CN108330368A - Organism implantation material, its ingredient and preparation method - Google Patents
Organism implantation material, its ingredient and preparation method Download PDFInfo
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- CN108330368A CN108330368A CN201810275750.8A CN201810275750A CN108330368A CN 108330368 A CN108330368 A CN 108330368A CN 201810275750 A CN201810275750 A CN 201810275750A CN 108330368 A CN108330368 A CN 108330368A
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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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
-
- 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
-
- 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
Abstract
The present disclosure generally relates to a kind of organism implantation material, its ingredient and preparation methods.The organism implantation material of degradable magnesium alloy by being made, it is particularly suitable as the fixing buckle of fixed ligamentaum cruciatum, the composition gross mass of its degradable magnesium alloy is 100%, the content of magnesium accounts for 96.49% to 98.9%, the content that the content of calcium accounts for 0.1% to 0.5%, zinc accounts for 1% to 3%, and the sum of content of remaining impurity is accounted for no more than 0.01%.The degradable magnesium alloy is obtained by the preparation method of vacuum metling, solution heat treatment, extrusion process, technique of swaging.The characteristic that the organism implantation material has high intensity, degradation rate low, is suitable as the material of organism implantation material.
Description
Technical field
The present invention relates to a kind of biomaterial for medical purpose, more particularly to one kind to be implanted into organism made of degradable magnesium alloy
Object, ingredient and preparation method.
Background technology
It is mainly the metal materials such as stainless steel, titanium or titanium alloy or can absorb currently, is clinically used for fixed material in bone
High molecule plastic material.For example, it is used for the implantation material fixing buckle of fixation implant in ligamentaum cruciatum operation, it is at present to adopt more
With metal materials such as titanium alloy material stainless steel, titanium or titanium alloys.But the gold such as the common stainless steel of the prior art, titanium or titanium alloy
Belong to elasticity modulus of materials and be far above people's bone, may cause stress-shielding effect for bone fixation, bone damage position is made to obtain not
To necessary stress stimulation, possible bone healing not exclusively causes healing delay, intensity to decline；And due to stainless steel, titanium and
Titanium alloy is bio-inert material, can be retained for a long time after being implanted into organism in vivo, in fluid environment slow release clast or
Toxic, irritating metal ion may cause the inflammatory reaction even tissue necrosis of implantation material surrounding tissue；In addition,
When stainless steel, titanium or titanium alloy are as provisional implant material, still need to second operation removal in the future and cause patient it is economical,
Psychology and burden physiologically；On the other hand, resorbable polymeric materials because its intensity it is weaker, and be applicable only to not stress or
The reparation and fixation of the smaller skeletal sites of stress.
Compared with stainless steel, titanium or titanium alloy and degradable high polymer material, the density and elasticity modulus of magnesium alloy and people
The density and elasticity modulus of body compact bone are closest, and therefore, magnesium alloy has good mechanical compatibility；In addition, magnesium alloy exists
React with body fluid after implantation human body, magnesium can gradual natural degradation in vivo, catabolite magnesium hydroxide (Mg (OH)2)
Magnesium chloride (MgCl can be converted in human body environment2) and be gradually substantially absorbed into the surrounding tissues with good bio-compatibility, therefore
Magnesium alloy implantation material be not required to second operation taking-up can reach medicine use purpose.
Ligamentaum cruciatum bears Main Load in kneed movement.In order to maintain kneed normal activity, to that will hand over
Fork ligament or bone fixation have tightened up requirement in the intensity of the fixing buckle on femur or shin bone, and with fixing buckle degradation into
Row, intensity still need to maintain healed completely to bone, ligament for 6 months to 12 months.If the intensity of fixing buckle is insufficient, graft is held
Fine motion in the roads Yi Gu, the roads Shi Gu expand, and insufficient contact between graft and bone road, influence blood vessel and grow into, to influence
Tendon heals with bone road.The expansion of Postoperative Bone road causes solid failure, infection that Cruciate ligament reconstruction is caused to fail.
Alloying is to improve the important means of magnesium alloy strength.Common alloy element has aluminium, manganese, zirconium, rare earth element
Deng.Especially aluminium is most commonly used to increase the intensity and corrosion resistance of magnesium base alloy, but aluminium is considered to have neurotoxicity, Ke Nengzao
At the brains relevant disease such as Alzheimer's disease.Therefore, magnesium alloy materials of the exploitation without aluminium, such as Chinese patent are transferred in many researchs
Shen Qing Publication case 105120907 disclose a kind of magnesium alloy include the zinc (Zn) of 3 weight %, 0.3 weight % calcium (Ca) and
The manganese of 0.48 weight %；Its right yield strength is between 53 megapascal (MPa) to 235 megapascal (MPa), while corrosion rate is quite high,
It can be seen that the low strength and degradation rate of the magnesium alloy are too fast, and it can not keep sufficiently strong before bone heals completely
Degree leads to medical implant premature failure, and manganese content is higher causes the nervous system disease doubt.Furthermore it is fixed with implantation material
In button for the fixing buckle of most common four hole, the maximum value of the anterior cruciate ligament stress value measured in being tested according to joint
136 newton (N) are used as maximum load power, stress distribution when analysis fixing buckle fixes ligament, during maximum stress appears in
Between holes and osseous tunnel junction.12.5 millimeters of length in being performed the operation according to ligamentaum cruciatum, 4 millimeters wide, four holes of 1.5 millimeters of thickness
Buckle structure, through finite element analysis, fixing buckle is 341.84 megapascal with osseous tunnel mouth contact surface maximum stress, is more than aforementioned magnesium alloy
The yield strength of material, as degradation carries out in service phase, it is more likely that occur to be plastically deformed and there are security risks.Therefore
It needs that degradable magnesium alloy material property is combined to redesign fixing buckle structure size.In addition, excessive rare earth element can be in body
Interior aggregation is not easy to excrete, and especially certain rare earth elements, which can be assembled, to be deposited in bone, with calcium formation competitive adsorption
Calcium constituent in substitution bone leads to healing delay.
