CN109966568A - A kind of Zn-Ge-X ternary bio-medical material and preparation method thereof - Google Patents
A kind of Zn-Ge-X ternary bio-medical material and preparation method thereof Download PDFInfo
- Publication number
- CN109966568A CN109966568A CN201910291761.XA CN201910291761A CN109966568A CN 109966568 A CN109966568 A CN 109966568A CN 201910291761 A CN201910291761 A CN 201910291761A CN 109966568 A CN109966568 A CN 109966568A
- Authority
- CN
- China
- Prior art keywords
- source
- alloy
- ternary
- ingot
- bio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/02—Inorganic materials
- A61L31/022—Metals or alloys
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—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
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- 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
-
- 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
- C22C18/02—Alloys based on zinc with copper as the next major constituent
-
- 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
Abstract
The invention discloses a kind of Zn-Ge-X ternary bio-medical materials and preparation method thereof, the Zn-Ge-X ternary bio-medical material is by mass percentage, including following composition: 0.5~6%wt.% of Ge, 0.1~1wt.% of X, the X is selected from least one of Mg, Cu, Mn, Sr, Fe, Ca, Ag, Ti, surplus Zn.The present invention is using traditional casting+deformation process as preparation method, pass through optimization deformation process and the composition of ternary material, the ternary Zn-Ge-X bio-medical material of preparation, have excellent mechanical property, good cell compatibility and suitable biodegradability, is expected to become potential degradable biological medical material.
Description
Technical field
The present invention relates to a kind of Zn-Ge-X ternary bio-medical materials and preparation method thereof, belong to bio-medical metal neck
Domain.
Background technique
With the development of field of biomedicine, the application of degradable biological metal material medically is very universal.It is this kind of
Material executes function instead of wound site tissue first after being implanted into human body, and the degradation then as material absorbs, cambium
Synchronous replacement is obtained, the purpose permanently treated is finally reached, eliminates the risk and pain of second operation, dramatically mention
High curative effect.In addition, degradable biological metal material is since the intensity for stretching and compressing is higher, ductility and impact resistance go out
Color, stable mechanical property, high reliablity, forming performance are excellent after implantation, can be made according to patient personalized demand
Complex-shaped structure, therefore it accounts for 40% or more of Implantable Medical Device material, is to need to bear the bone compared with big load
Tissue, Chi Deng sclerous tissues are treated and the preferred implantable material of interventional therapy bracket, is widely used in gear division, orthopaedics, painstaking effort
The medical fields such as the interventional therapy of pipe, and with the continuous propulsion of astogeny society, from now on to medical degradable implantation material application
Demand increasingly increase.
As a kind of novel degradable metal material, degradation speed is located at magnesium base alloy and ferrous alloy for zinc and its alloy
Between, there is suitable degradation speed, be more suitable for degradable biological medical material.Relative to magnesium and its alloy, zinc and zinc
Alloy has superior corrosion resistance and good biocompatibility, it is even more important that zinc closes during degradation in vivo
Gold will not generate gas, be more conducive to the healing of patient part.At the same time, since the fusing point of pure zinc is lower, chemical activity is not
Height, preparation process are simple.Have fusing point low using the zinc-containing alloy that other elements production is added as matrix in zinc, casting character is excellent,
Good mechanical properties, the technological process of production is short, and energy consumption is small, the cheap advantage of the prices of raw materials, these are also all used as zinc can
One spotlight of degradation biological medical alloy.Zn-ef ficiency participates in many physiology of human body as a kind of required microelement of human body
Activity, normal zinc content is 2~3 grams in human body.In addition, zinc early has been shown to have antibacterial action, relative to Tri-Biocin
Object has many advantages, such as that antibiotic property is stable, lasting, is less prone to drug resistance.Therefore, kirsite has as degradable biomaterial
Broad application prospect.However, pure zinc poor mechanical property, is not able to satisfy the demand of human body.It at present can be by being added into pure zinc
Alloying element, deformation processing and heat treatment appropriate are to improve mechanical property.In alloy element, germanium (Ge) element is as meals
Food microelement is present in human liver, is also recommended for treatment early-stage cancer.Ge element is added being capable of shape in magnesium alloy
At Mg-Ge alloy, show excellent biology performance in experiment in vitro and in vivo, and due at implantation Mg and Ge from
Sub- concentration can by body fluid dilute and make its in bone have good biocompatibility (bibliography: D.Bian,
W.R.Zhou,J.X.Deng,et al.Development of magnesium-based biodegradable metals
with dietary trace element germanium as orthopaedic implant applications[J]
.Acta Biomaterialia.2017,64:421-436.).In addition, organic Ge-132 plays centainly senile osteoporosis
Therapeutic effect, can enhance osteoblast activity, participate in alkaline phosphatase (ALP) metabolism, and prevent senile osteoporosis
In minerals decompose, and in MC3T3-E cell, Ge-132 is able to suppress patients with osteoporosis due to caused by PTH
The problem of bone amount is reduced (bibliography: 1, H.Matsumoto, H.Iwafuji, J.Yamane, et al.Restorative
effect of organic germanium compound(Ge–132)on dermal injury[J].Wound
Medicine.2016,15:6-10.2、A.Fujii,N.Kuboyama,J.Yamane,et al.Effect of organic
germanium compound(Ge–132)on experimental osteoporosis in rats[J].General
Pharmacology the Vascular System.1993,24(6):1527-1532.3、S.Naitou.Studies on
the effect of organogermanium compound Ge–132on bone resorptive activity of
neonatal mouse calvaria and cloned osteoblastic cell line,MC3T3-E1cells[J]
.Sei Marianna ikadaigaku Zasshi.1993,21:1144-1158.).Intake dosage for Ge element and
The research of long time integration, as the GeO of human body intake higher dosage2And (daily 600 when some organic compounds and long-term use
Milligram, 18 months), it will cause acute human renal failure fatal case (bibliography: N.Nagata,
T.Yoneyama,K.Yanagida,et al.Accumulation of germanium in the tissues of a
long-term user of germanium preparation died of acute renal failure[J]
.Journal of Toxicological Sciences.1985,10(4):333-341.).Germanium compound poisoning may cause
Renal failure, gastrointestinal disturbance, hepatosis, anaemia, (bibliography: B.E.L poison can for neurological disease, or even death etc.
