CN104498790B - Degradable magnesium alloy bio-implantation material and preparation method thereof - Google Patents
Degradable magnesium alloy bio-implantation material and preparation method thereof Download PDFInfo
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- CN104498790B CN104498790B CN201410733584.3A CN201410733584A CN104498790B CN 104498790 B CN104498790 B CN 104498790B CN 201410733584 A CN201410733584 A CN 201410733584A CN 104498790 B CN104498790 B CN 104498790B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
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- 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
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
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- 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
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
Abstract
The invention relates to a degradable magnesium alloy bio-implantation material which is characterized by consisting of the following components in percentage by mass: 0-12% of Zn, 0-10.5% of Ca and the balance of Mg and unavoidable impurities carried by the raw materials, wherein the total content of Zn and Ca is higher than or equal to 1.0%; the total content of unavoidable impurities is higher than or equal to 0.005%; in the unavoidable impurities, the content of Fe is lower than or equal to 0.0005%, the content of Ni is lower than or equal to 0.0005%, and the content of Cu is lower than or equal to 0.001%; and the invention also relates to a preparation method of the degradable magnesium alloy bio-implantation material. The degradable magnesium alloy bio-implantation material provided by the invention is non-toxic to a human body, has good corrosion resistance and good strength, and is suitable to be used for preparing magnesium alloy bio-implantation devices such as bone nails, bone plates and cardiovascular stents.
Description
Technical field
The present invention relates to a kind of biomedical alloy material, more particularly to a kind of degradable magnesium alloy biological implantation material and
Its preparation method.
Background technology
At present, clinically the implantation material of main application includes rustless steel, titanium or titanium alloy, Co-Cr alloys etc., but these
There is problems with material application clinically：(1) because the release for corroding the toxic metal ions or granule for causing causes
Inflammatory reaction；(2) elastic modelling quantity of metal material is significantly larger than the elastic modelling quantity of people's bone, local bone tissue is produced very big
" stress shielding " effect, may cause natural bone the functional deterioration even possibility of atrophy；(3) material such as rustless steel and titanium or titanium alloy
Material is bio-inert material, in vivo non-degradable, when as provisional implantation material such as intravascular stent, nail, hone lamella, bone
During pin, need to carry out second operation taking-up, increased painful, the psychological and financial burden of patient.
Biological degradable in vivo absorbing material is just becoming a study hotspot of biomaterial, the biology of current clinical practice
Degradable in vivo absorbing material is mainly polymer, some ceramic materials and metal material etc., wherein polymer such as polylactic acid, phosphorus
Sour calcium etc., its application due to low strength obtains huge restriction, and the plasticity and toughness of ceramic material are poor almost cannot use.In recent years
Come, the research of the medical metal material of new generation with biodegradable magnesium alloy as main representative receives people's concern.Magnesium is closed
Gold utensil has good mechanical compatibility, and proportion is little, and its density is about 1.738g/cm3, with people's bone density (about 1.75g/cm3) very
It is close to, is biomechanical property and the immediate metal material of human body bone, the springform of magnesium alloy in current all metal materials
Amount is about 45GPa, about the 1/2 of clinic titanium alloy, clinic with stainless 1/4～1/5, and with human body flexible bone modulus most
It is close, can effectively reduces " stress shielding " effect, promotes symphysis.While magnesium is used as nutrient needed by human, its
Content in human body is only second to Ca, Na, K, is the 4th bit element in human body, and intracellular level is only second to K+.Degradable biological magnesium
Alloy material dexterously realizes metal implant in body using the characteristic of magnesium alloy easy generation corrosion degradation in human body environment
Inside gradually degrade until the final clinical medicine purpose for disappearing, the pain that second operation can be avoided to bring to patient, especially to little
Children surgical department has special meaning, because trophophase of the child in human body, the use of conventional medical metal material is required secondary
Operation is taken out.In view of magnesium alloy materials have above-mentioned advantage, degradable medical magnesium alloy is described as " revolutionary metal biology material
Expect " and receive global concern.
At present, in terms of Medical magnesium alloy material research and development, domestic and international research worker is concentrated mainly on closes to existing commercial magnesium
Gold such as Mg-Al systems, Mg-RE systems, Mg-Mn-Zn systems carry out biomedical evaluation, and Europe comes into the heart of Human Clinical Study
Intravascular stent is mainly made using commercialization magnesium-rare earth WE43.Conventional commercialization magnesium alloy uses presence directly as biomaterial
Risk, is primarily due to commercial magnesium alloy and uses as structural material, is designed without considering the biocompatibility of material
The problems such as, such as：The Al elements contained in AZ series alloys are not belonging to the essential trace element of human body, are considered to have Nervous toxicity
Property, it is the factor for causing presenile dementia, it has been observed that moderate rejection when the magnesium alloy containing Al is tested in vivo.Comprehensive state
Inside and outside achievement in research, although indivedual magnesium alloy materials have started to clinical practice with regard to human body privileged sites, on the whole, researches and develops
Degradable magnesium alloy still there is problems with：(1) corrosion rate of magnesium alloy is too fast, it is easy in implantation material endothelialization
Start degraded before process stabilization, therefore be unable to reach expected degradation rate；(2) there is environment auxiliary in magnesium alloy implant material
Cracking (EAC) problem, also referred to as stress corrosion cracking (SCC) or the EAC of corrosion fatigue (CF), can cause material sudden failure
Phenomenon；(3) compared with the materials such as rustless steel, magnesium alloy fragility is big, and plastic deformation ability is poor.
The content of the invention
The technical problem to be solved be for prior art and provide it is a kind of to human body without any toxicity, corrosion resistant
The preferable degradable magnesium alloy biological implantation materials of combination property such as erosion, intensity and ductility.
Another technical problem to be solved by this invention is to provide a kind of above-mentioned degradable magnesium alloy biological implantation material
Preparation method.
The present invention solve the technical scheme that adopted of above-mentioned technical problem for：A kind of biological implantation material of degradable magnesium alloy
Material, it is characterised in that：The mass percent of each composition is consisted of in above-mentioned magnesium alloy biological implantation material：Zn 0～12%, Ca0
～10.5%, and the content of Zn and Ca and >=1.0%, remaining is Mg and the inevitable impurity brought into by raw material, no
Content sum≤0.005% of impurity can be avoided, Fe≤0.0005%, Ni≤0.0005%, Cu in the inevitable impurity≤
0.001%.
Preferably, in above-mentioned magnesium alloy biological implantation material：Zn 3.0%～6.5%, Ca 0.8%～1.5%.
Preferably, in above-mentioned magnesium alloy biological implantation material：Zn 0.6%～1.5%, Ca 1.2%～4.5%.
