectic Mg2A Ge phase.
As some examples of the present application, the reinforcing phase Mg in the composite material2The content of Ge may be 0.5 wt.%, 1 wt.%, 5 wt.%, 9 wt.%, 10 wt.%, etc.
Degradable in situ authigenic Mg as described herein2The Ge particle reinforced Zn-based composite material can be used as a medical material for bone repair and bone replacement implantation.
In particular, the degradable in situ authigenic Mg described herein2The Ge particle reinforced Zn-based composite material can be used as a bone repair and bone replacement implant material.
In addition, as shown in fig. 1, the present application also provides a degradable in situ authigenic Mg2A method for the preparation of a Ge particle reinforced Zn-based composite material for the preparation of the above composite material, the preparation method comprising the steps of:
s1, preparing materials: pure Zn ingot, single crystal Ge and pure Mg ingot are taken as raw materials, and the reinforcing phase Mg in the composite material is selected2Respectively weighing pure Zn ingots, single crystal Ge and pure Mg ingots according to the content of Ge for later use;
s2, smelting: sequentially adding pure Zn ingots, single crystal Ge and pure Mg ingots into a smelting furnace for smelting, and then pouring to obtain metal ingots;
s3, homogenization treatment: carrying out homogenization treatment on the metal ingot at the temperature of 250-320 ℃ for 4-20 h;
s4, hot rolling: cutting off the top and the bottom of a metal ingot, cutting to obtain a hot rolling metal plate, adjusting hot rolling process parameters to ensure that the deformation of the metal plate is 60-95%, and hot rolling the metal plateObtaining the degradable in-situ authigenic Mg2The Ge particles reinforce the Zn-based composite.
Specifically, the preparation method comprises the following steps:
s1, preparing materials: pure Zn ingot (99.99 wt.%), single crystal Ge (99.999 wt.%), pure Mg ingot (99.95 wt.%) are used as raw materials, a certain amount of pure Zn ingot is firstly weighed, the total amount of single crystal Ge and pure Mg ingot is calculated according to 0.5-10 wt.% of the mass of pure Zn ingot, and then the mass ratio of single crystal Ge to pure Mg ingot is 48: 73 respectively calculating the usage amount of the single crystal Ge and the usage amount of the pure Mg ingot, and weighing the single crystal Ge and the pure Mg ingot with corresponding amounts according to the calculation results;
s2, smelting: putting pure Zn ingot into a graphite crucible, putting the graphite crucible into a well type furnace for smelting, and putting the pure Zn ingot into Ar2Heating to 500-600 ℃ under the protection of atmosphere, such as 500 ℃, 520 ℃, 550 ℃ or 600 ℃ for smelting; adding single crystal Ge after pure Zn ingots are completely melted, pressing the single crystal Ge below the liquid level to avoid the phenomenon that the single crystal Ge floats upwards to cause infusibility, and simultaneously raising the temperature to 550-650 ℃, such as 550 ℃, 570 ℃, 600 ℃ or 650 ℃ for smelting; after the single crystal Ge is fully melted, adding a pure Mg ingot, pressing the pure Mg ingot below the liquid level by using a bell jar, and simultaneously reducing the temperature to 520-620 ℃, such as 520 ℃, 550 ℃, 560 ℃ or 620 ℃ for smelting; after the pure Mg ingot is completely melted, continuously stirring with a graphite rod, standing for 2-5min, such as 2min, 3min or 5min, slagging off, and reducing the casting temperature to 500-560 ℃, such as 500 ℃, 520 ℃, 550 ℃ or 560 ℃; finally pouring the mixture into a steel die preheated to 150-250 ℃ to obtain a metal ingot;
s3, homogenization treatment: homogenizing the ingot at 250-320 deg.C, such as 250 deg.C, 280 deg.C, 300 deg.C or 320 deg.C for 4-20 hr, such as 4 hr, 6 hr, 8 hr, 10 hr or 20 hr, and air cooling or water cooling the ingot to room temperature to improve Zn-XMg2Segregation of elements in the Ge alloy;
s4, hot rolling: cutting off the top and the bottom of an ingot by wire cutting, cutting out a metal plate for hot rolling, preheating the metal plate to 230-300 ℃ and keeping for 1-15 min before hot rolling, for example, preheating the metal plate to 230 ℃ and keeping for 15min before hot rolling, or preheating the metal plate to 300 ℃ and keeping for 1min before hot rolling, then carrying out multi-pass hot rolling, hot rolling the plate from 10mm to 4-0.5 mm in thickness with the reduction of 0.2-1 mm in hot rolling per pass to achieve the final deformation of 60-95%, and immediately heating the metal plate in a furnace for 1-5 min after deformation of each pass, preferably, immediately heating the metal plate in the furnace for 1-5 min after deformation of each pass, and preheating the metal plate to 230-300 ℃.