It can lead to renal failure, gastrointestinal disturbance, hepatosis, poor et al.Renal and other organ failure
caused by germanium intoxication[J].Nephrology,Dialysis,Transplantation:
Official Publication of the European Dialysis and Transplant Association-
European Renal Association.1999,14(10):2464-2468.).There are also some germanium poisoning cases (daily 90
Milligram GeO2, continue 6 to 20 months) cause human body renal damage and renal failure (bibliography: K.Okada,
K.Okagawa,K.Kawakami,et al.Renal failure caused by long-term use of a
germanium preparation as an elixir[J].Clinical Nephrology.1989,31(4):219-
224.).However, in these cases, when adult (0.4-3.4 milligrams) of Ge amount daily ingestion of several numbers lower than the dosage that causes a disease
When magnitude, it can be absorbed by alimentary canal, be excreted in 24~36h by urine and excrement, therefore suitable Ge element is
Belong to it is a kind of do not accumulate in vivo microelement (bibliography: 1, T.J.Chen, C.H.Lin.Germanium:
environmental pollution and health effects[J].Encyclopedia of Environmental
Health.2011,16(918):927-933.2、K.Yokoi,T.Kawaai,A.Konomi,et al.Dermal
absorption of inorganic germanium in rats[J].Regulatory Toxicology&
Pharmacology.2008,52(2):169-173.)。
To the research for the preparation and respective performances that yet there are no report Zn-Ge-X ternary alloy for mesh at present, therefore propose
Zn-Ge-X ternary alloy is used as to the application of the degradable biological medical material of next stage.
Summary of the invention
For the defects in the prior art, the purpose of the present invention is to provide a kind of with excellent mechanical property, good
Cell compatibility and the suitable Zn-Ge-X ternary biomaterial of biodegradation rate and preparation method thereof.
To achieve the goals above, the technical solution adopted by the present invention is as follows:
A kind of Zn-Ge-X ternary bio-medical material of the present invention, the Zn-Ge-X ternary bio-medical material press quality hundred
Point than meter, including following composition: 0.1~1wt.% of 0.5~6%wt.% of Ge, X, the X be selected from Mg, Cu, Mn, Sr, Fe,
At least one of Ca, Ag, Ti, surplus Zn.
What the present invention initiated provides a kind of Zn-Ge-X ternary bio-medical material, on the basis of Zn-Ge bianry alloy
On, the alloy element X of proper content can play alloying action to kirsite and can effectively improve cell activity, make
Obtaining Zn-Ge-X ternary alloy three-partalloy ratio Zn-Ge bianry alloy has higher mechanical property (including intensity, elongation percentage and hardness etc.)
With superior cell compatibility.
In the above ternary biomaterial, really to meet the various aspects of performance of bio-medical material, need effectively to control
The constituent content of Ge, X processed, it is weaker for the strengthening effect of matrix when the ingredient of Ge is too low, so that the mechanical property of alloy and hard
It spends all relatively low, it is difficult to meet the requirement of biomaterial.And Ge it is excessively high when, due to there is coarse eutectic Ge phase and just in alloy
Raw Ge phase, can isolate Zn matrix, lead to the mechanical property degradation of alloy.X element is mainly as alloy element, when it contains
When measuring too low, alloy is difficult to play the effect of alloying, so that the mechanical property of alloy and hardness promotion are unobvious.And work as
When X element excess, X element can form coarse XZn compound with Zn element, can also hinder dislocation mobile and isolate Zn matrix,
Lead to the mechanical properties decrease of alloy.
Preferred scheme, the Zn-Ge-X ternary bio-medical material by mass percentage, including following composition: Ge
2~5wt.%, X 0.5~1wt.%, the X are selected from least one of Mg, Cu, Fe, Ag, surplus Zn.
A kind of preparation method of Zn-Ge-X ternary bio-medical material of the present invention, includes the following steps: to match by design proportion
Take zinc source, ge source, the source X, the melting under protective atmosphere, cast molding obtains Zn-Ge-X cast alloy ingot, by cast alloy ingot into
Row Homogenization Treatments, then cool to room temperature, then the alloy pig after homogenization is processed into alloy sheets, and preheating, then progress is more
Passage hot rolling and circulating-heating processing.
The preheating temperature is 240~300 DEG C, preheating time≤15min；
Reduction in pass is 2~5% when the hot rolling, total deformation be between 50~80%, passage heating process be 220~
Heat preservation≤5min at 280 DEG C.
The present invention uses traditional casting+deformation process, by the technique in optimization deformation process, is had
The Zn-Ge-X of superior bio performance, be heat-treated in deformation process, between passage it is extremely important, due to kirsite cooling rate compared with
Fastly, the hot rolling treatment that a passage can only be carried out after rolling midway carries out single heat treatment, not can be carried out multi- pass rolling, keeps away
Exempt from kirsite roll plate rapid cooling cause to roll it is cracked.The heating between preheating temperature and passage before either rolling simultaneously
Temperature control when processing is also critically important, if be lower than this temperature range, since the resistance of deformation of kirsite is big, causes
It will appear micro-crack in the operation of rolling, more there will be severe the problem of side is split.And when being higher than this temperature range, crystalline substance can be caused
Grain is coarse, so as to cause the mechanical properties decrease of alloy.Meanwhile temperature is higher, the friction system of specimen surface during the rolling process
Number is higher, skull patch phenomenon easily occurs, leads to the disadvantages such as rolled parts surface quality is poor, dimensional accuracy is low.
Preferred scheme, the temperature of the Homogenization Treatments are 300~350 DEG C, and the time of Homogenization Treatments is 5~12h.
Preferred scheme, the type of cooling are air-cooled or water cooling.By alloy pig into air-cooled or water cooling to room temperature, it is therefore an objective to
To improve the segregation of element in Zn-Ge-X alloy.
Preferred scheme, when hot rolling pass number < 5, the threading speed of milling train is 8m/min~10m/min, works as hot rolling pass
When number >=5, the threading speed of milling train is 20m/min~30m/min.Inventors have found that use is slower when the hot rolling of initial passage
Milling train threading speed, sample front end can be caused to fly up to avoid due to threading excessive velocities, cause deformation uneven existing
As, and subsequent promotion threading speed, it on the one hand can accelerate rolling efficiency, on the other hand prevent sample tail temperature from declining
Fastly, be conducive to the stabilization of rolling deformation.
Preferred scheme, the preheating temperature are 240~270 DEG C, and preheating time is 5~15min.
Preferred scheme, reduction in pass is 5% when the hot rolling, total deformation heater between 60~80%, passage
Skill is that 3~5min is kept the temperature at 220~250 DEG C.
Preferred scheme, the zinc source is selected from Zn ingot or the alloy with X element composition, when the zinc source is selected from Zn ingot,
Mass fraction of the Zn in Zn ingot is 99.99wt.%.
Preferred scheme, the ge source are monocrystalline Ge, and mass fraction of the Ge in monocrystalline Ge is 99.999wt.%.