The preparation method of Mg-Zn or Mg-Ca magnesium alloys biological implantation material is comprised the following steps in such scheme：
(1) alloy raw material configuration is carried out by above-mentioned mass percent composition, wherein Zn, Ca, Mg adopts 99.99% purity
Raw material, will raw material soda acid cleaning, drying after it is standby；
(2) the low-carbon (LC) steel crucible without Ni and crucible internal walls coating BN coating are adopted, when crucible is heated to 650 DEG C,
Add pure Mg and in Ar+0.2%SF6Melting is carried out under protection；When pure Mg is completely melt and is warming up to 680 DEG C～700 DEG C, plus
Enter pure Zn or pure Ca is pressed in pure Mg liquations using graphite bell jar, 710 DEG C～730 DEG C are then heated to, using rotary blowing
It is stirred and purified treatment, spiral blowing gas are high-purity Ar gas, gas flow is 30～50ml/min, and the time is 10min
～15min, then treats that temperature reaches 700 DEG C～720 DEG C prepared alloy solutions standby；
(3) Mg-Zn, Mg-Ca alloy raw material is prepared using zone freezing technology：Inwall is scribbled into the low-carbon (LC) without Ni of BN
Steel mold is heated in resistance furnace, when mould is warmed up to 700 DEG C～720 DEG C, pours into a mould the alloy solution got ready, is then placed in adding
Hot stove, and adopt Ar+0.2%SF6Protection；When alloy temperature is stablized to 700 DEG C～720 DEG C, stove lower opening is opened, will
Mould is slowly immersed in water with the speed of 5mm/s～15mm/s, is taken out after cooling, repeated multiple times according to this to prepare Mg-Zn or Mg-
Ca alloy raw materials；
(4) Mg-Zn or Mg-Ca alloy raw materials will be prepared and removes head and afterbody, car removes blank material epidermis, and then soda acid is washed
Post-drying is stand-by；
(5) above-mentioned Mg-Zn or Mg- alloy raw materials are melted in graphite crucible using intermediate frequency furnace, using Ar+0.2%SF6
Protection melting, when alloy temperature is stablized to 710～730 DEG C, is then stirred and purified treatment using rotary blowing, is rotated
Blowing gas are high-purity Ar gas, and gas flow is 30～50ml/min, and the time is 10～15min, then treat temperature reach 700～
720 DEG C stand-by, and to alloy jet deposition is carried out；
(6) magnesium alloy ingot prepared by above-mentioned utilization jet deposition is removed into head and afterbody, and car removes ingot casting epidermis；So
Afterwards ingot casting is heated to into 360～400 DEG C of 2～4h of insulation, from needing the mould of size to be extruded, obtains Mg-Zn or Mg-Ca
Magnesium alloy biological implantation material.
The preparation method of Mg-Zn-Ca magnesium alloys biological implantation material is comprised the following steps in such scheme：
(1) alloy raw material configuration is carried out by above-mentioned mass percent composition, wherein Zn, Ca, Mg adopts 99.99% purity
Raw material, will raw material soda acid cleaning, drying after it is standby；
(2) the low-carbon (LC) steel crucible without Ni and crucible internal walls coating BN coating are adopted, when crucible is heated to 650 DEG C,
Add pure Mg and in Ar+0.2%SF6Melting is carried out under protection；When pure Mg is completely melt and is warming up to 680～700 DEG C, add
Pure Zn；After pure Zn is completely melt, using graphite bell jar will pure Ca be pressed into Mg-Zn alloy molten solutions in, then heat to 710 DEG C～
730 DEG C, then it is stirred using rotary blowing and purified treatment, spiral blowing gas are high-purity Ar gas, and gas flow is 30
～50ml/min, the time is 10min～15min, then treats that temperature reaches 700 DEG C～720 DEG C prepared alloy solutions standby；
(3) Mg-Zn-Ca alloy raw materials are prepared using zone freezing technology：Inwall is scribbled into the mild steel without Ni of BN
Mould is heated in resistance furnace, when mould is warmed up to 700～720 DEG C, pours into a mould the alloy solution got ready, is then placed in heating
Stove, and adopt Ar+0.2%SF6Protection；When alloy temperature is stablized to 700～720 DEG C, stove lower opening is opened, by mould
It is slowly immersed in water with the speed of 5～15mm/s, is taken out after cooling, it is repeated multiple times according to this to prepare Mg-Zn-Ca alloy raw materials；
(4) Mg-Zn-Ca alloy raw materials will be prepared and removes head and afterbody, car removes blank material epidermis, and then soda acid washes after bake
It is dry stand-by；
(5) above-mentioned Mg-Zn-Ca alloy raw materials are melted in graphite crucible using intermediate frequency furnace, is protected using Ar+0.2%SF6
Shield melting, when alloy temperature is stablized to 710～730 DEG C, is then stirred and purified treatment, rotation spray using rotary blowing
Blowing is high-purity Ar gas, and gas flow is 30～50ml/min, and the time is 10～15min, then treat temperature reach 700～
720 DEG C stand-by, and to alloy jet deposition is carried out；
(6) magnesium alloy ingot prepared by above-mentioned utilization jet deposition is removed into head and afterbody, and car removes ingot casting epidermis；So
Afterwards ingot casting is heated to into 360～400 DEG C of 2～4h of insulation, from needing the mould of size to be extruded, obtains the conjunction of Mg-Zn-Ca magnesium
Golden biological implantation material.
In the preparation method of above-mentioned each magnesium alloy biological implantation material, the processing parameter of the jet deposition is：Metal stream
Amount 6～8Kg/min, 20.5～23.5HZ of scanning speed, nitrogen gas 20～25Nm of flow3/ min, 8～10atm of nitrogen pressure,
650～750mm of jetting height, receives chassis 2.7～3.2r/s of rotary speed, receives chassis 0.6～0.8mm/s of translational speed.
Compared with prior art, it is an advantage of the current invention that：
1) in the present invention magnesium alloy biological implantation material with Mg, Zn, Ca as raw material, and Mg, Zn, Ca are that three-type-person's body must
Element is needed, ion can be formed in human body and is absorbed by the body or discharge, to human body without any toxicity；
2) using high-purity raw material, (purity reaches in magnesium alloy biological implantation material preparation method in the present invention
99.99%), and using zone freezing technology alloy material is prepared, strictly controls the impurity elements such as harmful element Fe, Ni, Cu
Content (impurity content≤0.005%), improve the decay resistance of magnesium alloy；
3) spray deposition technique can prepare the magnesium alloy blank of ultra-fine grain in the present invention, while improve Zn, Ca existing
The solid solubility of the solid solubility in magnesium alloy fused mass, particularly Ca, reduces the thermal fragmentation defect of magnesium alloy, substantially increases conjunction
The obdurability of gold；
4) extrusion technique is capable of the crystal grain and precipitated phase of further Refining Mg Alloy jet deposition blank, raising in the present invention
The combination property of magnesium alloy, is suitable for preparing the magnesium alloys such as nail, hone lamella, angiocarpy bracket biology implant devices.
Specific embodiment
The present invention is described in further detail below by way of specific embodiment.
Embodiment 1
Mass percent composition according to each composition in the magnesium alloy biological implantation material in the present invention carries out alloy raw material
Configuration, specifically comprises Ca 10.5%, and remaining is Mg, Impurity Fe≤0.0005%, Ni≤0.0005% in alloy,
Cu≤0.001%, impurity element total amount≤0.005%, raw material adopts 99.99%Mg, 99.99%Ca, and raw material is sharp
Cleaned with soda acid, drying and processing.