In addition, the prior art more attempt in magnesium metal increase alloying element ratio to adjust required engineering properties,
However alloying element and impurity can cause the formation of phase between different metal, the anode as primary battery in degradation to promote magnesium matrix
Corrosion causes magnesium alloy implantation material premature failure during military service.
Invention content
In view of the problems of the above-mentioned prior art, the purpose of the present invention is to propose to a kind of organism implantation material, the lifes
Body implant is made with degradable magnesium alloy, and the degradable magnesium alloy gross mass is 100%, and the content of magnesium accounts for 96.49%
To 98.9%, the content that the content of calcium accounts for 0.1% to 0.5%, zinc accounts for 1% to 3%, and the sum of content of remaining impurity, which accounts for, to be not more than
0.01%.
Preferably, the organism implantation material is bone plate, nail or fixing buckle.For example, the organism implantation material
System is used accurate engraving mode by degradable magnesium alloy or is processed and obtained with numerically-controlled machine tool.
Preferably, the fixing buckle is four hole fixing buckles.The intermediate holes of four hole fixing buckle is mounting hole, to solid
Determine ligament, two apertures of both sides are towing pad, for fixing buckle to be drawn and overturn in performing the operation.In order to increase fixing buckle and cortex
The contact surface of bone contact area, fixing buckle and bone-contact is plane；And another table of the fixing buckle relative to the contact surface
Face is the elliposoidal structure of the smooth of the edge, is that the arcuate structure thickeied is dropped with reducing by the junction between adjacent Kong Yukong
The mechanical property loss that solution is brought.
Oversized fixing buckle can increase bone road diameter, be unfavorable for graft and merged with bone road；And it is undersized, it deposits
Structure is imperfect after degradation, hidden danger of solid failure.Preferably, 12.5 millimeters of fixing buckle length, 3 millimeters to 4.5 millimeters of width,
1.5 millimeters to 3 millimeters of arc thickness at reinforcing between Kong Yukong.Meet the fixing buckle by adjustment width and reinforcing thickness and exist
Maximum stress of the fixation procedure through finite element analysis is less than 250 megapascal.
Preferably, the external degradation rate of the organism implantation material is less than 3 millimeters/year, and degradation rate is less than 1 in vivo
Millimeter/year.It is highly preferred that the internal degradation rate of the organism implantation material is less than 0.6 millimeter/year.
In order to which the surface machining marks and strain hardening layer of eliminating organism implantation material make surfacing, and energy
It allows the organism implantation material to be more prone to uniformly degradation after implanting rather than adds trace corrosion degradation along machine, it is preferable that
The organism implantation material uses electrochemical polish mode, and it includes that a bright minute surface is thrown to make the surface of the organism implantation material
Photosphere.
Another object of the present invention is to propose a kind of degradable magnesium alloy applied to above-mentioned organism implantation material, described to drop
Solving magnesium alloy has high intensity, even tissue and the low characteristic of degradation rate.
The technical solution that the present invention is proposed to reach above-mentioned purpose is to provide a kind of degradable magnesium alloy, and feature exists
In：With the degradable magnesium alloy gross mass for 100%, the content of magnesium accounts for 96.49% to 98.9%, and the content of calcium accounts for 0.1%
Content to 0.5%, zinc accounts for 1% to 3%, and the content summation of remaining impurity is accounted for no more than 0.01%.
The magnesium ion generated by degradable magnesium alloy degradation can promote osteoblast differentiation, induce New born formation.
In addition, the degradable magnesium alloy degradation causes local pH-value (pH) to increase, alkaline environment contributes to the elements such as calcium, phosphorus heavy
Product promotes bone repair and healing.Magnesium has facilitation to reparation and the reconstruction of bone and ligament tissue interface, graft.Together
When, zinc, calcium are also that common are beneficial element in human body.Therefore magnesium-zinc-calcium alloy has good as medical degradation material
Safety basis.
When the increase of alloying element type and quantity can form a large amount of second distributed mutually in magnesium matrix or grain boundaries, and institute
State the impurity such as impurity in degradable magnesium alloy, such as silicon, iron, nickel, copper be formed by second meet to be formed heterogeneous structure acceleration
Magnesium alloy substrate corrosion rate；Therefore, preferably, in the degradable magnesium alloy, the impurity include aluminium, iron, copper, manganese,
Silicon or nickel, and respectively content is all not more than 0.003% to aluminium, iron, copper, manganese, silicon or the nickel in the impurity.Preferably, described
In degradable magnesium alloy, the content summation of the impurity is not more than 0.008%.
In the degradable magnesium alloy, the zinc, calcium element content are too high or too low can be to mechanics mechanical performance and drop
Solution rate has an impact.On the one hand, the adverse effects such as the magnesium alloy of high-alloying can bring plasticity to decline, degradation rate increases.
For example, solid solubility of the calcium in magnesium is about 0.11 mass % under equilibrium state, as calcium content increases, super saturated solid solution effect
Fruit enhances, and the intensity and plasticity of the degradable magnesium alloy increase；But calcium content be more than 0.6 mass % when, it is described to drop
The plasticity and intensity for solving magnesium alloy deteriorate.May be extra calcium can form the second phase of brittleness in crystal boundary, can be dropped described in reduction
Solve the plasticity of magnesium alloy；The second phase of calcic can accelerate the degradable magnesium alloy to corrode as primary battery cathode simultaneously.Also, zinc
Solution strengthening effect in the magnesium alloy reaches peak when the mass percent of zinc accounts for 4%, is further added by Zn content, described to drop
The intensity of solution magnesium alloy reduces instead.On the other hand, when Zn content is less than 1%, solution strengthening effect unobvious so that
The hardness of the degradable magnesium alloy does not meet demand.Therefore it needs to adjust suitable zinc, calcium content to obtain good mechanics
Mechanical performance and degradation rate appropriate.Preferably, in the degradable magnesium alloy, the content of the calcium account for 0.1% to
0.2%.Preferably, in the degradable magnesium alloy, the content of the zinc accounts for 1% to 2.5%.