Preferred scheme, the source X in magnesium source, copper source, manganese source, barium source, source of iron, calcium source, Yin Yuan, titanium source at least
One kind, the magnesium source are Mg ingot, and mass fraction of the Mg in Mg ingot is 99.95wt.%；Copper source is Cu, and Cu is at Cu
In mass fraction be 99.99wt.%；The barium source is Sr ingot, and mass fraction of the Sr in Sr ingot is 99.99wt.%；It is described
Source of iron is Fe powder, and mass fraction of the Fe in Fe powder is 99.99wt.%；The calcium source is Ca ingot, quality of the Ca in Ca ingot point
Number is 99.99wt.%；The manganese source is Mn block, and mass fraction of the Mn in Mn block is 99.99wt.%；The titanium source is Zn-
3Ti intermediate alloy, mass fraction of the Ti in Zn-3Ti intermediate alloy are 3wt.%Ti, and surplus Zn, the silver source is
Ag block, mass fraction of the Ag in Ag block are 99.99wt.%；
Preferred scheme, the fusion process are, first by zinc source in 550~650 DEG C of progress meltings, until zinc source is completely molten
Ge source is added after change, 550~650 DEG C of progress meltings are continued to ge source, after ge source is completely melt, the source X, smelting temperature is added
On the basis of ge source smelting temperature reduce by 10~40 DEG C, to the source X carry out melting, after the source X is completely melt, stirring 1~5 minute,
It is then allowed to stand 5~10min, removes the slag of alloy melt liquid level, and on the basis of the smelting temperature of the source X, temperature is reduced by 10
It~30 DEG C, obtains to cast alloys melt；Protective atmosphere is continually fed into the fusion process.
Inventors have found that adjusting by temperature appropriate, the scaling loss in the source X be added can be effectively avoided.
In addition it in fusion process, need to be pressed under liquid level when ge source or the source X is added, avoid ge source or the source X from floating and cause not
The phenomenon that capable of melting.
The process of preferred scheme, the cast molding is that will pour and be cast from through 200 DEG C~300 DEG C to cast alloys melt
In the metal die of preheating, up to cast alloy ingot after molding.
As a further preference, the metal die is punching block.
Principle and advantage:
A kind of Zn-Ge-X ternary biomaterial of the present invention, the alloy are by appropriate with taking Ge, and appropriate
X (at least one of Mg, Cu, Mn, Sr, Fe, Ca, Ag) element is added, and what is formed has excellent mechanical performance, suitable degradation
Why the Zn-Ge-X ternary biomaterial of rate, good biological compatibility, can obtain excellent performance, on the one hand be
Reasonable component optimization is carried out, another aspect alloy is after deformation process appropriate, and the interphase of Zn-Ge-X alloy is along brilliant
It is in zonal distribution that grain, which elongates direction (deformation direction), and dynamic recrystallization occurs in the hot rolling, is deposited in the centre of grain boundaries
It can mutually play the role of that recrystal grain is inhibited to grow up, promote the mechanical property of alloy.Meanwhile the eutectic Ge phase that part is elongated
It is grinded up under the action of roll-force, the interphase being grinded up, the effect for hindering crystal grain mobile can be played, for improving alloy
Mechanical property it is apparent.Other second phase is mutually distributed more disperse, and alloy grain is uniform.
Ternary Zn-Ge-X bio-medical material prepared by the present invention has excellent mechanical property, good blood compatibility
Property and suitable biodegradability, be expected to become potential degradable biological medical material.
Preparation method of the invention is simply controllable, is suitable for large-scale industrial production.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention, for those of ordinary skill in the art, without any creative labor, according to
These attached drawings obtain other attached drawings and still fall within scope of the invention.
Fig. 1: the XRD diagram of as cast condition and rolled Zn-3Ge-0.5Mg alloy；
Fig. 2: the metallographic structure figure of as cast condition and rolled Zn-3Ge-0.5Mg alloy；Wherein Fig. 2 (a) is as cast condition Zn-3Ge-
The metallographic structure figure of 0.5Mg alloy, Fig. 2 (b) are the metallographic structure figure of as cast condition Zn-3Ge-0.5Mg alloy；
Fig. 3: the polarization curve of as cast condition and rolled Zn-3Ge-0.5Mg alloy and after being impregnated 1 month in Hanks ' solution
Corrosion rate figure；Wherein Fig. 3 (a) is the polarization curve of as cast condition and rolled Zn-3Ge-0.5Mg alloy, and Fig. 3 (b) is as cast condition
Corrosion rate figure after being impregnated 1 month in Hanks ' solution with rolled Zn-3Ge-0.5Mg alloy；
Fig. 4: the hemolysis rate comparison diagram of as cast condition and rolled Zn-3Ge-0.5Mg alloy.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention is made into one below in conjunction with attached drawing
Step ground detailed description.
In the examples below, the cast alloy refers to through cast molding acquisition Zn-Ge-X cast alloy ingot, and hot rolling
State alloy refers to the Zn-Ge-X biomaterial finished product for completing deformation process.
Embodiment 1
First using pure Zn ingot (99.99wt.%), monocrystalline Ge (99.999wt.%), pure Mg ingot (99.95wt.%) as original
Material, and weighed according to the mass ratio of three kinds of simple substance in ternary Zn-3Ge-0.5Mg alloying component.Pure zinc is put into stone later
Black crucible, which is placed in shaft furnace, carries out smelting, in Ar2550 DEG C of progress meltings are heated under atmosphere protection, it is all molten to pure zinc
Monocrystalline Ge is added after change, and monocrystalline Ge is pressed under liquid level, Ge floating is avoided to cause the phenomenon that cannot melting.It is abundant to monocrystalline germanium
After fusing, pure Mg ingot is pressed under liquid level, and adjust the temperature to 540 DEG C.After pure Mg ingot all fusing, persistently stirred with graphite rod
It mixes 2 minutes, standing carries out taking off Slag treatment after five minutes, and pouring temperature is made to be down to 520 DEG C.It is finally poured into and is preheated to 250 DEG C
In punching block, ingot is obtained after solidification.
Ingot keeps the temperature 10 hours progress Homogenization Treatments at 340 DEG C, to improve element in Zn-3Ge-0.5Mg alloy
Segregation, alloy pig is then air-cooled to room temperature.Ingot top and bottom are cut by wire cutting, metal plate is cut into and is used for heat
It rolls.Metal plate is preheated to 250 DEG C before hot rolling and is kept for 10 minutes, then with per pass for 5% drafts, so that plate
Final deformation amount reaches 80%.It requires to be put at once in the stove that temperature is 240 DEG C after deforming per pass and heat 3 minutes.Just
When beginning passage hot rolling, the threading speed of milling train is set as 8m/min, and since the 5th passage, the threading speed of milling train is promoted to
20m/min。
Implementation result
1, from table 1 it follows that Ge element in the Zn-3Ge-0.5Mg alloy measured with X-ray fluorescence spectra (XRF)
Relative mass content be 3.08%, Mg 0.521%, remaining is all Zn.
Table 1
2, from Fig. 1 XRD as can be seen that all there is the α-of close-packed hexagonal in as cast condition and rolled Zn-3Ge-0.5Mg alloy
Zn phase, eutectic Ge phase and Mg2Zn11Phase.
3, from Fig. 2 metallographic structure figure as can be seen that as cast condition Zn-3Ge-0.5Mg alloy in the irregular eutectic Ge of grey
The Zn crystal boundary that hands down is uniformly distributed, black fine particle shape Mg2Zn11Phase, Dispersed precipitate is on α-Zn matrix or crystal boundary.