The preparation of Mg-Ca alloys is using the mild steel crucible for smelting without Ni, and crucible internal walls apply BN, treats that crucible is heated
During to 650 DEG C, pure Mg is added to be melted, using Ar+0.2%SF6The lower melting of protection；Treat that pure Mg is completely melt to be warmed up to 680
DEG C when, pure Ca is pressed in Mg liquations using graphite bell jar, then heat to 710 DEG C, be stirred and only using rotary blowing
Change is processed, and spiral blowing gas are high-purity Ar gas, and gas flow is 30ml/min, and the time is 10min, treats that temperature reaches 720 DEG C
When be obtained alloy solution it is stand-by.
Mg-Ca alloy raw materials are prepared using zone freezing technology, inwall is scribbled into the low-carbon (LC) steel mold (Φ without Ni of BN
120mm × 200mm) heating in resistance furnace (under have opening, can be directly entered after opening in the cycle bucket below resistance furnace),
When mould is warmed up to 720 DEG C, the alloy solution got ready is poured into a mould, be then placed in heating furnace, and adopt Ar+0.2%SF6Protection；
When alloy temperature is stablized to 720 DEG C, stove lower opening is opened, mould is slowly immersed in water with the speed of 5mm/s, cooled down
After take out, it is repeated multiple times according to this to prepare Mg-Ca alloy raw materials；Alloy raw material will be prepared and remove head (30mm) and afterbody
(30mm), car removes blank material epidermis (radial direction 2mm), and then soda acid cleaning post-drying is stand-by.
High-purity Mg-Ca alloys prepared by above-mentioned utilization zone freezing technology are melted in graphite crucible using intermediate frequency furnace,
Using Ar+0.2%SF6Protection melting, whne alloy temperature it is stable to 730 DEG C when, be then stirred using rotary blowing and only
Change is processed, and spiral blowing gas are high-purity Ar gas, and gas flow is 30ml/min, and the time is 10min, then treats that temperature reaches
700 DEG C stand-by, and the design parameter of alloy jet deposition is as follows：Metal flow 6Kg/min (adopts flow-guiding mouth diameter of phi 5mm), sweeps
Retouch speed 21.5HZ, nitrogen gas flow 25Nm3/ min, nitrogen pressure 9atm, jetting height 650mm receives chassis rotation speed
Degree 2.7r/s, receives chassis translational speed 0.6mm/s.By above-mentioned parameter and method, Φ 250mm × 600mm can be prepared
High-purity fine grain jet deposition ingot casting.
Magnesium alloy ingot prepared by above-mentioned utilization jet deposition is removed into head (50mm) and afterbody (50mm), and Che Quzhu
Ingot epidermis (radial direction 5mm)；Then ingot casting is heated to into 400 DEG C of insulation 3h, is extruded from the mould of Φ 10mm, obtained
The Mg-Ca wire rods of Φ 10mm, mechanical experimental results show that tensile strength reaches 246MPa under room temperature, and yield strength is
198MPa, percentage elongation is 8%, can be degraded in simulation of human body liquid, and the corrosion rate after stablizing is only 0.035mm/a, this
Wire rod can prepare Mg-Ca magnesium alloys biology implant devices, such as nail, hone lamella, angiocarpy bracket etc. by following process.
Embodiment 2
Mass percent composition according to each composition in the magnesium alloy biological implantation material in the present invention carries out alloy raw material
Configuration, specifically comprises Ca 4.5%, and remaining is Mg, Impurity Fe≤0.0005%, Ni≤0.0005% in alloy, Cu
≤ 0.001%, impurity element total amount≤0.005%, raw material adopts 99.99%Mg, 99.99%Ca, and raw material is utilized
Soda acid cleaning, drying and processing.
The preparation of Mg-Ca alloys is using the mild steel crucible for smelting without Ni, and crucible internal walls apply BN, treats that crucible is heated
During to 650 DEG C, pure Mg is added to be melted, using Ar+0.2%SF6The lower melting of protection；Treat that pure Mg is completely melt to be warmed up to 690
DEG C when, pure Ca is pressed in Mg liquations using graphite bell jar, then heat to 730 DEG C, be stirred and only using rotary blowing
Change is processed, and spiral blowing gas are high-purity Ar gas, and gas flow is 30ml/min, and the time is 10min, treats that temperature reaches 700 DEG C
When be obtained alloy solution it is stand-by.
Mg-Ca alloy raw materials are prepared using zone freezing technology, inwall is scribbled into the low-carbon (LC) steel mold (Φ without Ni of BN
120mm × 200mm) heating in resistance furnace (under have opening, can be directly entered after opening in the cycle bucket below resistance furnace),
When mould is warmed up to 700 DEG C, the alloy solution got ready is poured into a mould, be then placed in heating furnace, and adopt Ar+0.2%SF6Protection；
When alloy temperature is stablized to 700 DEG C, stove lower opening is opened, mould is slowly immersed in water with the speed of 5mm/s, cooled down
After take out, it is repeated multiple times according to this to prepare Mg-Ca alloy raw materials；Alloy raw material will be prepared and remove head (30mm) and afterbody
(30mm), car removes blank material epidermis (radial direction 2mm), and then soda acid cleaning post-drying is stand-by.
High-purity Mg-Ca alloys prepared by above-mentioned utilization zone freezing technology are melted in graphite crucible using intermediate frequency furnace,
Using Ar+0.2%SF6Protection melting, whne alloy temperature it is stable to 710 DEG C when, be then stirred using rotary blowing and only
Change is processed, and spiral blowing gas are high-purity Ar gas, and gas flow is 30ml/min, and the time is 10min, then treats that temperature reaches
720 DEG C stand-by, and the design parameter of alloy jet deposition is as follows：Metal flow 6Kg/min (adopts flow-guiding mouth diameter of phi 5mm), sweeps
Retouch speed 21.5HZ, nitrogen gas flow 25Nm3/ min, nitrogen pressure 10atm, jetting height 650mm receives chassis rotation speed
Degree 2.7r/s, receives chassis translational speed 0.6mm/s.By above-mentioned parameter and method, Φ 250mm × 600mm can be prepared
High-purity fine grain jet deposition ingot casting.
Magnesium alloy ingot prepared by above-mentioned utilization jet deposition is removed into head (50mm) and afterbody (50mm), and Che Quzhu
Ingot epidermis (radial direction 5mm)；Then ingot casting is heated to into 400 DEG C of insulation 4h, is extruded from the mould of Φ 10mm, obtained
The Mg-Ca wire rods of Φ 10mm, mechanical experimental results show that tensile strength reaches 202MPa under room temperature, and yield strength is
159MPa, percentage elongation is 8.5%, can be degraded in simulation of human body liquid, and the corrosion rate after stablizing is only 0.038mm/a,
This wire rod can prepare Mg-Ca magnesium alloys biology implant devices, such as nail, hone lamella, angiocarpy bracket etc. by following process.
Embodiment 3
Mass percent composition according to each composition in the magnesium alloy biological implantation material in the present invention carries out alloy raw material
Configuration, it specifically comprises Zn 4.5%, Ca 1.2%, and remaining is Mg, Impurity Fe≤0.0005%, Ni in alloy≤
0.0005%th, Cu≤0.001%, impurity element total amount≤0.005% carries out configuring alloy original after calculating by this alloy ratio
Material, Mg-Zn-Ca magnesium alloy materials adopt 99.99%Mg, 99.99%Zn and 99.99%Ca, and raw material is utilized into soda acid
Cleaning, drying and processing.