As some examples of the present application, in the step S4, the reduction amount of hot rolling per pass may be 0.2mm, 0.5mm, 1mm, or the like.
As some examples of the present application, in the step S4, the thickness of the plate before hot rolling is not limited to 10mm, such as 5mm or 15 mm; the thickness of the hot-rolled plate needs to be 4-0.5 mm, such as 4mm, 2mm, 1mm or 0.5 mm.
As some examples of the present application, in the step S4, the final deformation of the metal plate during the hot rolling process is 60-95%, such as 60%, 70%, 80%, 90% or 95%.
Example 1
First, pure Zn ingot (99.99 wt.%), single crystal Ge (99.999 wt.%), and pure Mg ingot (99.95 wt.%) were used as raw materials, and 3 wt.% Mg was added to pure zinc2Ge to design Zn-3Mg2Ge composite and strictly according to Mg2The mass ratio of Mg to Ge elements in the Ge second phase is 48: 73, the raw materials are weighed. Then putting pure Zn ingot into a graphite crucible and putting the graphite crucible into a well type furnace for smelting, and putting the pure Zn ingot into Ar2Heating to 550 ℃ under the protection of atmosphere for smelting; adding single crystal Ge after pure Zn ingots are completely melted, pressing the single crystal Ge below the liquid level to avoid the phenomenon that the single crystal Ge floats upwards to cause infusibility, and raising the temperature to 600 ℃; after the single crystal Ge is fully melted, adding a pure Mg ingot, pressing the pure Mg ingot below the liquid level by using a bell jar, and reducing the temperature to 570 ℃; after the pure Mg ingot is completely melted, continuously stirring with a graphite rod, standing for 5min, slagging off, and reducing the casting temperature to 550 ℃; and finally pouring the mixture into a steel die preheated to 250 ℃ to obtain a metal ingot. The ingot is kept warm for 8 hours at 300 ℃ for homogenization treatment, then the ingot is cooled in air or water to the room temperature,to improve Zn-3Mg2Segregation of elements in the Ge composite. Thereafter, the top and bottom of the ingot were cut off by wire cutting, and a metal plate was cut out for hot rolling. Preheating a metal plate to 280 ℃ before hot rolling, keeping the temperature for 10min, immediately heating the metal plate in a furnace for 3min after each pass of deformation according to the reduction of 0.5mm in each pass, hot rolling the plate from 10mm to 1.5mm until the final deformation reaches 85%, and finally preparing Zn-3Mg2A Ge composite.