After hot rolling treatment, it is in band-like point that the interphase of Zn-3Ge-0.5Mg alloy, which elongates direction (deformation direction) along crystal grain,
Cloth, meanwhile, the elongated eutectic Ge phase in part is grinded up under the action of roll-force, Mg2Zn11Mutually distribution more disperse.In addition, rolling
The crystallite dimension of Zn-3Ge-0.5Mg alloy processed is slightly increased and is more evenly distributed than cast alloy.
4, it can be seen that the yield strength of as cast condition Zn-3Ge-0.5Mg alloy from 2 mechanical property of table and hardness data
(Rp0.2) it is 50.6MPa, tensile strength (UTS) is 70.9MPa, and elongation percentage (A) is 1.9%, Vickers hardness number 68.9HV.Heat
Roll the yield strength (Rp of state Zn-3Ge-0.5Mg alloy0.2) it is 188.1MPa, tensile strength (UTS) is 259.6MPa, elongation percentage
It (A) is 24.6%, Vickers hardness number 63.6HV.As can be seen that after hot rolling treatment of the present invention, Zn-3Ge-0.5Mg alloy
Mechanical property is substantially improved.
Table 2
5, from Fig. 3 (a) polarization curve, Fig. 3 (b) soak test comparison between corrosion figure and to the area Tafel in Fig. 3 (a)
Between be fitted in resulting corrosion parameter and (be shown in Table 3) as can be seen that in Hanks ' solution carry out the resulting as cast condition Zn- of polarimetric test
The corrosion potential of 3Ge-0.5Mg alloy, corrosion electric current density and corrosion rate are -1.034V, 27.9 μ A/cm2, 0.4079mm/
Y, the corrosion potential of rolled Zn-3Ge-0.5Mg alloy, corrosion electric current density and corrosion rate are -0.977V, 29.3 μ A/
cm2, 0.4296mm/y.The degradation rate of as cast condition Zn-3Ge-0.5Mg alloy is after soak test 1 month in Hanks ' solution
0.041mm/y, the degradation rate of rolled Zn-3Ge-0.5Mg alloy are 0.047mm/y.
Table 3
6, as can be seen that as cast condition and rolled Zn-3Ge-0.5Mg alloy leaching liquor from Fig. 4 alloy leaching liquor hemolysis rate
Hemolysis rate in mouse blood is respectively 2.54% and 2.99%.According to ASTMF756-08 standard, two states foam metal
The hemolysis rate of leaching liquor is below 5%, meets requirement of the clinical medical biomaterial to hemolysis rate.
Embodiment 2
First using pure Zn ingot (99.99wt.%), monocrystalline Ge (99.999wt.%), (99.99wt.%) Cu pure as original
Material, and weighed according to the mass ratio of three kinds of simple substance in ternary Zn-3Ge-0.5Cu alloying component.Pure zinc is put into stone later
Black crucible, which is placed in shaft furnace, carries out smelting, in Ar2590 DEG C of progress meltings are heated under atmosphere protection, it is all molten to pure zinc
Monocrystalline Ge is added after change, and monocrystalline Ge is pressed under liquid level, Ge floating is avoided to cause the phenomenon that cannot melting.It is abundant to monocrystalline germanium
After fusing, pure Cu is pressed under liquid level, and adjusts the temperature to 550 DEG C.After pure Cu all fusing, persistently stirred with graphite rod
It mixes 5 minutes, standing carries out taking off Slag treatment after ten minutes, and pouring temperature is made to be down to 520 DEG C.It is finally poured into and is preheated to 220 DEG C
Punching block in, ingot is obtained after solidification.
Ingot keeps the temperature 12 hours progress Homogenization Treatments at 320 DEG C, to improve element in Zn-3Ge-0.5Cu alloy
Segregation, then by alloy pig water cooling to room temperature.Ingot top and bottom are cut by wire cutting, metal plate is cut into and is used for heat
It rolls.Metal plate is preheated to 250 DEG C before hot rolling and is kept for 10 minutes, then with per pass for 5% drafts, so that plate
Final deformation amount reaches 70%.It requires to be put at once in the stove that temperature is 240 DEG C after deforming per pass and heat 5 minutes.Just
When beginning passage hot rolling, the threading speed of milling train is set as 9m/min, and since the 5th passage, the threading speed of milling train is promoted to
25m/min。
Implementation result
The phase for the Ge element that Zn-3Ge-0.5Cu alloy pig manufactured in the present embodiment is measured with X-ray fluorescence spectra (XRF)
It is 3.12%, Cu 0.496% to mass content, remaining is all Zn.The yield strength of as cast condition Zn-3Ge-0.5Cu alloy
(Rp0.2) it is 56.2MPa, tensile strength (UTS) is 77.1MPa, and elongation percentage (A) is 2.8%, Vickers hardness number 68.7HV.Heat
Roll the yield strength (Rp of state Zn-3Ge-0.5Cu alloy0.2) it is 192.4MPa, tensile strength (UTS) is 255.7MPa, elongation percentage
It (A) is 34.5%, Vickers hardness number 67.3HV.The resulting as cast condition Zn-3Ge- of polarimetric test is carried out in Hanks ' solution
The corrosion potential of 0.5Cu alloy, corrosion electric current density and corrosion rate are -1.015V, 15.4 μ A/cm2, 0.2255mm/y, heat
The corrosion potential of state Zn-3Ge-0.5Cu alloy is rolled, corrosion electric current density and corrosion rate are -1.001V, 16.5 μ A/cm2,
0.2415mm/y.The degradation rate of as cast condition Zn-3Ge-0.5Cu alloy is after soak test 1 month in Hanks ' solution
0.025mm/y, the degradation rate of rolled Zn-3Ge-0.5Cu alloy are 0.029mm/y.As cast condition and rolled Zn-3Ge-
Hemolysis rate of the 0.5Cu alloy leaching liquor in mouse blood is respectively 3.16% and 3.04%.
Embodiment 3
First using pure Zn ingot (99.99wt.%), monocrystalline Ge (99.999wt.%), pure Fe powder (99.99wt.%) as original
Material, and weighed according to the mass ratio of three kinds of simple substance in ternary Zn-2Ge-0.7Fe alloying component.Pure zinc is put into stone later
Black crucible, which is placed in shaft furnace, carries out smelting, in Ar2640 DEG C of progress meltings are heated under atmosphere protection, it is all molten to pure zinc
Monocrystalline Ge is added after change, and monocrystalline Ge is pressed under liquid level, Ge floating is avoided to cause the phenomenon that cannot melting.It is abundant to monocrystalline germanium
After fusing, pure Fe powder is pressed under liquid level, and adjust the temperature to 600 DEG C.After pure Fe powder all fusing, persistently stirred with graphite rod
It mixes 2 minutes, standing carries out taking off Slag treatment after five minutes, and pouring temperature is made to be down to 550 DEG C.It is finally poured into and is preheated to 250 DEG C
In punching block, ingot is obtained after solidification.