The preparation of Mg-Zn-Ca alloys is using the mild steel crucible for smelting without Ni, and crucible internal walls apply BN, treat crucible
When being heated to 650 DEG C, pure Mg is added to be melted, using Ar+0.2%SF6The lower melting of protection；Treat that pure Mg is completely melt to be warmed up to
When 680 DEG C, pure Zn is added；Until completely melted, pure Ca is pressed in Mg-Zn alloy molten solutions using graphite bell jar, is then heated up
To 710 DEG C；Then it is stirred using rotary blowing and purified treatment, spiral blowing gas are high-purity Ar gas, gas flow is
50ml/min, the time is 15min, alloy solution is then obtained when temperature reaches 700 DEG C stand-by.
Mg-Zn-Ca alloy raw materials are prepared using zone freezing technology, inwall is scribbled into the low-carbon (LC) steel mold without Ni of BN
(Φ 120mm × 200mm) in resistance furnace (under have opening, can be directly entered after opening in the cycle bucket below resistance furnace) plus
Heat, when mould is warmed up to 700 DEG C, pours into a mould the alloy solution got ready, is then placed in heating furnace, and adopts Ar+0.2%SF6Protect
Shield；When alloy temperature is stablized to 700 DEG C, stove lower opening is opened, mould is slowly immersed in water with the speed of 8mm/s,
Take out after cooling, it is repeated multiple times according to this to prepare Mg-Zn-Ca alloy raw materials；To prepare alloy raw material remove head (30mm) and
Afterbody (30mm), car removes blank material epidermis (radial direction 2mm), and then soda acid cleaning post-drying is stand-by.
The high-purity Mg-Zn-Ca alloys for being prepared above-mentioned utilization zone freezing technology using intermediate frequency furnace are melted in graphite crucible
Change, using Ar+0.2%SF6Protection melting, whne alloy temperature it is stable to 710 DEG C when, be then stirred using rotary blowing and
Purified treatment, spiral blowing gas are high-purity Ar gas, and gas flow is 50ml/min, and the time is 10min, then treats that temperature reaches
700 DEG C stand-by, and the design parameter of alloy jet deposition is as follows：Metal flow 7.5Kg/min (adopts flow-guiding mouth diameter of phi 5mm),
Scanning speed 23.5HZ, nitrogen gas flow 25Nm3/ min, nitrogen pressure 8atm, jetting height 650mm receives chassis rotation
Speed 3.0r/s, receives chassis translational speed 0.7mm/s.By above-mentioned parameter and method, Φ 250mm × 500 can be prepared
High-purity fine grain jet deposition ingot casting of～650mm.
Mg-Zn-Ca magnesium alloy ingots prepared by above-mentioned utilization jet deposition are removed into head (50mm) and afterbody (50mm),
And car removes ingot casting epidermis (radial direction 5mm)；Then ingot casting is heated to into 360 DEG C of insulation 2h, from the mould of 100mm × 10mm
Extruded, obtained Mg-Zn-Ca magnesium alloy extrusion sheet materials, mechanical experimental results are shown that tensile strength reaches under room temperature
354MPa, yield strength is 301MPa, and percentage elongation is 16%, can be degraded in simulation of human body liquid, and the corrosion speed after stablizing
Rate is only 0.046mm/a, and then this sheet material can be prepared into the magnesium alloys such as hone lamella biology implant devices, such as bone by following process
Nail, hone lamella, angiocarpy bracket etc..
Embodiment 4
Mass percent composition according to each composition in the magnesium alloy biological implantation material in the present invention carries out alloy raw material
Configuration, it specifically comprises Zn 6.5%, Ca 1.2%, and remaining is Mg, Impurity Fe≤0.0005%, Ni in alloy≤
0.0005%th, Cu≤0.001%, impurity element total amount≤0.005% carries out configuring alloy original after calculating by this alloy ratio
Material, Mg-Zn-Ca magnesium alloy materials adopt 99.99%Mg, 99.99%Zn and 99.99%Ca, and raw material is utilized into soda acid
Cleaning, drying and processing.
The preparation of Mg-Zn-Ca alloys is using the mild steel crucible for smelting without Ni, and crucible internal walls apply BN, treat crucible
When being heated to 650 DEG C, pure Mg is added to be melted, using Ar+0.2%SF6The lower melting of protection；Treat that pure Mg is completely melt to be warmed up to
When 680 DEG C, pure Zn is added；Until completely melted, pure Ca is pressed in Mg-Zn alloy molten solutions using graphite bell jar, is then heated up
To 730 DEG C；Then it is stirred using rotary blowing and purified treatment, spiral blowing gas are high-purity Ar gas, gas flow is
50ml/min, the time is 15min, alloy solution is then obtained when temperature reaches 720 DEG C stand-by.
Mg-Zn-Ca alloy raw materials are prepared using zone freezing technology, inwall is scribbled into the low-carbon (LC) steel mold without Ni of BN
(Φ 120mm × 200mm) in resistance furnace (under have opening, can be directly entered after opening in the cycle bucket below resistance furnace) plus
Heat, when mould is warmed up to 720 DEG C, pours into a mould the alloy solution got ready, is then placed in heating furnace, and adopts Ar+0.2%SF6Protect
Shield；When alloy temperature is stablized to 720 DEG C, stove lower opening is opened, mould is slowly immersed in water with the speed of 8mm/s,
Take out after cooling, it is repeated multiple times according to this to prepare Mg-Zn-Ca alloy raw materials；To prepare alloy raw material remove head (30mm) and
Afterbody (30mm), car removes blank material epidermis (radial direction 2mm), and then soda acid cleaning post-drying is stand-by.
The high-purity Mg-Zn-Ca alloys for being prepared above-mentioned utilization zone freezing technology using intermediate frequency furnace are melted in graphite crucible
Change, using Ar+0.2%SF6Protection melting, whne alloy temperature it is stable to 730 DEG C when, be then stirred using rotary blowing and
Purified treatment, spiral blowing gas are high-purity Ar gas, and gas flow is 50ml/min, and the time is 15min, then treats that temperature reaches
720 DEG C stand-by, and the design parameter of alloy jet deposition is as follows：Metal flow 7.5Kg/min (adopts flow-guiding mouth diameter of phi 5mm),
Scanning speed 23.5HZ, nitrogen gas flow 25Nm3/min, nitrogen pressure 10atm, jetting height 650mm receives chassis rotation
Speed 3.0r/s, receives chassis translational speed 0.7mm/s.By above-mentioned parameter and method, Φ 250mm × 500 can be prepared
High-purity fine grain jet deposition ingot casting of～650mm.
Mg-Zn-Ca magnesium alloy ingots prepared by above-mentioned utilization jet deposition are removed into head (50mm) and afterbody (50mm),
And car removes ingot casting epidermis (radial direction 5mm)；Then ingot casting is heated to into 360 DEG C of insulation 4h, from the mould of 100mm × 10mm
Extruded, obtained Mg-Zn-Ca magnesium alloy extrusion sheet materials, mechanical experimental results are shown that tensile strength reaches under room temperature
371MPa, yield strength is 296MPa, and percentage elongation is 12%, can be degraded in simulation of human body liquid, and the corrosion speed after stablizing
Rate is only 0.048mm/a, and then this sheet material can be prepared into the magnesium alloys such as hone lamella biology implant devices, such as bone by following process
Nail, hone lamella, angiocarpy bracket etc..