Example 2
First, pure Zn ingot (99.99 wt.%), single crystal Ge (99.999 wt.%), and pure Mg ingot (99.95 wt.%) were used as raw materials, and 5 wt.% Mg was added to pure zinc2Ge to design Zn-5Mg2Ge composite and strictly according to Mg2The mass ratio of Mg to Ge elements in the Ge second phase is 48: 73, the raw materials are weighed. Then putting pure Zn ingot into a graphite crucible and putting the graphite crucible into a well type furnace for smelting, and putting the pure Zn ingot into Ar2Heating to 600 ℃ under the protection of atmosphere for smelting; adding single crystal Ge after pure Zn ingots are completely melted, pressing the single crystal Ge below the liquid level to avoid the phenomenon that the single crystal Ge floats upwards to cause infusibility, and raising the temperature to 630 ℃; after the single crystal Ge is fully melted, adding a pure Mg ingot, pressing the pure Mg ingot below the liquid level by using a bell jar, and reducing the temperature to 580 ℃; after the pure Mg ingot is completely melted, continuously stirring with a graphite rod, standing for 5min, slagging off, and reducing the casting temperature to 550 ℃; and finally pouring the mixture into a steel die preheated to 200 ℃ to obtain a metal ingot. Keeping the ingot at 320 deg.C for 10 hr for homogenization, and cooling the ingot to room temperature by air cooling or water cooling to improve Zn-5Mg2Segregation of elements in the Ge composite. Thereafter, the top and bottom of the ingot were cut off by wire cutting, and a metal plate was cut out for hot rolling. Preheating a metal plate to 280 ℃ before hot rolling, keeping the temperature for 15min, immediately heating the metal plate in a furnace for 3min after each pass is deformed by the reduction of 1mm in each pass, hot rolling the plate from 10mm to 1.5mm to reach the final deformation of 85%, and finally preparing Zn-5Mg2A Ge composite.
Example 3
Pure Zn ingot (99.99 wt.%), single crystal Ge (99.999 wt.%), pure Mg ingot (99.95 wt.%) were first used asRaw material, adding 8 wt.% Mg into pure zinc2Ge to design Zn-8Mg2Ge composite and strictly according to Mg2The mass ratio of Mg to Ge elements in the Ge second phase is 48: 73, the raw materials are weighed. Then putting pure Zn ingot into a graphite crucible and putting the graphite crucible into a well type furnace for smelting, and putting the pure Zn ingot into Ar2Heating to 580 ℃ under the protection of atmosphere for smelting; adding single crystal Ge after pure Zn ingots are completely melted, pressing the single crystal Ge below the liquid level to avoid the phenomenon that the single crystal Ge floats upwards to cause infusibility, and raising the temperature to 630 ℃; after the single crystal Ge is fully melted, adding a pure Mg ingot, pressing the pure Mg ingot below the liquid level by using a bell jar, and reducing the temperature to 550 ℃; after the pure Mg ingot is completely melted, continuously stirring with a graphite stick, standing for 3min, slagging off, and reducing the casting temperature to 520 ℃; and finally pouring the mixture into a steel die preheated to 250 ℃ to obtain a metal ingot. The ingot is kept at 280 ℃ for 8 hours for homogenization treatment, and then the ingot is cooled in air or water to room temperature for improving Zn-8Mg2Segregation of elements in the Ge composite. Thereafter, the top and bottom of the ingot were cut off by wire cutting, and a metal plate was cut out for hot rolling. Preheating a metal plate to 300 ℃ and keeping the temperature for 10min before hot rolling, then immediately placing the metal plate into a furnace for heating for 5min after each pass of deformation according to the reduction of 0.5mm in each pass, hot rolling the plate thickness from 10mm to 2mm to reach the final deformation of 80%, and finally preparing Zn-8Mg2A Ge composite.