The size of the degradable magnesium alloy crystal grain can influence its degradation rate and intensity.The drop of the degradable magnesium alloy
Solution rate increases with the increase of crystallite dimension, and smaller crystallite dimension is then conducive to degradable magnesium alloy and uniformly degrades,
Also, smaller crystal grain, which can carry, keeps the intensity of material higher.But when crystal particle scale as low as sub-micron, Nano grade, material is strong
Degree deviates Hall-Page relationship, and refined crystalline strengthening effect declines；And since crystal boundary proportion increases, bulk inner defect concentration
Increase, degradation rate increases instead.Therefore, preferably, the crystallite dimension in the degradable magnesium alloy is 5 microns to 20 micro-
Rice can make the degradable magnesium alloy have intensity appropriate and degradation rate.
The promotion of tensile strength, yield strength, elongation after fracture or the contraction percentage of area indicates that the degradable magnesium alloy is cured
Stress can be carried, and more there is toughness, it is ensured that the degradable magnesium alloy has corrosion resistance and good plastic deformation
Ability.Preferably, the tensile strength of the degradable magnesium alloy is more than the surrender of 300MPa and the degradable magnesium alloy
Intensity is more than 250MPa.Preferably, the elongation after fracture of the degradable magnesium alloy is more than 10% and the degradable magnesium
The contraction percentage of area of alloy is more than 10%.More preferably, the tensile strength of the degradable magnesium alloy is more than 300MPa but not
The yield strength of big what 390MPa and the degradable magnesium alloy is more than 250MPa but little what 390MPa.More preferably,
The elongation after fracture of the degradable magnesium alloy is more than 10% but less the section of what 21% and the degradable magnesium alloy is received
Shrinkage is more than 10% but less what 30%.In the Real of the present invention applies mode, the tensile strength As of the degradable magnesium alloy
390MPa, yield strength As 390MPa, contraction percentage of area As 10.9% and contraction percentage of area As 23% Time, it is described degradable
The alloy Strong degree highests of magnesium alloy；In another Real of the present invention applies mode, the tensile strength As of the degradable magnesium alloy
320MPa, 30% Time of yield strength As 320MPa, contraction percentage of area As 21% and contraction percentage of area As, the degradable magnesium
The plasticity of alloy is best.
The degradable magnesium alloy need to could replace the work of the bone support of organism, protection with enough hardness
With.Therefore, preferably, the microhardness of the degradable magnesium alloy is more than 60 Vickers hardnesses (Hv).
It is a further object of the present invention to provide a kind of preparation methods of above-mentioned degradable magnesium alloy.
The technical solution that the present invention is proposed to reach above-mentioned purpose is to provide a kind of preparation method of degradable magnesium alloy,
It the described method comprises the following steps:
(1) magnesium raw material, calcium raw material, zinc raw material are subjected to vacuum metling step, obtain a uniformly mixed metallic solution, it will
The metallic solution cast is to obtain the first ingot casting；Wherein, the purity of the alloy raw material is all more than 99.9%；
(2) first ingot casting is subjected to solution heat treating step, obtains the second ingot casting；
(3) second ingot casting is subjected to extrusion process step, obtains a bar；And
(4) bar is subjected to processing step of swaging, to obtain the degradable magnesium alloy；Wherein, it is dropped with described
It is 100% to solve magnesium alloy gross mass, and the content of magnesium accounts for 96.49% to 98.9%, and the content of calcium accounts for containing for 0.1% to 0.5%, zinc
Amount accounts for 1% to 3%, and the sum of content of remaining impurity is accounted for no more than 0.01%.
Preferably, in the step of preparation method (2), solution heat treatment temperature circle in 350 DEG C to 450 DEG C,
Soaking time circle waited after the completion of keeping the temperature in 20 hours to 48 hours with air cooling.By this step, second casting of acquisition
In ingot, the alloying elements such as zinc, calcium are dissolved into α-magnesium matrix as far as possible, and remaining second phase is distributed in the graininess disperseed
Intra-die or crystal boundary.Second phase is the Ca that size is less than 5 microns2Mg6Zn3, including being dissolved the MgZn or Mg of Ca2Zn3Xiang Huo
The mixed phase of three.Preferably, in the step of preparation method (3), the extrusion process is forward extrusion, squeezes temperature
Boundary is in 250 DEG C to 350 DEG C, and extrusion speed circle is in 0.2 mm/second (mm/s) to 2 mm/seconds (mm/s), and extrusion ratio is more than 10:
1.By this step, the tensile strength of the bar of acquisition is more than 200MPa, and the yield strength of the bar is more than 170MPa,
The elongation after fracture of the bar is more than 10%, and the contraction percentage of area of the bar is more than 10%.
Preferably, in the step of preparation method (4), the technique of swaging be when swaging preincubation boundary in 15 points
Clock was to 30 minutes, and holding temperature circle is in 250 DEG C to 350 DEG C, and for temperature circle of swaging in 250 DEG C to 350 DEG C, frequency of swaging is 30 hertz
(Hz) to 50 hertz (Hz), pass reduction are 10% to 40%, and deflection of swaging is more than 80%.It is highly preferred that between passage
Soaking time 3 minutes to 60 minutes.
Preferably, the crystallite dimension of the degradable magnesium alloy of acquisition is 5 microns to 20 microns.