Embodiment 5
Mass percent composition according to each composition in the magnesium alloy biological implantation material in the present invention carries out alloy raw material
Configuration, it specifically comprises Zn 3.0%, Ca 0.8%, and remaining is Mg, Impurity Fe≤0.0005%, Ni in alloy≤
0.0005%th, Cu≤0.001%, impurity element total amount≤0.005% carries out configuring alloy original after calculating by this alloy ratio
Material, Mg-Zn-Ca magnesium alloy materials adopt 99.99%Mg, 99.99%Zn and 99.99%Ca, and raw material is utilized into soda acid
Cleaning, drying and processing.
The preparation of Mg-Zn-Ca alloys is using the mild steel crucible for smelting without Ni, and crucible internal walls apply BN, treat crucible
When being heated to 650 DEG C, pure Mg is added to be melted, using the lower melting of Ar+0.2%SF6 protections；Treat that pure Mg is completely melt to be warmed up to
When 690 DEG C, pure Zn is added；Until completely melted, pure Ca is pressed in Mg-Zn alloy molten solutions using graphite bell jar, is then heated up
To 720 DEG C；Then it is stirred using rotary blowing and purified treatment, spiral blowing gas are high-purity Ar gas, gas flow is
50ml/min, the time is 15min, alloy solution is then obtained when temperature reaches 710 DEG C stand-by.
Mg-Zn-Ca alloy raw materials are prepared using zone freezing technology, inwall is scribbled into the low-carbon (LC) steel mold without Ni of BN
(Φ 120mm × 200mm) in resistance furnace (under have opening, can be directly entered after opening in the cycle bucket below resistance furnace) plus
Heat, when mould is warmed up to 710 DEG C, pours into a mould the alloy solution got ready, is then placed in heating furnace, and adopts Ar+0.2%SF6Protect
Shield；When alloy temperature is stablized to 710 DEG C, stove lower opening is opened, mould is slowly immersed in water with the speed of 8mm/s,
Take out after cooling, it is repeated multiple times according to this to prepare Mg-Zn-Ca alloy raw materials；To prepare alloy raw material remove head (30mm) and
Afterbody (30mm), car removes blank material epidermis (radial direction 2mm), and then soda acid cleaning post-drying is stand-by.
The high-purity Mg-Zn-Ca alloys for being prepared above-mentioned utilization zone freezing technology using intermediate frequency furnace are melted in graphite crucible
Change, using Ar+0.2%SF6Protection melting, whne alloy temperature it is stable to 720 DEG C when, be then stirred using rotary blowing and
Purified treatment, spiral blowing gas are high-purity Ar gas, and gas flow is 50ml/min, and the time is 12min, then treats that temperature reaches
710 DEG C stand-by, and the design parameter of alloy jet deposition is as follows：Metal flow 7.5Kg/min (adopts flow-guiding mouth diameter of phi 5mm),
Scanning speed 23.5HZ, nitrogen gas flow 25Nm3/ min, nitrogen pressure 9atm, jetting height 650mm receives chassis rotation
Speed 3.0r/s, receives chassis translational speed 0.7mm/s.By above-mentioned parameter and method, Φ 250mm × 500 can be prepared
High-purity fine grain jet deposition ingot casting of～650mm.
Mg-Zn-Ca magnesium alloy ingots prepared by above-mentioned utilization jet deposition are removed into head (50mm) and afterbody (50mm),
And car removes ingot casting epidermis (radial direction 5mm)；Then ingot casting is heated to into 360 DEG C of insulation 3h, from the mould of 100mm × 10mm
Extruded, obtained Mg-Zn-Ca magnesium alloy extrusion sheet materials, mechanical experimental results are shown that tensile strength reaches under room temperature
213MPa, yield strength is 154MPa, and percentage elongation is 11.5%, can be degraded in simulation of human body liquid, and the corrosion after stablizing
Speed is only 0.041mm/a, and then this sheet material can be prepared into the magnesium alloys such as hone lamella biology implant devices by following process, for example
Nail, hone lamella, angiocarpy bracket etc..
Embodiment 6
Mass percent composition according to each composition in the magnesium alloy biological implantation material in the present invention carries out alloy raw material
Configuration, it specifically comprises Zn 1.5%, Ca 4.5%, and remaining is Mg, Impurity Fe≤0.0005%, Ni in alloy≤
0.0005%th, Cu≤0.001%, impurity element total amount≤0.005% carries out configuring alloy original after calculating by this alloy ratio
Material, Mg-Zn-Ca magnesium alloy materials adopt 99.99%Mg, 99.99%Zn and 99.99%Ca, and raw material is utilized into soda acid
Cleaning, drying and processing.
The preparation of Mg-Zn-Ca alloys is using the mild steel crucible for smelting without Ni, and crucible internal walls apply BN, treat crucible
When being heated to 650 DEG C, pure Mg is added to be melted, using Ar+0.2%SF6The lower melting of protection；Treat that pure Mg is completely melt to be warmed up to
When 680 DEG C, pure Zn is added；Until completely melted, pure Ca is pressed in Mg-Zn alloy molten solutions using graphite bell jar, is then heated up
To 710 DEG C；Then it is stirred using rotary blowing and purified treatment, spiral blowing gas are high-purity Ar gas, gas flow is
50ml/min, the time is 15min, then treat temperature reach 700 DEG C it is stand-by.
Mg-Zn-Ca alloy raw materials are prepared using zone freezing technology, inwall is scribbled into the low-carbon (LC) steel mold without Ni of BN
(Φ 120mm × 200mm) in resistance furnace (under have opening, can be directly entered after opening in the cycle bucket below resistance furnace) plus
Heat, when mould is warmed up to 700 DEG C, pours into a mould the alloy solution got ready, is then placed in heating furnace, and adopts Ar+0.2%SF6Protect
Shield；When alloy temperature is stablized to 700 DEG C, stove lower opening is opened, mould is slowly immersed in water with the speed of 8mm/s,
Take out after cooling, it is repeated multiple times according to this to prepare Mg-Zn-Ca alloy raw materials；To prepare alloy raw material remove head (30mm) and
Afterbody (30mm), car removes blank material epidermis (radial direction 2mm), and then soda acid cleaning post-drying is stand-by.
The high-purity Mg-Zn-Ca alloys for being prepared above-mentioned utilization zone freezing technology using intermediate frequency furnace are melted in graphite crucible
Change, using Ar+0.2%SF6Protection melting, whne alloy temperature it is stable to 710 DEG C when, be then stirred using rotary blowing and
Purified treatment, spiral blowing gas are high-purity Ar gas, and gas flow is 50ml/min, and the time is 10min, then treats that temperature reaches
700 DEG C stand-by, and the design parameter of alloy jet deposition is as follows：Metal flow 7.5Kg/min (adopts flow-guiding mouth diameter of phi 5mm),
Scanning speed 23.5HZ, nitrogen gas flow 25Nm3/min, nitrogen pressure 8atm, jetting height 650mm receives chassis rotation
Speed 3.0r/s, receives chassis translational speed 0.7mm/s.By above-mentioned parameter and method, Φ 250mm × 500 can be prepared
High-purity fine grain jet deposition ingot casting of～650mm.