Example 4
First, pure Zn ingot (99.99 wt.%), single crystal Ge (99.999 wt.%), and pure Mg ingot (99.95 wt.%) were used as raw materials, and 1 wt.% Mg was added to pure zinc2Ge to design Zn-1Mg2Ge composite and strictly according to Mg2The mass ratio of Mg to Ge elements in the Ge second phase is 48: 73, the raw materials are weighed. Then putting pure Zn ingot into a graphite crucible and putting the graphite crucible into a well type furnace for smelting, and putting the pure Zn ingot into Ar2Heating to 520 ℃ under the protection of atmosphere for smelting; adding single crystal Ge after pure Zn ingots are completely melted, pressing the single crystal Ge below the liquid level to avoid the phenomenon that the single crystal Ge floats upwards to cause infusibility, and raising the temperature to 550 ℃; adding pure Mg ingot after the single crystal Ge is fully melted, pressing the pure Mg ingot below the liquid level by using a bell jar, and reducing the temperature to 520 DEG CDEG C; after the pure Mg ingot is completely melted, continuously stirring with a graphite rod, standing for 5min, slagging off, and reducing the casting temperature to 500 ℃; and finally pouring the mixture into a steel die preheated to 250 ℃ to obtain a metal ingot. The ingot is kept at 280 ℃ for 8 hours for homogenization treatment, and then the ingot is cooled in air or water to room temperature for improving Zn-1Mg2Segregation of elements in the Ge composite. Thereafter, the top and bottom of the ingot were cut off by wire cutting, and a metal plate was cut out for hot rolling. Preheating a metal plate to 280 ℃ before hot rolling, keeping the temperature for 10min, immediately heating the metal plate in a furnace for 5min after each pass is deformed by the reduction of 1mm in each pass, hot rolling the plate from 10mm to 1mm until the final deformation is 90%, and finally preparing Zn-1Mg2A Ge composite.
Test example 1
The as-cast and hot-rolled Zn-3Mg prepared in example 1 above2The Ge composite materials are respectively subjected to X-ray diffraction detection to obtain an XRD pattern shown in fig. 2, and as can be seen from fig. 2: as-cast and hot rolled Zn-3Mg2The Ge composite materials all have a close-packed hexagonal alpha-Zn phase and Mg2A Ge phase. Further, the phase types in the composite material before and after hot rolling are not greatly different.
Test example 2
The as-cast and hot-rolled Zn-3Mg prepared in example 1 above2And respectively carrying out metallographic detection on the Ge composite material to obtain a metallographic structure diagram shown in figure 3, wherein the metallographic structure diagram shown in figure 3 shows that: as-cast and hot rolled Zn-3Mg2The Ge composite materials mainly comprise white alpha-Zn matrix and black regular blocky nascent Mg2Eutectic Mg with Ge phase and dark grey Chinese character shape2Ge phase composition, wherein, in the as-cast sample, primary Mg is formed2The Ge phase size is about 28.6 μm.
After hot rolling treatment, Mg2The Ge second phase is distributed mainly parallel to the rolling direction.
In the hot rolled sample, as-grown Mg2The phase size of the Ge phase was reduced to about 25.2 μm relative to the as-cast sample; eutectic Mg2The Ge phase is changed into point-shaped particles from the original Chinese character shape, and the phase size tends to be refined.
Test example 3
The as-cast and hot-rolled Zn-3Mg prepared in example 1 above2And respectively carrying out mechanical property and hardness detection on the Ge composite material to obtain detection results shown in the following table 1:
TABLE 1 as-cast and as-hot rolled Zn-3Mg2Mechanical property and hardness detection result of Ge composite material
Figure BDA0003475571790000101
As can be seen from table 1 above: as-cast Zn-3Mg2Yield strength (Rp) of Ge composite0.2) 55.6MPa, tensile strength (Rm) 117.4MPa, elongation (A) 2.5%, Vickers Hardness (HV) 87.4HV, Brinell Hardness (HB) 80.8 HB.
Hot rolled Zn-3Mg2Yield strength (Rp) of Ge composite0.2) 162.3MPa, tensile strength (Rm) 264.3MPa, elongation (A) 10.9%, Vickers Hardness (HV) 90.5HV, Brinell Hardness (HB) 83.9 HB.
Test example 4
The hot rolled Zn-3Mg prepared in example 1 was added2The polarization curve of the Ge composite material obtained by performing a polarization test in Hanks' solution is shown in fig. 4, and the corrosion parameters obtained by Tafel interval fitting in the polarization curve chart of fig. 4 are shown in the following table 2:
TABLE 2 Hot Rolling Zn-3Mg2Corrosion parameters of Ge composites
Figure BDA0003475571790000102
Figure BDA0003475571790000111
As can be seen from table 2 above: hot-rolled Zn-3Mg obtained by carrying out polarization test in Hanks' solution2The corrosion potential, corrosion current density, polarization resistance and corrosion rate of the Ge composite material are respectively-0.755V and 24.5μA/cm2、1.5kΩ·cm2And 347 μm/a. Hot rolled Zn-3Mg in Hanks' solution after 14 and 30 days of immersion test2The Ge composite degradation rates were 126.7 and 62.8 μm/a, respectively.