Preferably, the tensile strength of the degradable magnesium alloy of acquisition is more than 300MPa, the degradable magnesium alloy
Yield strength is more than 250MPa, and the elongation after fracture of the degradable magnesium alloy is more than 10%, and the degradable magnesium alloy breaks
Face shrinking percentage is more than 10% and the microhardness of the degradable magnesium alloy is more than 60Hv.
Description of the drawings
Figure 1A to Fig. 1 C is embodiment 1 to 3 respectively in the scanning electron micrograph after solution heat treating step；
Fig. 2A to Fig. 2 C is that embodiment 1 to 3 is amplifying 400 times of metallograph after processing step of swaging respectively；
Fig. 3 A to Fig. 3 C are embodiment 1 to 3 respectively in the ess-strain after extrusion process step and processing step of swaging
Curve graph；
Fig. 4 A to Fig. 4 C are the sectional view, vertical view and schematic side view of the fixing buckle of embodiment 1 respectively；
Fig. 5 A to Fig. 5 B are the sectional view and vertical view of the direct-connected miniplate in four holes of embodiment 2 respectively；And
Fig. 6 A to Fig. 6 C are the side view, vertical view and stereogram of the nail of embodiment 3 respectively.
Reference numeral involved by attached drawing is as follows:
1 fixing buckle；11 ellipsoids；111 long side semi arch edges；112 short side semi arch edges；12 is solid
Determine hole；13 towing pads；The 14 fixing buckle surfaces contacted with diaphysis；L length；W maximum widths；
H1 maximum gauges；H2 minimum thickness；2 bone plates；3 nails.
Specific implementation mode
Coordinate schema and the preferred embodiments of the invention below, the present invention is further explained to reach predetermined goal of the invention institute
The technological means taken.
Test equipment and test method：
1. inductively coupled plasma atomic emission spectrometer (ICP-AES)：Test metal component contained by the first ingot casting and
Its content；
2. scanning electron microscope：Model JEOL JSM-6390A, to observe the second ingot casting Cross Section Morphology；
3. metallographic microscope：To identify and analyze the degradable magnesium alloy internal structure of the gained after processing step of swaging
Tissue；
4. metal material tensile test at room temperature：With standard GB/T/T228 test methods measure through extrusion process step with
And after processing step of swaging gained degradable magnesium alloy tensile strength, yield strength, elongation after fracture and the contraction percentage of area,
Wherein, it is rodlike to be made Tourniquet clamping head for sample, and rate of extension is 1 mm/min during experiment；
5. Vickers Hardness Test of Metallic Materials：The dimension of degradable magnesium alloy is measured with standard GB/T/T4340 test methods
Family name's hardness, wherein test loading force is 100 grams, protects and carries 15 seconds time；
6. degradable magnesium alloy external degradation speed trial：2 weeks are impregnated with 37 DEG C of constant water bath box simulated body fluids, weekly more
Change a simulated body fluid；Wherein, each litre of the simulated body fluid include 5.403 grams of (g) sodium chloride, 0.504 gram of sodium bicarbonate,
0.426 gram of sodium carbonate, 0.225 gram of potassium chloride, 0.230 gram of dipotassium hydrogen phosphate trihydrate, 0.311 gram of magnesium chloride hexahydrate,
0.293 gram of calcium chloride, 0.072 gram of sodium sulphate, 17.892 grams of 4- hydroxyethyl piperazineethanesulfonic acids (HEPES), 100 milliliters of 0.2M hydrogen
Sodium hydroxide solution is used in combination the strong caustic of 1 molar concentration (M) that the pH value of the simulated body fluid is adjusted to 7.4；
7. finite element analysis software：The Ansys 15.0 of Ansys companies of the U.S., magnesium alloy materials constant are elasticity modulus
42.1 hundred million pas (GPa), Poisson's ratio 0.31.
Embodiment 1
First raw material configuration is carried out according to following alloy raw material:Magnesium ingot of the purity more than 99.9% is more than as magnesium raw material, purity
99.9% -5.66% calcium intermediate alloy of magnesium (Mg-Ca intermediate alloys) is more than 99.9% zinc granule conduct as calcium raw material, purity
Zinc raw material.
It is put into intermediate frequency furnace (rated frequency 2500Hz) after cast iron die is dried 2 hours at 200 DEG C, in addition, will
Graphite crucible is put into the induction furnace after preliminary drying dehumidifying in 20 minutes through being closed among pickling and the magnesium ingot and Mg-Ca dried
Gold；And zinc granule is added in secondary charging bucket.Start to vacuumize after closing bell, starts to be filled with argon when vacuum degree reaches 0.02 pa
Gas to pressure gauge is shown as -0.076 megapascal, starts power transmission, 15 kilowatts of electrical power (KW) to 17KW at this time；It waits for described after ten minutes
Magnesium ingot and the intermediate alloy have melted, and just suspend power transmission, and zinc granule to be added is further continued for power transmission 5 minutes, and electrical power 15KW is extremely
17KW makes zinc granule be completely melt, obtains the homogeneous metal solution for being mixed with magnesium, Mg-Ca intermediate alloys and zinc.Again by the metal
Solution injects cast iron die to obtain the first ingot casting when 720 DEG C.
The alloying component of the first ingot casting is analyzed using ICP-AES, and analysis result is recorded in table 1.
Using chamber type electric resistance furnace under protection of argon gas to the first ingot casting in 450 DEG C of temperature, soaking time is consolidated for 20 hours
Molten heat treatment；Wait cooling down with air at room temperature after the completion of keeping the temperature, and remove the peel to diameter 90mm, and surface be visible by naked eyes shrinkage cavity,
Stomata, be mingled with etc. casting flaws with the second ingot casting.The second ingot casting Cross Section Morphology, result are observed using scanning electron microscope
As shown in Figure 1A.