Ingot keeps the temperature 12 hours progress Homogenization Treatments at 350 DEG C, to improve element in Zn-2Ge-0.7Fe alloy
Segregation, then by alloy pig water cooling to room temperature.Ingot top and bottom are cut by wire cutting, metal plate is cut into and is used for heat
It rolls.Metal plate is preheated to 270 DEG C before hot rolling and is kept for 5 minutes, then with per pass for 5% drafts, so that plate
Final deformation amount reaches 80%.It requires to be put at once in the stove that temperature is 250 DEG C after deforming per pass and heat 4 minutes.Just
When beginning passage hot rolling, the threading speed of milling train is set as 10m/min, and since the 5th passage, the threading speed of milling train is promoted to
30m/min。
Implementation result
The phase for the Ge element that Zn-2Ge-0.7Fe alloy pig manufactured in the present embodiment is measured with X-ray fluorescence spectra (XRF)
It is 1.94%, Fe 0.667% to mass content, remaining is all Zn.The yield strength of as cast condition Zn-2Ge-0.7Fe alloy
(Rp0.2) it is 51.6MPa, tensile strength (UTS) is 61.2MPa, and elongation percentage (A) is 0.9%, Vickers hardness number 70.4HV.Heat
Roll the yield strength (Rp of state Zn-2Ge-0.7Fe alloy0.2) it is 204.6MPa, tensile strength (UTS) is 266.8MPa, elongation percentage
It (A) is 12.4%, Vickers hardness number 72.6HV.The resulting as cast condition Zn-2Ge- of polarimetric test is carried out in Hanks ' solution
The corrosion potential of 0.7Fe alloy, corrosion electric current density and corrosion rate are -0.994V, 80.6 μ A/cm2, 1.1797mm/y, heat
The corrosion potential of state Zn-2Ge-0.7Fe alloy is rolled, corrosion electric current density and corrosion rate are -1.105V, 87.1 μ A/cm2,
1.2748mm/y.The degradation rate of as cast condition Zn-2Ge-0.7Fe alloy is after soak test 1 month in Hanks ' solution
0.142mm/y, the degradation rate of rolled Zn-2Ge-0.7Fe alloy are 0.167mm/y.As cast condition and rolled Zn-2Ge-
Hemolysis rate of the 0.7Fe alloy leaching liquor in mouse blood is respectively 4.05% and 4.33%.
Embodiment 4
First using pure Zn ingot (99.99wt.%), monocrystalline Ge (99.999wt.%), pure Ag block (99.99wt.%) as original
Material, and weighed according to the mass ratio of three kinds of simple substance in ternary Zn-5Ge-1Ag alloying component.Pure zinc is put into graphite later
Crucible, which is placed in shaft furnace, carries out smelting, in Ar2It is heated to 560 DEG C of progress meltings under atmosphere protection, is all melted to pure zinc
Monocrystalline Ge is added afterwards, and monocrystalline Ge is pressed under liquid level, Ge floating is avoided to cause the phenomenon that cannot melting.It is sufficiently molten to monocrystalline germanium
After change, pure Ag block is pressed under liquid level, and adjust the temperature to 520 DEG C.After pure Ag block all fusing, persistently stirred with graphite rod
It mixes, standing carries out taking off Slag treatment after ten minutes, and pouring temperature is made to be down to 500 DEG C.It is finally poured into and is preheated to 200 DEG C of punching block
In, ingot is obtained after solidification.
Ingot keeps the temperature 8 hours progress Homogenization Treatments at 300 DEG C, to improve the inclined of element in Zn-5Ge-1Ag alloy
Analysis, is then air-cooled to room temperature for alloy pig.Ingot top and bottom are cut by wire cutting, is cut into metal plate for hot rolling.
Metal plate is preheated to 240 DEG C before hot rolling and is kept for 15 minutes, then with per pass for 5% drafts, so that plate is most
Whole deflection reaches 60%.It requires to be put at once in the stove that temperature is 220 DEG C after deforming per pass and heat 5 minutes.Initially
When passage hot rolling, the threading speed of milling train is set as 8m/min, and since the 5th passage, the threading speed of milling train is promoted to
20m/min。
Implementation result
The Ge element that Zn-5Ge-1Ag alloy pig manufactured in the present embodiment is measured with X-ray fluorescence spectra (XRF) it is opposite
Mass content is 4.975%, Ag 1.012%, remaining is all Zn.Yield strength (the Rp of as cast condition Zn-5Ge-1Ag alloy0.2) be
74.6MPa, tensile strength (UTS) are 85.9MPa, and elongation percentage (A) is 1.3%, Vickers hardness number 77.6HV.Rolled Zn-
Yield strength (the Rp of 5Ge-1Ag alloy0.2) it is 216.4MPa, tensile strength (UTS) is 255.4MPa, and elongation percentage (A) is
18.6%, Vickers hardness number 74.4HV.The resulting as cast condition Zn-5Ge-1Ag alloy of polarimetric test is carried out in Hanks ' solution
Corrosion potential, corrosion electric current density and corrosion rate are -0.972V, 74.6 μ A/cm2, 1.0919mm/y, rolled Zn-
The corrosion potential of 5Ge-1Ag alloy, corrosion electric current density and corrosion rate are -1.043V, 70.2 μ A/cm2, 1.0274mm/y.
The degradation rate of as cast condition Zn-5Ge-1Ag alloy is 0.152mm/y, rolled after soak test 1 month in Hanks ' solution
The degradation rate of Zn-5Ge-1Ag alloy is 0.148mm/y.As cast condition and rolled Zn-5Ge-1Ag alloy leaching liquor are in mouse blood
Hemolysis rate in liquid is respectively 3.49% and 3.63%.
Comparative example 1
First using pure Zn ingot (99.99wt.%), monocrystalline Ge (99.999wt.%), (99.99wt.%) Cu pure as original
Material, and weighed according to the mass ratio of three kinds of simple substance in ternary Zn-7Ge-0.5Cu alloying component.Pure zinc is put into stone later
Black crucible, which is placed in shaft furnace, carries out smelting, in Ar2590 DEG C of progress meltings are heated under atmosphere protection, it is all molten to pure zinc
Monocrystalline Ge is added after change, and monocrystalline Ge is pressed under liquid level, Ge floating is avoided to cause the phenomenon that cannot melting.It is abundant to monocrystalline germanium
After fusing, pure Cu is pressed under liquid level, and adjusts the temperature to 550 DEG C.After pure Cu all fusing, persistently stirred with graphite rod
It mixes 5 minutes, standing carries out taking off Slag treatment after ten minutes, and pouring temperature is made to be down to 520 DEG C.It is finally poured into and is preheated to 220 DEG C
Punching block in, ingot is obtained after solidification.
Ingot keeps the temperature 12 hours progress Homogenization Treatments at 320 DEG C, to improve element in Zn-7Ge-0.5Cu alloy
Segregation, then by alloy pig water cooling to room temperature.Ingot top and bottom are cut by wire cutting, metal plate is cut into and is used for heat
It rolls.Metal plate is preheated to 250 DEG C before hot rolling and is kept for 10 minutes, then with per pass for 5% drafts, so that plate
Final deformation amount reaches 70%.It requires to be put at once in the stove that temperature is 240 DEG C after deforming per pass and heat 5 minutes.