Test example 5
For the hot rolled Zn-3Mg obtained in example 12Carrying out a cell compatibility test on the Ge composite material: the cell compatibility test was carried out using the CCK-8 method and was carried out strictly under the guidance of the GB/T16886.5 standard. Wherein the preparation of the leach liquor is according to ISO 10993-12 standard.
Hot rolled Zn-3Mg produced by working example 1 above2Cell compatibility tests of the Ge composite material show that: in undiluted hot rolled state Zn-3Mg2In the Ge composite leaching solution, the survival rate of MC3T3-E1 cells is 39.2%, and the cell toxicity is relatively high.
When the leaching solution is diluted to 25%, the cell activity of MC3T3-E1 cells is remarkably improved relative to the undiluted leaching solution, the cell survival rate is 88.5%, and the grade 1 cytotoxicity grade is shown.
The leaching liquor is continuously diluted to 12.5 percent, the cell survival rate of MC3T3-E1 cells reaches 110.3 percent, and the cell compatibility is excellent.
Test example 6
The as-cast and hot-rolled Zn-5Mg prepared in example 2 above2And carrying out metallographic detection on the Ge composite material to obtain: as-cast and hot rolled Zn-5Mg2The Ge composite materials mainly comprise white alpha-Zn matrix and black regular blocky nascent Mg2Eutectic Mg with Ge phase and dark grey Chinese character shape2Ge phase composition, wherein, in the as-cast sample, primary Mg is formed2The Ge phase size is about 33.4 μm.
After hot rolling treatment, Mg2The Ge second phase is distributed mainly parallel to the rolling direction.
In the hot rolled sample, as-grown Mg2The phase size of the Ge phase was reduced to about 27.8 μm relative to the as-cast sample; eutectic Mg2The Ge phase is changed into point-shaped particles from the original Chinese character shape, and the phase size tends to be refined.
Test example 7
The as-cast and hot-rolled Zn-5Mg prepared in example 2 above2And respectively carrying out mechanical property and hardness detection on the Ge composite material to obtain detection results shown in the following table 3:
TABLE 3 as-cast and Hot-rolled Zn-5Mg2Mechanical property and hardness detection result of Ge composite material
Figure BDA0003475571790000121
As can be seen from table 3 above: as-cast Zn-5Mg2Yield strength (Rp) of Ge composite0.2) 44.5MPa, tensile strength (Rm) 100.9MPa, elongation (A) 2.2%, Vickers hardness number (HV) 104.1HV, Brinell hardness number (HB) 97.4 HB.
Hot rolled Zn-5Mg2Yield strength (Rp) of Ge composite0.2) 128.8MPa, tensile strength (Rm) 224.0MPa, elongation (A) 4.8%, Vickers hardness number (HV) 107.1HV, Brinell hardness number (HB) 100.5 HB.
Test example 8
The hot rolled Zn-5Mg obtained in example 22The Ge composite was subjected to a polarization test in Hanks' solution, and the corrosion parameters obtained by fitting Tafel intervals in the polarization curve are shown in Table 4 below:
TABLE 4 Hot Rolling Zn-5Mg2Corrosion parameters of Ge composites
Figure BDA0003475571790000122
As can be seen from table 4 above: hot rolled Zn-5Mg obtained by polarization test in Hanks' solution2The corrosion potential, corrosion current density, polarization resistance and corrosion rate of the Ge composite material are respectively-0.845V and 30.1 mu A/cm2、1.2kΩ·cm2And 426 μm/a. Hot rolled Zn-5Mg in Hanks' solution after 14 and 30 days of immersion test2The Ge composite degradation rates were 151.8 and 76.6 μm/a, respectively.