By the second ingot casting with 320 DEG C of temperature 3 hours in the resistance furnace, at the same by gasket, mold with it is described
Second ingot casting is kept the temperature together.Then, extrusion cylinder is being warming up to 320 DEG C, is using extrusion speed for 0.7mm/s to 0.8mm/s, squeezed
Pressure ratio is 35：1 forward extrusion technique obtains a bar of a length 3mm, diameter 16mm.
Using metal material tensile test at room temperature, the mechanical property of the bar is measured, and analysis result is recorded in table
2, and draw stress-strain curve As-extruded curve as shown in Figure 3A.
Then, the temperature 15 minutes by the bar before swaging in 250 DEG C, then with the frequency 40Hz that swages, swage
The condition that 250 DEG C of temperature is deformed through 16 passages, and pass reduction is 10.2% to 27.5%, and soaking time is 3 minutes between passage
Technique of swaging was carried out to 30 minutes, finally obtains the rodlike degradable magnesium alloys of the diameter 4.5mm of total deformation 93.1%.It uses
The metallographic structure of degradable magnesium alloy, result such as Fig. 2A institutes described in the metallographic electron microscope observation that enlargement ratio is 400 times
Show.
The even tissue of the degradable alloy of magnesium, recrystallization is complete, and intra-die has a small amount of twin.It is surveyed using intercept method
Obtain 14.3 microns of average grain size.
Using metal material tensile test at room temperature, the mechanical property of the degradable magnesium alloy is measured, and by analysis result
It is recorded in table 2, and draws stress-strain curve state curve of swaging as shown in Figure 3A.
Using Vickers Hardness Test of Metallic Materials, measures the Vickers hardness of the degradable magnesium alloy and be recorded in table 2.
It is impregnated 2 weeks using simulated body fluid, the external degradation rate of the degradable magnesium alloy is 1.0 millimeters/year.
Then, use the accurate mode carved that the degradable magnesium alloy is processed into a length L as 12.5mm, maximum width
Degree W is 4.3mm and includes the fixing buckle 1 in four holes, constructs the fixing buckle 1 as shown in Fig. 4 A to Fig. 4 C.In the fixing buckle 1
Between between two mounting holes 12 in ellipsoid protrusion, the maximum gauge H1 of the fixing buckle 1 is 2.0mm, the minimum of the fixing buckle 1
Thickness H2 is 1.0mm.1 edge of the fixing buckle is arc-shaped structure, and two short side semi arch edges 112 are diameter 3.5mm semicircles
Arc, it is concentric with two towing pads 13 respectively, two long side semi arch edges 111 by the tangent connection of circular arc of two radius 27.26mm,
Form 11 outer profile of ellipsoid of fixing buckle 1.The ellipsoid 11 of the fixing buckle 1, with the intersection across four through-bore axis planes
Curve is a long axis 12.5mm, the semiellipse of short axle 2mm, 11 curve rounding off of ellipsoid and successively perpendicular through long side semicircle
Arc side edge 111, top semiellipse line limit the ellipsoid structure of the fixing buckle 1 with short side semi arch edge 112 jointly.It is described
The fixing buckle surface 14 that fixing buckle 1 is contacted with diaphysis is planar, thereby increases connecing for the fixing buckle 1 and diaphysis (not shown)
Contacting surface is accumulated, it is ensured that the fixing buckle 1 will not fall off；In addition, another surface of the fixing buckle 1 relative to the contact surface is edge
Smooth ellipsoid structure helps to increase support strength, reduces drop by the ellipsoid protrusion between intermediate two mounting holes 12
The loss of mechanical property that solution is brought can ensure enough fixing intensities in degradation process after the implantation.
The fixing buckle 1 of the present embodiment is when loading 136 newton maximum, force, due to there is protrusion to add at intermediate two mounting holes 12
By force, maximum stress only 232 megapascal on the fixing buckle 1 are far below the yield strength (317.5MPa) of the degradable magnesium alloy,
The considerations of meeting Strength Safety.
Next, the method using electrochemical polish is surface-treated the fixing buckle 1：Cathode is stainless steel annular
Electrode, anode are fixing buckle 1.At 0 DEG C, it is electrolysed with direct current power source voltage 6 volts (V), wherein the polishing fluid packet used
Containing volume ratio 7：1 absolute ethyl alcohol and perchloric acid, the citric acid of a concentration of 2 gram/liter (g/L) and a concentration of 0.1g/L's
Glucose content.After electrolysis 30 seconds, the surface of the fixing buckle 1 obtains one layer of bright mirror finish layer (not shown).
Ligament injury model, the fixing buckle 1 after implantation disinfection are established in beasle dog right rear leg.Wait for art the latter moon,
The fixing buckle 1 of implantation is without obvious degradation, and 1 surrounding of fixing buckle being implanted into is generated without apparent bubble, and operative site also has no inflammatory
Reaction, and it is implanted into the beasle dog activity of fixing buckle 1 freely.After six months, the fixation of implantation is buckled with signs of degradation, but this is fixed
Button 1 is still kept fixed function.The fixing buckle 1 and surrounding tissue good knitting that implantation can be found after dissection, have begun to occur
Ligament.Visible a large amount of neocartilages, indicate the catabolite of the fixing buckle 1 of the implantation inside femur end interface and osseous tunnel
Bone road can be promoted to be merged with the fixing buckle 1.Postoperative six months, the fixing buckle 1 of implantation was averaged degradation rate as 0.383 milli in vivo
Rice/year.
Embodiment 2
First raw material configuration is carried out according to following alloy raw material:Magnesium ingot of the purity more than 99.9% is more than as magnesium raw material, purity
99.9% -5.66% calcium intermediate alloy of magnesium (Mg-Ca intermediate alloys) is more than 99.9% zinc granule conduct as calcium raw material, purity
Zinc raw material.