Comparative example implementation result
The phase for the Ge element that the Zn-7Ge-0.5Cu alloy pig of this comparative example preparation is measured with X-ray fluorescence spectra (XRF)
It is 6.93%, Cu 0.504% to mass content, remaining is all Zn.It can be seen that Ge component content of the present invention is excessively high, test knot
Fruit shows, the yield strength (Rp of as cast condition Zn-7Ge-0.5Cu alloy0.2) it is 55.7MPa, tensile strength (UTS) is 69.3MPa,
Elongation percentage (A) is 0.8%, Vickers hardness number 68.2HV.Yield strength (the Rp of rolled Zn-7Ge-0.5Cu alloy0.2) be
188.1MPa, tensile strength (UTS) are 247.6MPa, and elongation percentage (A) is 10.4%, Vickers hardness number 66.2HV.?
The corrosion potential of the resulting as cast condition Zn-7Ge-0.5Cu alloy of polarimetric test, corrosion electric current density and corruption are carried out in Hanks ' solution
Erosion rate is -0.998V, 20.9 μ A/cm2, 0.3060mm/y, the corrosion potential of rolled Zn-7Ge-0.5Cu alloy, corrosion electricity
Current density and corrosion rate are -0.993V, 25.7 μ A/cm2, 0.3763mm/y.In Hanks ' solution after soak test 1 month
The degradation rate of as cast condition Zn-7Ge-0.5Cu alloy is 0.042mm/y, and the degradation rate of rolled Zn-3Ge-0.5Cu alloy is
0.048mm/y.The hemolysis rate of as cast condition and rolled Zn-7Ge-0.5Cu alloy leaching liquor in mouse blood is respectively 3.94%
With 3.55%.
Comparative example 2
First using pure Zn ingot (99.99wt.%), monocrystalline Ge (99.999wt.%), pure Mg ingot (99.95wt.%) as original
Material, and weighed according to the mass ratio of three kinds of simple substance in ternary Zn-3Ge-1.5Mg alloying component.Pure zinc is put into stone later
Black crucible, which is placed in shaft furnace, carries out smelting, in Ar2550 DEG C of progress meltings are heated under atmosphere protection, it is all molten to pure zinc
Monocrystalline Ge is added after change, and monocrystalline Ge is pressed under liquid level, Ge floating is avoided to cause the phenomenon that cannot melting.It is abundant to monocrystalline germanium
After fusing, pure Mg ingot is pressed under liquid level, and adjust the temperature to 540 DEG C.After pure Mg ingot all fusing, persistently stirred with graphite rod
It mixes 2 minutes, standing carries out taking off Slag treatment after five minutes, and pouring temperature is made to be down to 520 DEG C.It is finally poured into and is preheated to 250 DEG C
In punching block, ingot is obtained after solidification.
Ingot keeps the temperature 10 hours progress Homogenization Treatments at 340 DEG C, to improve element in Zn-3Ge-1.5Mg alloy
Segregation, alloy pig is then air-cooled to room temperature.Ingot top and bottom are cut by wire cutting, metal plate is cut into and is used for heat
It rolls.Metal plate is preheated to 250 DEG C before hot rolling and is kept for 10 minutes, then with per pass for 5% drafts, so that plate
Final deformation amount reaches 80%.It requires to be put at once in the stove that temperature is 240 DEG C after deforming per pass and heat 3 minutes.
Implementation result
The phase for the Ge element that the Zn-3Ge-1.5Mg alloy pig of this comparative example preparation is measured with X-ray fluorescence spectra (XRF)
It is 2.98%, Mg 1.48% to mass content, remaining is all Zn.It can be seen that Mg too high levels of the invention, as cast condition Zn-
3Ge-1.5Mg yield strength (the Rp of alloy0.2) it is 58.6MPa, tensile strength (UTS) is 65.6MPa, and elongation percentage (A) is
0.3%, Vickers hardness number 83.6HV.Yield strength (the Rp of rolled Zn-3Ge-1.5Mg alloy0.2) it is 176.5MPa, resist
Tensile strength (UTS) is 220.9MPa, and elongation percentage (A) is 5.7%, Vickers hardness number 81.2HV.It is carried out in Hanks ' solution
The corrosion potential of the resulting as cast condition Zn-3Ge-1.5Mg alloy of polarimetric test, corrosion electric current density and corrosion rate are -1.106V,
165.6μA/cm2, 2.4248mm/y, the corrosion potential of rolled Zn-3Ge-1.5Mg alloy, corrosion electric current density and corrosion are fast
Rate is -1.094V, 134.8 μ A/cm2, 1.9738mm/y.The as cast condition Zn-3Ge- after soak test 1 month in Hanks ' solution
The degradation rate of 1.5Mg alloy is 0.261mm/y, and the degradation rate of rolled Zn-3Ge-1.5Mg alloy is 0.275mm/y.Casting
The hemolysis rate of state and rolled Zn-3Ge-1.5Mg alloy leaching liquor in mouse blood is respectively 5.75% and 5.62%, haemolysis
Rate has been more than 5%, it is difficult to meet requirement of the clinical medical biomaterial to hemolysis rate.
Comparative example 3
First using pure Zn ingot (99.99wt.%), monocrystalline Ge (99.999wt.%), (99.99wt.%) Cu pure as original
Material, and weighed according to the mass ratio of three kinds of simple substance in ternary Zn-3Ge-0.5Cu alloying component.Pure zinc is put into stone later
Black crucible, which is placed in shaft furnace, carries out smelting, in Ar2590 DEG C of progress meltings are heated under atmosphere protection, it is all molten to pure zinc
Monocrystalline Ge is added after change, and monocrystalline Ge is pressed under liquid level, Ge floating is avoided to cause the phenomenon that cannot melting.It is abundant to monocrystalline germanium
After fusing, pure Cu is pressed under liquid level, and adjusts the temperature to 550 DEG C.After pure Cu all fusing, persistently stirred with graphite rod
It mixes 5 minutes, standing carries out taking off Slag treatment after ten minutes, and pouring temperature is made to be down to 520 DEG C.It is finally poured into and is preheated to 220 DEG C
Punching block in, ingot is obtained after solidification.
Ingot keeps the temperature 12 hours progress Homogenization Treatments at 320 DEG C, to improve element in Zn-3Ge-0.5Cu alloy
Segregation, then by alloy pig water cooling to room temperature.Ingot top and bottom are cut by wire cutting, metal plate is cut into and is used for heat
It rolls.Metal plate is preheated to 250 DEG C before hot rolling and is kept for 10 minutes, then with per pass for 5% drafts, so that plate
Final deformation amount reaches 70%.It requires to be put at once in the stove that temperature is 300 DEG C after deforming per pass and heat 5 minutes.