Test example 9
For the hot rolled Zn-5Mg obtained in example 22The Ge composite was subjected to cell compatibility test in accordance with the method described in test example 5 above.
By subjecting the hot rolled Zn-5Mg obtained in example 2 above to2Cell compatibility tests of the Ge composite material show that: in undiluted hot rolled state Zn-5Mg2In the Ge composite leaching solution, the survival rate of MC3T3-E1 cells is 29.5%, and the cell toxicity is relatively high. When the leaching solution is diluted to 25%, the cell activity of MC3T3-E1 cells is remarkably improved relative to the undiluted leaching solution, the cell survival rate is 77.8%, and the grade 1 cytotoxicity grade is shown. The leaching solution is continuously diluted to 12.5%, the cell survival rate of MC3T3-E1 cells reaches 94.5%, and the cell compatibility is excellent.
Test example 10
The as-cast and hot-rolled Zn-8Mg prepared in example 3 above2And carrying out metallographic detection on the Ge composite material to obtain: as-cast and hot rolled Zn-8Mg2The Ge composite materials mainly comprise white alpha-Zn matrix and black regular blocky nascent Mg2Eutectic Mg with Ge phase and dark grey Chinese character shape2Ge phase composition, wherein, in the as-cast sample, primary Mg is formed2The Ge phase size is about 59.7 μm.
After hot rolling treatment, Mg2The Ge second phase is distributed mainly parallel to the rolling direction.
In the hot rolled sample, as-grown Mg2The phase size of the Ge phase was reduced relative to the as-cast sample, to about 42.6 μm; eutectic Mg2The Ge phase is changed into point-shaped particles from the original Chinese character shape, and the phase size tends to be refined.
Test example 11
The as-cast and hot-rolled Zn-8Mg prepared in example 3 above2And respectively carrying out mechanical property and hardness detection on the Ge composite material to obtain detection results shown in the following table 5:
TABLE 5 as-cast and as-rolled Zn-8Mg2Mechanical property and hardness detection result of Ge composite material
Figure BDA0003475571790000131
Figure BDA0003475571790000141
As can be seen from table 5 above: as-cast Zn-8Mg2Yield strength (Rp) of Ge composite0.2) 77.9MPa, tensile strength (Rm) 121.3MPa, elongation (A) 1.1%, Vickers Hardness (HV) 179.6HV, Brinell Hardness (HB) 164.1 HB.
Hot rolled Zn-8Mg2Yield strength (Rp) of Ge composite0.2) 202.6MPa, a tensile strength (Rm) of 265.5MPa, an elongation (A) of 2.6%, a Vickers Hardness Value (HV) of 183.5HV, and a Brinell hardness value (HB) of 168.5 HB.
Test example 12
The hot rolled Zn-8Mg prepared in example 3 was added2The Ge composite was subjected to polarization tests in Hanks' solution and corrosion parameters fitted to Tafel intervals in the polarization plots are shown in Table 6 below:
TABLE 6 Hot Rolling Zn-8Mg2Corrosion parameters of Ge composites
Figure BDA0003475571790000142
As can be seen from table 6 above: hot rolled Zn-8Mg by polarization test in Hanks' solution2The corrosion potential, corrosion current density, polarization resistance and corrosion rate of the Ge composite material are respectively-0.768V and 39.3 mu A/cm2、0.9kΩ·cm2And 563. mu.m/a. Hot rolled Zn-8Mg in Hanks' solution for 14 and 30 days after immersion test2The Ge composite degradation rates were 195.2 and 98.2 μm/a, respectively.
Test example 13
For the hot rolled Zn-8Mg obtained in example 32The Ge composite was subjected to cell compatibility test in accordance with the method described in test example 5 above.
Hot rolled Zn-8Mg produced by the above example 32Cell compatibility tests of the Ge composite material show that: in undiluted hot rolled state Zn-8Mg2In the Ge composite leaching solution, the survival rate of MC3T3-E1 cells is 27.9%, and the cell toxicity is relatively high. When the leaching solution is diluted to 25%, the cell activity of MC3T3-E1 cells is remarkably improved relative to the undiluted leaching solution, the cell survival rate is 75.9%, and the grade 1 cytotoxicity grade is shown. The leaching liquor is continuously diluted to 12.5%, the cell survival rate of MC3T3-E1 cells reaches 96.9%, and the cell compatibility is excellent.