Mg-Zn-Ca magnesium alloy ingots prepared by above-mentioned utilization jet deposition are removed into head (50mm) and afterbody (50mm),
And car removes ingot casting epidermis (radial direction 5mm)；Then ingot casting is heated to into 360 DEG C of insulation 3h, from the mould of 100mm × 10mm
Extruded, obtained Mg-Zn-Ca magnesium alloy extrusion sheet materials, mechanical experimental results are shown that tensile strength reaches under room temperature
286MPa, yield strength is 219MPa, and percentage elongation is 13.2%, can be degraded in simulation of human body liquid, and must be corroded after stablizing
Speed is only 0.04mm/a, and then this sheet material can be prepared into the magnesium alloys such as hone lamella biology implant devices by following process, for example
Nail, hone lamella, angiocarpy bracket etc..
Embodiment 7
Mass percent composition according to each composition in the magnesium alloy biological implantation material in the present invention carries out alloy raw material
Configuration, it specifically comprises Zn 0.6%, Ca 1.5%, and remaining is Mg, Impurity Fe≤0.0005%, Ni in alloy≤
0.0005%th, Cu≤0.001%, impurity element total amount≤0.005% carries out configuring alloy original after calculating by this alloy ratio
Material, Mg-Zn-Ca magnesium alloy materials adopt 99.99%Mg, 99.99%Zn and 99.99%Ca, and raw material is utilized into soda acid
Cleaning, drying and processing.
The preparation of Mg-Zn-Ca alloys is using the mild steel crucible for smelting without Ni, and crucible internal walls apply BN, treat crucible
When being heated to 650 DEG C, pure Mg is added to be melted, using Ar+0.2%SF6The lower melting of protection；Treat that pure Mg is completely melt to be warmed up to
When 700 DEG C, pure Zn is added；Until completely melted, pure Ca is pressed in Mg-Zn alloy molten solutions using graphite bell jar, is then heated up
To 730 DEG C；Then it is stirred using rotary blowing and purified treatment, spiral blowing gas are high-purity Ar gas, gas flow is
50ml/min, the time is 15min, then treat temperature reach 720 DEG C it is stand-by.
Mg-Zn-Ca alloy raw materials are prepared using zone freezing technology, inwall is scribbled into the low-carbon (LC) steel mold without Ni of BN
(Φ 120mm × 200mm) in resistance furnace (under have opening, can be directly entered after opening in the cycle bucket below resistance furnace) plus
Heat, when mould is warmed up to 720 DEG C, pours into a mould the alloy solution got ready, is then placed in heating furnace, and is protected using Ar+0.2%SF6
Shield；When alloy temperature is stablized to 720 DEG C, stove lower opening is opened, mould is slowly immersed in water with the speed of 8mm/s,
Take out after cooling, it is repeated multiple times according to this to prepare Mg-Zn-Ca alloy raw materials；To prepare alloy raw material remove head (30mm) and
Afterbody (30mm), car removes blank material epidermis (radial direction 2mm), and then soda acid cleaning post-drying is stand-by.
The high-purity Mg-Zn-Ca alloys for being prepared above-mentioned utilization zone freezing technology using intermediate frequency furnace are melted in graphite crucible
Change, using Ar+0.2%SF6Protection melting, whne alloy temperature it is stable to 730 DEG C when, be then stirred using rotary blowing and
Purified treatment, spiral blowing gas are high-purity Ar gas, and gas flow is 50ml/min, and the time is 15min, then treats that temperature reaches
720 DEG C stand-by, and the design parameter of alloy jet deposition is as follows：Metal flow 7.5Kg/min (adopts flow-guiding mouth diameter of phi 5mm),
Scanning speed 23.5HZ, nitrogen gas flow 25Nm3/min, nitrogen pressure 10atm, jetting height 650mm receives chassis rotation
Speed 3.0r/s, receives chassis translational speed 0.7mm/s.By above-mentioned parameter and method, Φ 250mm × 500 can be prepared
High-purity fine grain jet deposition ingot casting of～650mm.
Mg-Zn-Ca magnesium alloy ingots prepared by above-mentioned utilization jet deposition are removed into head (50mm) and afterbody (50mm),
And car removes ingot casting epidermis (radial direction 5mm)；Then ingot casting is heated to into 360 DEG C of insulation 4h, from the mould of 100mm × 10mm
Extruded, obtained Mg-Zn-Ca magnesium alloy extrusion sheet materials, mechanical experimental results are shown that tensile strength reaches under room temperature
336MPa, yield strength is 261MPa, and percentage elongation is 9.7%, can be degraded in simulation of human body liquid, and must corrode speed after stablizing
Rate is only 0.05mm/a, and then this sheet material can be prepared into the magnesium alloys such as hone lamella biology implant devices, such as bone by following process
Nail, hone lamella, angiocarpy bracket etc..
Embodiment 8
Mass percent composition according to each composition in the magnesium alloy biological implantation material in the present invention carries out alloy raw material
Configuration, specifically comprises Zn 12%, and remaining is Mg, Impurity Fe≤0.0005%, Ni≤0.0005% in alloy, Cu
≤ 0.001%, impurity element total amount≤0.005% carries out configuration alloy raw material after calculating, Mg-Zn magnesium alloy materials are adopted
99.99%Mg, 99.99%Zn, and by raw material using soda acid cleaning, drying and processing.
The preparation of Mg-Zn alloys is using the mild steel crucible for smelting without Ni, and crucible internal walls apply BN, treats that crucible is heated
During to 650 DEG C, pure Mg is added to be melted, using Ar+0.2%SF6The lower melting of protection；Treat that pure Mg is completely melt to be warmed up to 700
DEG C when, add pure Zn, then heat to 710 DEG C；Then it is stirred using rotary blowing and purified treatment, spiral blowing gas
For high-purity Ar gas, gas flow is 50ml/min, and the time is 15min, then treat temperature reach 700 DEG C it is stand-by.
Mg-Zn alloy raw materials are prepared using zone freezing technology, inwall is scribbled into the low-carbon (LC) steel mold (Φ without Ni of BN
120mm × 200mm) heating in resistance furnace (under have opening, can be directly entered after opening in the cycle bucket below resistance furnace),
When mould is warmed up to 700 DEG C, the alloy solution got ready is poured into a mould, be then placed in heating furnace, and adopt Ar+0.2%SF6Protection；
When alloy temperature is stablized to 700 DEG C, stove lower opening is opened, mould is slowly immersed in water with the speed of 10mm/s, it is cold
But take out afterwards, it is repeated multiple times according to this to prepare Mg-Zn alloy raw materials；Alloy raw material will be prepared and remove head (30mm) and afterbody
(30mm), car removes blank material epidermis (radial direction 2mm), and then to wash post-drying stand-by for soda acid.