It is put into intermediate frequency furnace after cast iron die is dried 2 hours at 200 DEG C, in addition, by graphite crucible in the sense
It answers in stove and is put into through pickling and the magnesium ingot dried, Mg-Ca intermediate alloys after preliminary drying dehumidifying in 20 minutes；And secondary add is added in zinc granule
In hopper.Start to vacuumize after closing bell, start to be filled with when vacuum degree reaches 0.02 pa argon gas to pressure gauge be shown as-
0.074 megapascal starts power transmission, electrical power 20KW to 24KW at this time；Wait for that the magnesium ingot after ten minutes and the intermediate alloy have melted
Change, just suspend power transmission, zinc granule to be added is further continued for power transmission 5 minutes, and electrical power 15KW to 20KW makes zinc granule be completely melt, obtains
It is mixed with the homogeneous metal solution of magnesium, Mg-Ca intermediate alloys and zinc.The metallic solution is injected into pig mold in 725 DEG C when again
Tool is to obtain the first ingot casting.
The alloying component of the first ingot casting is analyzed using ICP-AES, and analysis result is recorded in table 1.
Using chamber type electric resistance furnace under protection of argon gas to the first ingot casting in 450 DEG C of temperature, soaking time is consolidated for 20 hours
Molten heat treatment；Wait cooling down with air at room temperature after the completion of keeping the temperature, and remove the peel to diameter 90mm, and surface be visible by naked eyes shrinkage cavity,
Stomata, be mingled with etc. casting flaws with the second ingot casting.The second ingot casting Cross Section Morphology, result are observed using scanning electron microscope
As shown in Figure 1B.
By the second ingot casting with 350 DEG C of temperature 3.3 hours in the resistance furnace, while by gasket, mold and institute
The second ingot casting is stated to keep the temperature together.Then, extrusion cylinder is warming up to 350 DEG C, uses extrusion speed for 0.2mm/s to 0.4mm/s,
Extrusion ratio is 35：1 forward extrusion technique obtains a bar of a length 3mm, diameter 16mm.
Using metal material tensile test at room temperature, the mechanical property of the bar is measured, and analysis result is recorded in table
2, and draw stress-strain curve As-extruded curve as shown in Figure 3B.
Then, the temperature 15 minutes by the bar before swaging in 300 DEG C, then with the frequency 50Hz that swages, swage
The condition that 300 DEG C of temperature is deformed through 8 passages, and pass reduction is 16.4% to 31.9%, and soaking time is 5 minutes between passage
Technique of swaging was carried out to 30 minutes, finally obtains the rodlike degradable magnesium alloys of the diameter 5.7mm of total deformation 87.3%.It uses
The metallographic structure of degradable magnesium alloy, result such as Fig. 2 B institutes described in the metallographic electron microscope observation that enlargement ratio is 400 times
Show.
The even tissue of the degradable magnesium alloy, recrystallization is complete, and intra-die has a small amount of twin.It is surveyed using intercept method
Obtain 7.3 microns of average grain size.
Using metal material tensile test at room temperature, the mechanical property of the degradable magnesium alloy is measured, and by analysis result
It is recorded in table 2, and draws stress-strain curve state curve of swaging as shown in Figure 3B.
Using Vickers Hardness Test of Metallic Materials, measures the Vickers hardness of the degradable magnesium alloy and be recorded in table 2.
It is impregnated 2 weeks using simulated body fluid, the external degradation rate of the degradable magnesium alloy is 2.3 millimeters/year.
Then, it uses the accurate mode carved that the degradable magnesium alloy is processed into a length to be for 25.5mm, width
2.5mm, the direct-connected miniplate in four holes 2 that thickness is 0.6mm.A diameter of 4.5mm of the 2 outermost cambered surface of bone plate, construction
The direct-connected miniplate in four holes as shown in Fig. 5 A to Fig. 5 B 2.
Next, the method using electrochemical polish is surface-treated the bone plate 2：Cathode is stainless steel annular electro
Pole, anode are the bone plate 2.It at 20 DEG C, is electrolysed with direct current power source voltage 7V, wherein the polishing fluid occlusion body used
Product ratio 9：The glucose of 1 absolute ethyl alcohol and perchloric acid, the citric acid of a concentration of 5g/L and a concentration of 0.5g/L.Electrolysis 45
After second, the surface of the bone plate 2 obtains one layer of bright mirror finish layer.
It is implanted into the bone plate 2 in miniature pig mandibular, and corresponding nail is coordinated to fix, through postoperative January, the implantation
Bone plate 2 without obvious degradation, and 2 surrounding of bone plate of the implantation is generated without apparent bubble, and operative site also has no inflammatory reaction,
Indicate that the bone plate 2 and surrounding tissue compatibility are good.Postoperative three months, the bone plate 2 of implantation was averaged degradation rate in vivo
For 0.522 millimeter/year.
Embodiment 3
First raw material configuration is carried out according to following alloy raw material:Magnesium ingot of the purity more than 99.9% is more than as magnesium raw material, purity
99.9% -5.58% calcium intermediate alloy of magnesium (Mg-Ca intermediate alloys) is more than 99.9% zinc granule conduct as calcium raw material, purity
Zinc raw material.
It is put into intermediate frequency furnace after cast iron die is dried 2 hours at 200 DEG C, in addition, by graphite crucible in the sense
It answers in stove and is put into through pickling and the magnesium ingot dried, Mg-Ca intermediate alloys after preliminary drying dehumidifying in 20 minutes；And secondary add is added in zinc granule
In hopper.Start to vacuumize after closing bell, start to be filled with when vacuum degree reaches 0.02 pa argon gas to pressure gauge be shown as-
0.068 megapascal starts power transmission, electrical power 20KW to 22KW at this time；Wait for that the magnesium ingot after ten minutes and the intermediate alloy have melted
Change, just suspend power transmission, zinc granule to be added is further continued for power transmission 5 minutes, and electrical power 17KW to 20KW makes zinc granule be completely melt, obtains
It is mixed with the homogeneous metal solution of magnesium, Mg-Ca intermediate alloys and zinc.The metallic solution is injected into pig mold in 720 DEG C when again
Tool is to obtain the first ingot casting.
The alloying component of the first ingot casting is analyzed using ICP-AES, and analysis result is recorded in table 1.
Using chamber type electric resistance furnace under protection of argon gas to the first ingot casting in 400 DEG C of temperature, soaking time is consolidated for 20 hours
Molten heat treatment；Wait cooling down with air at room temperature after the completion of keeping the temperature, and remove the peel to diameter 50mm, and surface be visible by naked eyes shrinkage cavity,
Stomata, be mingled with etc. casting flaws with the second ingot casting.The second ingot casting Cross Section Morphology, result are observed using scanning electron microscope
As shown in Figure 1 C.
By the second ingot casting with 330 DEG C of temperature 2.25 hours in the resistance furnace, while by gasket, mold and institute
The second ingot casting is stated to keep the temperature together.Then, extrusion cylinder is warming up to 330 DEG C, uses extrusion speed for 0.3mm/s, extrusion ratio is
17：1 forward extrusion technique obtains a bar of a length 1mm, diameter 12mm.
Using metal material tensile test at room temperature, the mechanical property of the bar is measured, and analysis result is recorded in table
2, and draw stress-strain curve As-extruded curve as shown in Figure 3 C.
Then, the temperature 15 minutes by the bar before swaging in 350 DEG C, then with the frequency 50Hz that swages, swage
The condition that 350 DEG C of temperature is deformed through 6 passages, and pass reduction is 26.2% to 34.2%, and soaking time is 5 minutes between passage
Technique of swaging was carried out to 30 minutes, finally obtains the rodlike degradable magnesium alloys of the diameter 4.3mm of total deformation 87.2%.It uses
The metallographic structure of degradable magnesium alloy, result described in the metallography microscope sem observation that enlargement ratio is 400 times are as shown in Figure 2 C.
The even tissue of the degradable magnesium alloy, recrystallization is complete, and intra-die has a small amount of twin.It is surveyed using intercept method
Obtain 5.3 microns of average grain size.
Using metal material tensile test at room temperature, the mechanical property of the degradable magnesium alloy is measured, and by analysis result
It is recorded in table 2, and draws stress-strain curve state curve of swaging as shown in Figure 3 C.
Using Vickers Hardness Test of Metallic Materials, measures the Vickers hardness of the degradable magnesium alloy and be recorded in table 2.
It is impregnated 2 weeks using simulated body fluid, the external degradation rate of the degradable magnesium alloy is 2.6 millimeters/year.
Then, use numerically-controlled machine tool that the degradable magnesium alloy is processed into a length as the tool spiral shell of 5mm, a diameter of 2mm
The nail 3 of line constructs the nail 3 as shown in Fig. 6 A to Fig. 6 C.The nail 3 can coordinate the bone plate 2 of embodiment 2 to use.
Next, the method using electrochemical polish is surface-treated the nail 3：Cathode is stainless steel annular electro
Pole, anode are the nail 3.It at 25 DEG C, is electrolysed with direct current power source voltage 10V, wherein the polishing fluid occlusion body used
Product ratio 10：The glucose of 1 absolute ethyl alcohol and perchloric acid, the citric acid of a concentration of 8g/L and a concentration of 1g/L.Electrolysis 90 seconds
Afterwards, the surface of the nail 3 obtains one layer of bright mirror finish layer.
It is implanted into the bone plate 2 and the nail 3 in miniature pig mandibular, through postoperative January, the nail 3 of the implantation is without bright
Aobvious degradation, and 3 surrounding of nail of the implantation is generated without apparent bubble, operative site also has no inflammatory reaction, indicate described in
Nail 3 and surrounding tissue compatibility are good.Postoperative three months, the nail 3 of implantation was averaged degradation rate as 0.477 milli in vivo
Rice/year.
The metal component and its content of 1 embodiment 1 to 3 of table
Metal Mechanic Property of 2 embodiment 1 to 3 of table after implementing extrusion process and technique of swaging
From above-mentioned experimental result it is recognised that by the present invention degradable magnesium alloy certain content ratio, it is described can
Degradation magnesium alloy mainly includes magnesium, calcium and the zinc of human essential elements, not only has good bio-compatibility, and can provide rush
Into the element of bone growth；In addition, the degradable magnesium alloy need not deliberately add to human body there may be the aluminium of toxin or
Manganese can obtain good mechanical mechanics property, provide required hardness, support strength and toughness；And penetrating can described in limitation
Impurity content, the uniform metal structure of formation in degradation magnesium alloy, promote the corrosion resistance of the degradable magnesium alloy.
The above is only presently preferred embodiments of the present invention, not does limitation in any form to the present invention, though
So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, any technology people for being familiar with this profession
Member, in the range of not departing from technical solution of the present invention, when the technology contents using the disclosure above make a little change or repair
Decorations are the equivalent embodiment of equivalent variations, as long as being the content without departing from technical solution of the present invention, technology according to the present invention is real
Any simple modification, equivalent change and modification made by confrontation above example still fall within the range of technical solution of the present invention
It is interior.
Claims (21)
1. a kind of organism implantation material, it is characterised in that：The organism implantation material is made with degradable magnesium alloy, described to drop
It is 100% to solve magnesium alloy gross mass, and the content of magnesium accounts for 96.49% to 98.9%, and the content of calcium accounts for containing for 0.1% to 0.5%, zinc
Amount accounts for 1% to 3%, and the sum of content of remaining impurity is accounted for no more than 0.01%.
2. organism implantation material according to claim 1, it is characterised in that：The organism implantation material is bone plate, nail
Or fixing buckle.
3. organism implantation material according to claim 2, it is characterised in that：The organism implantation material is fixing buckle, institute
It is four hole fixing buckles to state fixing buckle；The upper surface of four hole fixing buckle be the smooth of the edge elliposoidal structure, adjacent hole with
Junction between hole is the arcuate structure thickeied.
4. organism implantation material according to claim 1, it is characterised in that：The surface of the organism implantation material includes one
Mirror-finish layer.
5. organism implantation material according to any one of claim 1 to 4, it is characterised in that：The organism implantation material
Degradation in vivo rate is less than 1 millimeter/year.
6. a kind of degradable magnesium alloy applied to the organism implantation material described in any one of claim 1 to 5, feature exists
In：With the degradable magnesium alloy gross mass for 100%, the content of magnesium accounts for 96.49% to 98.9%, and the content of calcium accounts for 0.1%
Content to 0.5%, zinc accounts for 1% to 3%, and the sum of content of remaining impurity is accounted for no more than 0.01%.
7. degradable magnesium alloy according to claim 6, it is characterised in that：The impurity include aluminium, iron, copper, manganese, silicon or
Nickel, respectively content is all not more than 0.003% for aluminium, iron, copper, manganese, silicon or nickel in the impurity.
8. degradable magnesium alloy according to claim 6, it is characterised in that：The content of the calcium accounts for 0.1% to 0.2%.
9. degradable magnesium alloy according to claim 6, it is characterised in that：The content of the zinc accounts for 1% to 2.5%.
10. the degradable magnesium alloy according to any one of claim 6 to 9, it is characterised in that：The content of the impurity is total
With no more than 0.008%.
11. the degradable magnesium alloy according to any one of claim 6 to 9, it is characterised in that：The degradable magnesium alloy
Crystallite dimension be 5 microns to 20 microns.
12. the degradable magnesium alloy according to any one of claim 6 to 9, it is characterised in that：The degradable magnesium alloy
Tensile strength be more than 300 megapascal, the yield strength of the degradable magnesium alloy is more than 250 megapascal.
13. the degradable magnesium alloy according to any one of claim 6 to 9, it is characterised in that：The degradable magnesium alloy
Elongation after fracture be more than 10%, the contraction percentage of area of the degradable magnesium alloy is more than 10%.
14. the degradable magnesium alloy according to any one of claim 6 to 9, it is characterised in that：The degradable magnesium alloy
Microhardness be more than 60 Vickers hardnesses.
15. the degradable magnesium alloy according to any one of claim 6 to 9, it is characterised in that：The degradable magnesium alloy
External degradation rate be less than 3 millimeters/year.
16. a kind of preparation method of degradable magnesium alloy comprising following steps:
(1) magnesium raw material, calcium raw material, zinc raw material are subjected to vacuum metling step, obtain a uniformly mixed metallic solution, it will be described
Metallic solution cast is to obtain the first ingot casting；Wherein, the purity of the alloy raw material is all more than 99.9%；
(2) first ingot casting is subjected to solution heat treating step, obtains the second ingot casting；
(3) second ingot casting is subjected to extrusion process step, obtains a bar；And
(4) bar is subjected to processing step of swaging, to obtain the degradable magnesium alloy；Wherein, with the degradable magnesium
Alloy gross mass is 100%, and the content of magnesium accounts for 96.49% to 98.9%, and the content that the content of calcium accounts for 0.1% to 0.5%, zinc accounts for
1% to 3%, the sum of content of remaining impurity is accounted for no more than 0.01%.
17. preparation method according to claim 16, it is characterised in that：In step (2), solution heat treatment temperature circle
In 350 DEG C to 450 DEG C, soaking time circle waited after the completion of keeping the temperature in 20 hours to 48 hours with air cooling.
18. preparation method according to claim 16, it is characterised in that：The extrusion process is forward extrusion, squeezes temperature
Boundary is spent in 250 DEG C to 350 DEG C, and extrusion speed circle is in 0.2 mm/second to 2 mm/seconds, and extrusion ratio is more than 10:1.
19. preparation method according to claim 16, it is characterised in that：The technique of swaging is boundary when swaging preincubation
In 15 minutes to 30 minutes, holding temperature circle was in 250 DEG C to 350 DEG C, frequency of swaging in 250 DEG C to 350 DEG C, temperature circle of swaging
30 hertz to 50 hertz, pass reduction is 10% to 40%, and deflection of swaging is more than 80%.
20. the preparation method according to any one of claim 16 to 19, it is characterised in that：The degradable magnesium alloy
Crystallite dimension is 5 microns to 20 microns.
21. the preparation method according to any one of claim 16 to 19, it is characterised in that：The degradable magnesium alloy
Tensile strength is more than 300 megapascal, and the yield strength of the degradable magnesium alloy is more than 250 megapascal, the degradable magnesium alloy
Elongation after fracture is more than 10%, and the contraction percentage of area is more than 10% and the microhardness of the degradable magnesium alloy is more than 60 dimensions
Family name's hardness.
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| CN109022843A (en) * | 2018-08-01 | 2018-12-18 | 郑州大学第附属医院 | Medical embedded degradable composite bar of one kind and preparation method thereof |
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| CN111455248B (en) * | 2020-05-22 | 2021-09-24 | 北京工业大学 | Magnesium air battery anode material and preparation method thereof |
| CN111455248A (en) * | 2020-05-22 | 2020-07-28 | 北京工业大学 | Magnesium air battery anode material and preparation method thereof |
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| CN112481533A (en) * | 2020-11-10 | 2021-03-12 | 江苏理工学院 | Biomedical magnesium alloy and preparation method thereof |
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| CN113171209B (en) * | 2021-04-27 | 2023-10-20 | 山东大学 | Additive manufacturing nickel-titanium alloy femoral stem prosthesis and preparation method thereof |
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