Test example 14
The as-cast and hot-rolled Zn-1Mg prepared in example 4 above2And carrying out metallographic detection on the Ge composite material to obtain: as-cast and hot-rolled Zn-1Mg2The Ge composite materials mainly comprise white alpha-Zn matrix and black regular blocky nascent Mg2Eutectic Mg with Ge phase and dark grey Chinese character shape2Ge phase composition, wherein, in the as-cast sample, primary Mg is formed2The Ge phase size is about 15.7 μm.
After hot rolling treatment, Mg2The Ge second phase is distributed mainly parallel to the rolling direction.
In the hot rolled sample, as-grown Mg2The phase size of the Ge phase was reduced to about 11.2 μm relative to the as-cast sample; eutectic Mg2The Ge phase is changed into point-shaped particles from the original Chinese character shape, and the phase size tends to be refined.
Test example 15
The as-cast and hot-rolled Zn-1Mg prepared in example 4 above2And respectively carrying out mechanical property and hardness detection on the Ge composite material to obtain detection results shown in the following table 7:
TABLE 7 as-cast and Hot-rolled Zn-1Mg2Mechanical property and hardness detection result of Ge composite material
Figure BDA0003475571790000151
As can be seen from table 7 above: as-cast Zn-1Mg2Yield strength of Ge composite(Rp0.2) 42.3MPa, tensile strength (Rm) 66.3MPa, elongation (A) 1.6%, Vickers Hardness (HV) 73.5HV, Brinell Hardness (HB) 62.4 HB.
Hot rolled Zn-1Mg2Yield strength (Rp) of Ge composite0.2) 124.6MPa, a tensile strength (Rm) of 213.8MPa, an elongation (A) of 13.9%, a Vickers Hardness Value (HV) of 77.6HV, and a Brinell hardness value (HB) of 68.5 HB.
Test example 16
The hot rolled Zn-1Mg prepared in example 4 above2The Ge composite was subjected to polarization tests in Hanks' solution and corrosion parameters fitted to Tafel intervals in the polarization plots are shown in Table 8 below:
TABLE 8 Hot Rolling Zn-1Mg2Corrosion parameters of Ge composites
Figure BDA0003475571790000161
As can be seen from table 8 above: hot-rolled Zn-1Mg obtained by carrying out polarization test in Hanks' solution2The corrosion potential, corrosion current density, polarization resistance and corrosion rate of the Ge composite material are respectively-0.736V and 17.4 mu A/cm2、2.1kΩ·cm2And 242 μm/a. Hot rolled Zn-1Mg in Hanks' solution after immersion test for 14 days and 30 days2The Ge composite degradation rates were 96.8 and 50.2 μm/a, respectively.
Test example 17
For the hot rolled Zn-1Mg prepared in example 42The Ge composite was subjected to cell compatibility test in accordance with the method described in test example 5 above.
Hot rolled Zn-1Mg prepared by the above example 42Cell compatibility tests of the Ge composite material show that: zn-1Mg in undiluted hot rolled state2In the Ge composite leaching solution, the survival rate of MC3T3-E1 cells is 32.4%, and the cell toxicity is relatively high. When the leaching solution is diluted to 25%, the cell activity of MC3T3-E1 cells is remarkably improved relative to the undiluted leaching solution, the cell survival rate is 87.2%, and grade 1 is shownGrade of cytotoxicity. The leaching liquor is continuously diluted to 12.5%, the cell survival rate of MC3T3-E1 cells reaches 103.9%, and the cell compatibility is excellent.