High-purity Mg-Zn alloys prepared by above-mentioned utilization zone freezing technology are melted in graphite crucible using intermediate frequency furnace,
Melting is protected using Ar+0.2%SF6, whne alloy temperature it is stable to 710 DEG C when, be then stirred using rotary blowing and only
Change is processed, and spiral blowing gas are high-purity Ar gas, and gas flow is 50ml/min, and the time is 15min, then treats that temperature reaches
700 DEG C stand-by, and the design parameter of alloy jet deposition is as follows：Metal flow 8Kg/min (adopts flow-guiding mouth diameter of phi 6mm), sweeps
Speed 23.5HZ is retouched, nitrogen gas flow 25Nm3/min, nitrogen pressure 8atm, jetting height 650mm receives chassis rotation speed
Degree 3.2r/s, receives chassis translational speed 0.8mm/s.By above-mentioned parameter and method, can prepare Φ 250mm × 500～
High-purity fine grain jet deposition ingot casting of 650mm.
Magnesium alloy ingot prepared by above-mentioned utilization jet deposition is removed into head (50mm) and afterbody (50mm), and Che Quzhu
Ingot epidermis (radial direction 5mm)；Then ingot casting is heated to into 380 DEG C of insulation 2h, from needing Φ 10mm moulds to be extruded, is obtained
To Mg-Zn magnesium alloy bar/wire rods, mechanical experimental results show, tensile strength reaches 283MPa under room temperature, and yield strength is
234MPa, percentage elongation is 10.5%, can be degraded in simulation of human body liquid, and the corrosion rate after stablizing is only 0.058mm/a,
This wire rod can prepare the magnesium alloy biological implantation material for needing size by following process.
Embodiment 9
Mass percent composition according to each composition in the magnesium alloy biological implantation material in the present invention carries out alloy raw material
Configuration, specifically comprises Zn 6.5%, and remaining is Mg, Impurity Fe≤0.0005%, Ni≤0.0005% in alloy, Cu
≤ 0.001%, impurity element total amount≤0.005% carries out configuration alloy raw material after calculating, Mg-Zn magnesium alloy materials are adopted
99.99%Mg, 99.99%Zn, and by raw material using soda acid cleaning, drying and processing.
The preparation of Mg-Zn alloys is using the mild steel crucible for smelting without Ni, and crucible internal walls apply BN, treats that crucible is heated
During to 650 DEG C, pure Mg is added to be melted, using Ar+0.2%SF6The lower melting of protection；Treat that pure Mg is completely melt to be warmed up to 700
DEG C when, add pure Zn, then heat to 730 DEG C；Then it is stirred using rotary blowing and purified treatment, spiral blowing gas
For high-purity Ar gas, gas flow is 50ml/min, and the time is 15min, then treat temperature reach 700 DEG C it is stand-by.
Mg-Zn alloy raw materials are prepared using zone freezing technology, inwall is scribbled into the low-carbon (LC) steel mold (Φ without Ni of BN
120mm × 200mm) heating in resistance furnace (under have opening, can be directly entered after opening in the cycle bucket below resistance furnace),
When mould is warmed up to 720 DEG C, the alloy solution got ready is poured into a mould, be then placed in heating furnace, and protected using Ar+0.2%SF6；
When alloy temperature is stablized to 720 DEG C, stove lower opening is opened, mould is slowly immersed in water with the speed of 15mm/s, it is cold
But take out afterwards, it is repeated multiple times according to this to prepare Mg-Zn alloy raw materials；Alloy raw material will be prepared and remove head (30mm) and afterbody
(30mm), car removes blank material epidermis (radial direction 2mm), and then to wash post-drying stand-by for soda acid.
The high-purity Mg-Zn-Ca alloys for being prepared above-mentioned utilization zone freezing technology using intermediate frequency furnace are melted in graphite crucible
Change, using Ar+0.2%SF6Protection melting, whne alloy temperature it is stable to 730 DEG C when, be then stirred using rotary blowing and
Purified treatment, spiral blowing gas are high-purity Ar gas, and gas flow is 50ml/min, and the time is 15min, then treats that temperature reaches
720 DEG C stand-by, and the design parameter of alloy jet deposition is as follows：Metal flow 8Kg/min (adopts flow-guiding mouth diameter of phi 6mm), sweeps
Speed 23.5HZ is retouched, nitrogen gas flow 25Nm3/min, nitrogen pressure 10atm, jetting height 650mm receives chassis rotation speed
Degree 3.2r/s, receives chassis translational speed 0.8mm/s.By above-mentioned parameter and method, can prepare Φ 250mm × 500～
High-purity fine grain jet deposition ingot casting of 650mm.
Magnesium alloy ingot prepared by above-mentioned utilization jet deposition is removed into head (50mm) and afterbody (50mm), and Che Quzhu
Ingot epidermis (radial direction 5mm)；Then ingot casting is heated to into 380 DEG C of insulation 2h, from needing Φ 10mm moulds to be extruded, is obtained
To Mg-Zn magnesium alloy bar/wire rods, mechanical experimental results show, tensile strength reaches 257MPa under room temperature, and yield strength is
191MPa, percentage elongation is 13.2%, can be degraded in simulation of human body liquid, and it is only 0.053mm/a that corrosion rate is obtained after stablizing,
This wire rod can prepare the magnesium alloy biological implantation material for needing size by following process.
Claims (2)
1. a kind of preparation method of degradable magnesium alloy biological implantation material, it is characterised in that the biological implantation material of the magnesium alloy
The mass percent of each composition is consisted of in material：Zn 0～12%, Ca 4.5～10.5%, and the content of Zn and Ca and >=
1.0%, remaining is Mg and the inevitable impurity brought into by raw material, the content sum of inevitable impurity≤
0.005%, Fe≤0.0005%, Ni≤0.0005%, Cu≤0.001% in the inevitable impurity, the magnesium alloy biological plants
The preparation method for entering material is comprised the following steps：
(1) alloy raw material configuration is carried out by above-mentioned mass percent composition, wherein Zn, Ca, Mg are using the original of 99.99% purity
Material, will be standby after the cleaning of raw material soda acid, drying；
(2) the low-carbon (LC) steel crucible without Ni and crucible internal walls coating BN coating are adopted, when crucible is heated to 650 DEG C, is added
Pure Mg and in Ar+0.2%SF6Melting is carried out under protection；When pure Mg is completely melt and is warming up to 680 DEG C～700 DEG C, using stone
Black bell jar is pressed into pure Ca in pure Mg liquations, then heats to 710 DEG C～730 DEG C, is stirred using rotary blowing and is purified
Process, spiral blowing gas are high-purity Ar gas, gas flow is 30～50ml/min, and the time is 10min～15min, is then treated
It is standby that temperature reaches 700 DEG C～720 DEG C prepared alloy solutions；
(3) Mg-Ca alloy raw materials are prepared using zone freezing technology：Inwall is scribbled into the low-carbon (LC) steel mold without Ni of BN in electricity
Heat in resistance stove, when mould is warmed up to 700 DEG C～720 DEG C, pour into a mould the alloy solution got ready, be then placed in heating furnace, and adopt
Use Ar+0.2%SF6Protection；Whne alloy temperature it is stable to 700 DEG C～720 DEG C when, open stove lower opening, by mould with
The speed of 5mm/s～15mm/s is slowly immersed in water, is taken out after cooling, repeated multiple times according to this to prepare Mg-Ca alloy raw materials；
(4) Mg-Ca alloy raw materials will be prepared and removes head and afterbody, car removes blank material epidermis, and then to wash post-drying stand-by for soda acid；
(5) above-mentioned Mg-Ca alloy raw materials are melted in graphite crucible using intermediate frequency furnace, using Ar+0.2%SF6Protection melting,
When alloy temperature is stablized to 710～730 DEG C, it is stirred using rotary blowing and purified treatment, spiral blowing gas are height
Pure Ar gas, gas flow be 30～50ml/min, the time be 10～15min, then treat temperature reach 700～720 DEG C it is stand-by, it is right
Alloy carries out jet deposition；The processing parameter of the jet deposition is：6～8Kg/min of metal flow, scanning speed 20.5～
23.5HZ, nitrogen gas 20～25Nm of flow3/ min, 8～10atm of nitrogen pressure, 650～750mm of jetting height, receive chassis
2.7～3.2r/s of rotary speed, receives chassis 0.6～0.8mm/s of translational speed；
(6) magnesium alloy ingot prepared by above-mentioned utilization jet deposition is removed into head and afterbody, and car removes ingot casting epidermis；Then will
Ingot casting is heated to 360～400 DEG C of 2～4h of insulation, from needing the mould of size to be extruded, obtains Mg-Ca magnesium alloys biological
Implantation material.