Implementation result
The phase for the Ge element that the Zn-3Ge-0.5Cu alloy pig of this comparative example preparation is measured with X-ray fluorescence spectra (XRF)
It is 3.16%, Cu 0.581% to mass content, remaining is all Zn.This comparative example is equivalent to embodiment 2, is only in hot rolling road
Heating temperature is excessively high between secondary, the results show that the yield strength (Rp of as cast condition Zn-3Ge-0.5Cu alloy0.2) it is 50.7MPa, tension
Intensity (UTS) is 68.9MPa, and elongation percentage (A) is 1.3%, Vickers hardness number 68.7HV.Rolled Zn-3Ge-0.5Cu alloy
Yield strength (Rp0.2) it is 175.6MPa, tensile strength (UTS) is 226.8MPa, and elongation percentage (A) is 13.7%, Vickers hardness
Value is 64.9HV.The corrosion potential of the resulting as cast condition Zn-3Ge-0.5Cu alloy of polarimetric test is carried out in Hanks ' solution, it is rotten
It loses current density and corrosion rate is -1.003V, 16.9 μ A/cm2, 0.2475mm/y, rolled Zn-3Ge-0.5Cu alloy
Corrosion potential, corrosion electric current density and corrosion rate are -0.986V, 14.2 μ A/cm2, 0.2079mm/y.In Hanks ' solution
The degradation rate of as cast condition Zn-3Ge-0.5Cu alloy is 0.037mm/y after soak test 1 month, and rolled Zn-3Ge-0.5Cu is closed
The degradation rate of gold is 0.036mm/y.The haemolysis of as cast condition and rolled Zn-3Ge-0.5Cu alloy leaching liquor in mouse blood
Rate is respectively 4.77% and 4.61%.
Claims (10)
1. a kind of Zn-Ge-X ternary bio-medical material, it is characterised in that: the Zn-Ge-X ternary bio-medical material presses matter
Measure percentages, including following composition: Ge0.5~6%wt.%, X0.1~1wt.%, the X be selected from Mg, Cu, Mn, Sr, Fe,
At least one of Ca, Ag, Ti, surplus Zn.
2. a kind of Zn-Ge-X ternary bio-medical material according to claim 1, it is characterised in that: the Zn-Ge-X tri-
By mass percentage, including following composition: Ge2~5wt.%, X0.5~1wt.%, the X are selected from first bio-medical material
At least one of Mg, Cu, Fe, Ag, surplus Zn.
3. preparing a kind of method of Zn-Ge-X ternary bio-medical material as claimed in claim 1 or 2, which is characterized in that packet
Include following steps: by design proportion with zinc source, ge source, the source X, the melting under protective atmosphere is taken, cast molding obtains Zn-Ge-X casting
Cast alloy ingot is carried out Homogenization Treatments, then cooled to room temperature, then the alloy pig after homogenization is processed by state alloy pig
Then alloy sheets, preheating carry out multistage hot deformation and circulating-heating processing.
The preheating temperature is 240~300 DEG C, preheating time≤15min.
Reduction in pass is 2~5% when the hot rolling, and total deformation is that heating process is 220~280 between 50~80%, passage
Heat preservation≤5min at DEG C.
4. a kind of preparation method of Zn-Ge-X ternary bio-medical material according to claim 3, it is characterised in that: institute
The temperature for stating Homogenization Treatments is 300~350 DEG C, and the time of Homogenization Treatments is 5~12h.
5. a kind of preparation method of Zn-Ge-X ternary bio-medical material according to claim 3, it is characterised in that: heat
When mill train number<5, the threading speed of milling train is 8m/min~10m/min, when hot rolling pass number>=5, the threading speed of milling train
For 20m/min~30m/min.
6. a kind of preparation method of Zn-Ge-X ternary bio-medical material according to claim 3, it is characterised in that: institute
Stating preheating temperature is 240~270 DEG C, and preheating time is 5~15min；Reduction in pass is 5% when the hot rolling, total deformation
Heating process is 3~5min of heat preservation at 220~250 DEG C between 60~80%, passage.
7. a kind of preparation method of Zn-Ge-X ternary bio-medical material according to claim 3, it is characterised in that: institute
It states zinc source and is selected from Zn ingot or the alloy with X element composition, when the zinc source is selected from Zn ingot, mass fraction of the Zn in Zn ingot is
99.99wt.%；The ge source is monocrystalline Ge, and mass fraction of the Ge in monocrystalline Ge is 99.999wt.%.
8. a kind of preparation method of Zn-Ge-X ternary bio-medical material according to claim 3, it is characterised in that: institute
It states the source X and is selected from least one of magnesium source, copper source, manganese source, barium source, source of iron, calcium source, Yin Yuan, titanium source, the magnesium source is Mg ingot,
Mass fraction of the Mg in Mg ingot is 99.95wt.%；Copper source is Cu, and mass fraction of the Cu in Cu is
99.99wt.%；The barium source is Sr ingot, and mass fraction of the Sr in Sr ingot is 99.99wt.%；The source of iron is Fe powder, Fe
Mass fraction in Fe powder is 99.99wt.%；The calcium source is Ca ingot, and mass fraction of the Ca in Ca ingot is
99.99wt.%；The manganese source is Mn block, and mass fraction of the Mn in Mn block is 99.99wt.%；The titanium source is in Zn-3Ti
Between alloy, mass fraction of the Ti in Zn-3Ti intermediate alloy is 3wt.%Ti, surplus Zn, and the silver source is Ag block,
Mass fraction of the Ag in Ag block is 99.99wt.%.
9. a kind of preparation method of Zn-Ge-X ternary bio-medical material according to claim 3, it is characterised in that: institute
Stating fusion process is, first by zinc source in 550~650 DEG C of progress meltings, until ge source is added after being completely melt in zinc source, to ge source after
Continue in 550~650 DEG C of progress meltings, after ge source is completely melt, the source X is added, smelting temperature is on the basis of ge source smelting temperature
10~40 DEG C are reduced, melting is carried out to the source X, after the source X is completely melt, stirs 1~5 minute, be then allowed to stand 5~10min, remove
The slag of alloy melt liquid level, and on the basis of the smelting temperature of the source X, temperature is reduced by 10~30 DEG C, is obtained to cast alloys
Melt；Protective atmosphere is continually fed into the fusion process.