Although the present invention is disclosed above, the present invention is not limited thereto. In the description herein, references to the description of the term "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples" or the like mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Various changes and modifications may be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. Degradable in-situ authigenic Mg2The Ge particle reinforced Zn-based composite material is characterized in that a matrix of the composite material is Zn, and a reinforcing phase of the composite material is Mg2Ge。
2. Composite material according to claim 1, characterized in that the reinforcing phase Mg in the composite material2The content of Ge is 0.5-10 wt.%.
3. Composite material according to claim 1 or 2, characterized in that the reinforcing phase Mg2Ge comprises nascent Mg2Ge phase and eutectic Mg2A Ge phase.
4. The composite material of claim 1, wherein the composite material is used as a medical material for bone repair and bone replacement implants.
5. ADegradable in-situ authigenic Mg2A method for producing a Ge particle-reinforced Zn-based composite material, characterized in that the method is used for producing the composite material according to any one of claims 1 to 4, and the production method comprises the steps of:
s1, preparing materials: pure Zn ingot, single crystal Ge and pure Mg ingot are taken as raw materials, and the reinforcing phase Mg in the composite material is selected2Respectively weighing pure Zn ingots, single crystal Ge and pure Mg ingots according to the content of Ge for later use;
s2, smelting: sequentially adding pure Zn ingots, single crystal Ge and pure Mg ingots into a smelting furnace for smelting, and then pouring to obtain metal ingots;
s3, homogenization treatment: carrying out homogenization treatment on the metal ingot at the temperature of 250-320 ℃ for 4-20 h;
s4, hot rolling: cutting off the top and the bottom of a metal ingot, cutting to obtain a metal plate for hot rolling, adjusting hot rolling process parameters to ensure that the deformation of the metal plate is 60-95%, and hot rolling to obtain the degradable in-situ authigenic Mg2The Ge particles reinforce the Zn-based composite.
6. The preparation method according to claim 5, wherein in the step S1, the mass ratio of the single crystal Ge to the pure Mg ingot is 48: 73.
7. the production method according to claim 5, wherein in the step S2:
firstly, adding the pure Zn ingot weighed in the step S1 into a smelting furnace, and adding the pure Zn ingot into Ar2Heating to 500-600 ℃ under the protection of atmosphere for smelting;
adding single crystal Ge after the pure Zn ingot is completely melted, and raising the temperature to 550-650 ℃ for smelting;
after the single crystal Ge is completely melted, adding a pure Mg ingot, and cooling to 520-620 ℃ for smelting;
and after the pure Mg ingot is completely melted, carrying out slag skimming treatment, reducing the pouring temperature to 500-560 ℃, and finally pouring into a steel die preheated to 150-250 ℃ to obtain the metal ingot.
8. The method according to claim 5, wherein in step S3, the ingot is air-cooled or water-cooled to room temperature after the ingot is subjected to homogenization treatment by keeping the ingot at 250 to 320 ℃ for 4 to 20 hours.
9. The method according to claim 5, wherein in the step S4, the metal sheet is preheated to 230 to 300 ℃ and maintained for 1 to 15min before hot rolling; the hot rolling process is multi-pass hot rolling, the reduction of each pass of hot rolling is 0.2-1 mm, and the metal plate is immediately placed into a heating furnace to be heated for 1-5 min after each pass of hot rolling.
10. The manufacturing method according to claim 9, wherein in the step S4, the metal plate is finally rolled to a thickness of 4 to 0.5mm by multi-pass hot rolling.
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CN105925848A (en) * 2016-06-28 2016-09-07 东北大学 Biomedical degradable zinc alloy inner implantation material and preparation method of sheet material of biomedical degradable zinc alloy inner implantation material
CN109966568A (en) * 2019-04-11 2019-07-05 湘潭大学 A kind of Zn-Ge-X ternary bio-medical material and preparation method thereof
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CN109966568A (en) * 2019-04-11 2019-07-05 湘潭大学 A kind of Zn-Ge-X ternary bio-medical material and preparation method thereof
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CN114703398A (en) * 2022-04-13 2022-07-05 温州医科大学附属口腔医院 Ultrasonic wave and alterant combined refining degradable Zn-XMg2Ge composite material and preparation method thereof

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