2. a kind of preparation method of degradable magnesium alloy biological implantation material, it is characterised in that the biological implantation material of the magnesium alloy
The mass percent of each composition is consisted of in material：Zn 0～12%, Ca 4.5～10.5%, and the content of Zn and Ca and >=
1.0%, remaining is Mg and the inevitable impurity brought into by raw material, the content sum of inevitable impurity≤
0.005%, Fe≤0.0005%, Ni≤0.0005%, Cu≤0.001% in the inevitable impurity, the magnesium alloy biological plants
The preparation method for entering material is comprised the following steps：
(1) alloy raw material configuration is carried out by above-mentioned mass percent composition, wherein Zn, Ca, Mg are using the original of 99.99% purity
Material, will be standby after the cleaning of raw material soda acid, drying；
(2) the low-carbon (LC) steel crucible without Ni and crucible internal walls coating BN coating are adopted, when crucible is heated to 650 DEG C, is added
Pure Mg and in Ar+0.2%SF6Melting is carried out under protection；When pure Mg is completely melt and is warming up to 680～700 DEG C, add pure
Zn；After pure Zn is completely melt, using graphite bell jar will pure Ca be pressed into Mg-Zn alloy molten solutions in, then heat to 710 DEG C～
730 DEG C, then it is stirred using rotary blowing and purified treatment, spiral blowing gas are high-purity Ar gas, and gas flow is 30
～50ml/min, the time is 10min～15min, then treats that temperature reaches 700 DEG C～720 DEG C prepared alloy solutions standby；
(3) Mg-Zn-Ca alloy raw materials are prepared using zone freezing technology：Inwall is scribbled into the low-carbon (LC) steel mold without Ni of BN
Heat in resistance furnace, when mould is warmed up to 700～720 DEG C, pour into a mould the alloy solution got ready, be then placed in heating furnace, and
Using Ar+0.2%SF6Protection；Whne alloy temperature it is stable to 700～720 DEG C when, open stove lower opening, by mould with 5～
The speed of 15mm/s is slowly immersed in water, is taken out after cooling, repeated multiple times according to this to prepare Mg-Zn-Ca alloy raw materials；
(4) Mg-Zn-Ca alloy raw materials will be prepared and removes head and afterbody, car removes blank material epidermis, and then soda acid is washed post-drying and treated
With；
(5) above-mentioned Mg-Zn-Ca alloy raw materials are melted in graphite crucible using intermediate frequency furnace, using Ar+0.2%SF6Protection is molten
Refining, when alloy temperature is stablized to 710～730 DEG C, is then stirred and purified treatment using rotary blowing, and rotation spray is blown
Body is high-purity Ar gas, and gas flow is 30～50ml/min, and the time is 10～15min, then treats that temperature reaches 700～720 DEG C
It is stand-by, jet deposition is carried out to alloy；The processing parameter of the jet deposition is：6～8Kg/min of metal flow, scanning speed
20.5～23.5HZ, nitrogen gas 20～25Nm of flow3/ min, 8～10atm of nitrogen pressure, 650～750mm of jetting height, connect
Chassis 2.7～3.2r/s of rotary speed is received, chassis 0.6～0.8mm/s of translational speed is received；
(6) magnesium alloy ingot prepared by above-mentioned utilization jet deposition is removed into head and afterbody, and car removes ingot casting epidermis；Then will
Ingot casting is heated to 360～400 DEG C of 2～4h of insulation, from needing the mould of size to be extruded, obtains the life of Mg-Zn-Ca magnesium alloys
Thing is implanted into material.
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| CN105385912A (en) * | 2015-11-13 | 2016-03-09 | 无锡清杨机械制造有限公司 | Magnesium alloy sheet and preparing method thereof |
| DE102015120514A1 (en) * | 2015-11-26 | 2017-06-01 | Syntellix Ag | Bioresorbable fixation nail |
| CN105803282B (en) * | 2016-03-22 | 2017-12-08 | 中国兵器科学研究院宁波分院 | A kind of single-phase Multielement rare-earth magnesium alloy biodegradation material and preparation method thereof |
| CN110191971A (en) | 2017-01-10 | 2019-08-30 | 不二轻金属株式会社 | Magnesium alloy |
| JP6671731B2 (en) * | 2017-01-30 | 2020-03-25 | 株式会社 日本医療機器技研 | High performance bioabsorbable stent |
| CN108330368A (en) * | 2018-03-30 | 2018-07-27 | 西安卓恰医疗器械有限公司 | Organism implantation material, its ingredient and preparation method |
| CN108236495B (en) * | 2018-03-30 | 2023-09-22 | 西安卓恰医疗器械有限公司 | Low-alloying degradable miniature internal fixation assembly and magnesium alloy preparation method |
| CA3104447C (en) | 2018-07-09 | 2022-02-15 | Japan Medical Device Technology Co., Ltd. | Magnesium alloy |
| CN109295365B (en) * | 2018-10-23 | 2019-09-06 | 西安卓恰医疗器械有限公司 | A kind of degradable magnesium alloy molding embryo material, Preparation equipment, preparation method and the forcing screw prepared by the molding embryo material |
| CN109295367A (en) * | 2018-12-10 | 2019-02-01 | 南京工程学院 | A kind of high-strength anticorrosion Biological magnesium alloy and preparation method thereof |
| CN109280828B (en) * | 2018-12-10 | 2021-03-02 | 南京工程学院 | High-strength degradable composite material for implanting instrument and preparation method thereof |
| CN111321331B (en) * | 2018-12-13 | 2021-04-02 | 有研工程技术研究院有限公司 | Preparation method of Mg-Zn-Ca biomedical magnesium alloy |
| CN110157966B (en) * | 2019-05-09 | 2021-04-23 | 宁夏中太镁业科技有限公司 | Magnesium alloy pot and manufacturing method thereof |
| CN111228577A (en) * | 2020-01-15 | 2020-06-05 | 太原科技大学 | Medical magnesium alloy capable of being degraded in short term and preparation method thereof |
| CN115198155B (en) * | 2022-05-30 | 2023-04-25 | 宁波市第一医院 | High-performance degradable biological magnesium alloy material and preparation method thereof |
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