10. a kind of preparation method of Zn-Ge-X ternary bio-medical material according to claim 3, it is characterised in that: institute
The process for stating cast molding is will to be poured in the metal die for casting from and preheating through 200 DEG C~300 DEG C to cast alloys melt, molding
Afterwards up to cast alloy ingot.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910291761.XA CN109966568B (en) | 2019-04-11 | 2019-04-11 | Zn-Ge-X ternary biomedical material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910291761.XA CN109966568B (en) | 2019-04-11 | 2019-04-11 | Zn-Ge-X ternary biomedical material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109966568A true CN109966568A (en) | 2019-07-05 |
| CN109966568B CN109966568B (en) | 2021-08-06 |
Family
ID=67084298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910291761.XA Active CN109966568B (en) | 2019-04-11 | 2019-04-11 | Zn-Ge-X ternary biomedical material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109966568B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110273084A (en) * | 2019-07-24 | 2019-09-24 | 西安交通大学 | A kind of preparation method of biodegradable kirsite |
| CN111529761A (en) * | 2020-05-12 | 2020-08-14 | 浙江工贸职业技术学院 | Degradable Zn-Ti binary biomedical material and preparation method thereof |
| CN113797396A (en) * | 2021-10-08 | 2021-12-17 | 温州医科大学附属口腔医院 | Preparation method of porous zinc biological composite coating for degradable bone scaffold |
| CN114042898A (en) * | 2021-11-10 | 2022-02-15 | 温州医科大学附属口腔医院 | Preparation method of biomedical degradable metal skeleton reinforced Zn-based composite material with large-area galvanic corrosion structure |
| CN114395713A (en) * | 2022-01-18 | 2022-04-26 | 温州医科大学附属口腔医院 | Degradable in-situ authigenic Mg2Ge particle reinforced Zn-based composite material and preparation method thereof |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102978494A (en) * | 2012-12-13 | 2013-03-20 | 北京大学 | Mg-Ge magnesium alloy and preparation method thereof |
| CN105986146A (en) * | 2015-01-30 | 2016-10-05 | 乐普（北京）医疗器械股份有限公司 | Degradable medical implant metal material and preparation method thereof |
| CN109128064A (en) * | 2018-09-21 | 2019-01-04 | 北京科技大学 | A kind of biodegradable Zn-Na system kirsite and preparation method thereof |
-
2019
- 2019-04-11 CN CN201910291761.XA patent/CN109966568B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102978494A (en) * | 2012-12-13 | 2013-03-20 | 北京大学 | Mg-Ge magnesium alloy and preparation method thereof |
| CN105986146A (en) * | 2015-01-30 | 2016-10-05 | 乐普（北京）医疗器械股份有限公司 | Degradable medical implant metal material and preparation method thereof |
| CN109128064A (en) * | 2018-09-21 | 2019-01-04 | 北京科技大学 | A kind of biodegradable Zn-Na system kirsite and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| XIAN TONG等: ""Microstructure, mechanical properties, biocompatibility, and in vitro corrosion and degradation behavior of a new Zn-5Ge alloy for biodegradable implant materials", 《ACTA BIOMATERIALIA》 * |
| ZHANG-ZHI SHI等: "Effects of Ag, Cu or Ca addition on microstructure and comprehensive properties of biodegradable Zn-0.8Mn alloy", 《MATERIALS SCIENCE & ENGINEERING C》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110273084A (en) * | 2019-07-24 | 2019-09-24 | 西安交通大学 | A kind of preparation method of biodegradable kirsite |
| CN110273084B (en) * | 2019-07-24 | 2020-09-08 | 西安交通大学 | Preparation method of biodegradable zinc alloy |
| CN111529761A (en) * | 2020-05-12 | 2020-08-14 | 浙江工贸职业技术学院 | Degradable Zn-Ti binary biomedical material and preparation method thereof |
| CN113797396A (en) * | 2021-10-08 | 2021-12-17 | 温州医科大学附属口腔医院 | Preparation method of porous zinc biological composite coating for degradable bone scaffold |
| CN113797396B (en) * | 2021-10-08 | 2023-03-03 | 温州医科大学附属口腔医院 | Preparation method of porous zinc biological composite coating for degradable bone scaffold |
| CN114042898A (en) * | 2021-11-10 | 2022-02-15 | 温州医科大学附属口腔医院 | Preparation method of biomedical degradable metal skeleton reinforced Zn-based composite material with large-area galvanic corrosion structure |
| CN114042898B (en) * | 2021-11-10 | 2023-02-28 | 温州医科大学附属口腔医院 | Preparation method of biomedical degradable metal skeleton reinforced Zn-based composite material with large-area galvanic corrosion structure |
| CN114395713A (en) * | 2022-01-18 | 2022-04-26 | 温州医科大学附属口腔医院 | Degradable in-situ authigenic Mg2Ge particle reinforced Zn-based composite material and preparation method thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109966568B (en) | 2021-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109966568A (en) | A kind of Zn-Ge-X ternary bio-medical material and preparation method thereof | |
| CN109097629B (en) | Biodegradable Zn-Mo series zinc alloy and preparation method thereof | |
| Li et al. | The synergistic effect of trace Sr and Zr on the microstructure and properties of a biodegradable Mg-Zn-Zr-Sr alloy | |
| CN102433477B (en) | Biomedical Mg-Sn-Zn-Mn magnesium alloy and preparation method thereof | |
| CN109128064A (en) | A kind of biodegradable Zn-Na system kirsite and preparation method thereof | |
| CN106702212A (en) | Medical degradable Zn-Cu-X alloy material and preparation method thereof | |
| CN104120320B (en) | A kind of degradable magnesium-rare earth biomaterial for medical purpose and preparation method | |
| CN111020295B (en) | High-performance biodegradable Zn-Cu-Li-X alloy and preparation and application methods thereof | |
| CN108588484A (en) | High-strength high-plastic biodegradable Zn-Mn-Mg systems kirsite of one kind and preparation method thereof | |
| CN111187943A (en) | Biomedical Zn-Cu-Mg alloy and preparation method thereof | |
| CN111155013B (en) | Medical three-dimensional printing alloy material and preparation method thereof | |
| CN105349858A (en) | Degradable magnesium alloy implanting material for bone fixation and preparing method of degradable magnesium alloy implanting material | |
| CN102258806B (en) | Degradable magnesium-base biomedical material for implantation in orthopaedics, and preparation method thereof | |
| CN106544563B (en) | A kind of biodegradable Mg-Ca-Mn-Sn magnesium alloy materials and preparation method and application | |
| CN110241330A (en) | A kind of degradable Zn-Ag system kirsite and the preparation method and application thereof | |
| CN108754232A (en) | High-strength high-plastic biodegradable Zn-Mn-Li systems kirsite of one kind and application thereof | |
| CN108950336B (en) | High-plasticity degradable biomedical Mg-Zn-Zr-Ca-Fe alloy material and preparation method thereof | |
| CN111286656B (en) | Multi-element small-amount degradable antibacterial magnesium alloy and preparation method thereof | |
| CN108165782B (en) | Medical zinc-based alloy strip and preparation method thereof | |
| CN105803282B (en) | A kind of single-phase Multielement rare-earth magnesium alloy biodegradation material and preparation method thereof | |
| Yang et al. | Laser additive manufacturing of zinc: formation quality, texture, and cell behavior | |
| US20200232079A1 (en) | Fe-mn absorbable implant alloys with increased degradation rate | |
| CN109778035B (en) | Degradable biomedical Mg-Bi-Zn-Ca alloy and preparation method thereof | |
| CN110512117B (en) | Medical zinc alloy material and preparation method thereof | |
| JP2024513622A (en) | Rare earth element-free biodegradable magnesium alloy, its manufacturing method and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |