CN106987747A - A kind of even corrosion resistant Biological magnesium alloy and preparation method thereof - Google Patents
A kind of even corrosion resistant Biological magnesium alloy and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of uniform, corrosion resistant magnesium alloy, the magnesium alloy is made up of Mg, Zn, Nd, Ca, Sm element.The mass percent component of wherein each element is：Zn:5.0 7.0%, Nd:0.2 1.5%, Ca:0.1 2.0%, Sm:0.1 1.0%, surplus is Mg and inevitable impurity element；For magnesium alloy the problem of the severe local corrosion existed in terms of bio-medical, the Corrosion Behaviors of Magnesium Alloys mode that the present invention is provided is homogeneous corrosion, alloy is set preferably to preserve the integrality of its structure after being on active service, corrosion resistance is significantly improved, and the catabolite of alloy does not have toxic side effect, can be applied in bone Biological magnesium alloy field.
Description
Technical field
The present invention relates to biological medical magnesium alloy technical field, and in particular to a kind of even corrosion resistant Biological magnesium alloy and its
Preparation method.
Background technology
Magnesium alloy makes it in bio-medical because it is in the characteristic of people's degradable in vivo, and excellent biocompatibility
Aspect has broad prospects, and certain achievement is also had been achieved at present, but be accompanied by clinical practice, magnesium alloy degraded speed
Too fast rate is to hinder the major issue that it further develops always.The electrode potential of magnesium is -2.37V, is easily occurred with oxygen and water
Reaction, and containing Cl-Concentration exceedes to be very easy to be corroded in 30mmol/L solution.Cl in human body fluid-At concentrations up to
180mmol/L, therefore magnesium alloy degradation rate in human body is too fast, thus be easily caused implant site degraded ion concentration it is too high with
And H2Accumulation, patient is occurred local inflammation and cause pain, and along with the failure of implantation component, or even cause secondary wound
Evil.And due to Cl-Presence be very easy to cause the local corrosion of magnesium alloy, make component partial occur heavy corrosion to lose
Go effect.Therefore effective homogeneous corrosion magnesium alloy method is developed, and grasps Corrosion Behaviors of Magnesium Alloys mechanism mechanism, be biological doctor
Use magnesium alloy materials urgent problem to be solved.
The content of the invention
The present invention solve the problem of be, for magnesium alloy in human body severe local corrosion, easily lose asking for its globality
Inscribe there is provided the biological medical magnesium alloy material that a kind of forms of corrosion is general corrosion, can at utmost retain the entirety of alloy
Property.
Another technical problem that the present invention is solved is to provide the preparation method of above-mentioned biological medical magnesium alloy, covers preparation side
Method is improved the microstructure of alloy, crystal grain refinement, and second is mutually evenly distributed on crystal boundary, makes the corrosion resistance of alloy
It can be significantly improved, meet requirement of the Biological magnesium alloy to corrosive nature.
The technical scheme is that：
A kind of even corrosion resistant Biological magnesium alloy, the Biological magnesium alloy is made up of Mg, Zn, Nd, Ca, Sm；Wherein each element
Mass percent component is：Zn 5.0-7.0%, Nd 0.2-1.5%, Ca 0.1-2.0%, Sm 0.1-1.0%, surplus is for Mg and not
Evitable impurity element.
Preferably, the mass percent component of each element is Zn 6.1%, Nd 0.4%, Ca in above-mentioned Biological magnesium alloy
0.9%, Sm 0.3%, remaining is magnesium and micro impurity element；It is by the chemical formula of atomic percentage
Mg96.92Zn2.38Nd0.07Ca0.57Sm0.05。
Further, the forms of corrosion of the even corrosion resistant Biological magnesium alloy is general corrosion.
A kind of preparation method of above-mentioned even corrosion resistant Biological magnesium alloy, using following steps：
（1）Each raw material are weighed by formula, in CO2+SF6 Under mixed gas protected, high-purity magnesium ingot is placed in graphite-clay crucible
700-710 DEG C is inside heated to, Mg-Ca intermediate alloys, Mg-Nd intermediate alloys and Mg-Sm are sequentially added after high-purity magnesium ingot melts
Intermediate alloy, is warming up to 740-750 DEG C, and pure zinc ingot is added after raw material are completely melt, after 10-12 minutes, removes liquation table
The waste residue in face, and stir, then it is cooled to 735 ± 2 DEG C of insulations and stands 25-30 minutes；
(2) alloy melt for being incubated standing is cooled to 710-715 DEG C, in SF6And CO2Under mixed gas protected, it is cast to pre-
Into 395-405 DEG C of mould the female ingot of Mg-Zn-Nd-Ca-Sm cast alloy is made, wherein described SF in heat6And CO2Volume ratio
For 1:130；
（3）By step（2）The female ingot of the Mg-Zn-Nd-Ca-Sm cast alloy of preparation cuts into fritter, takes the quartzy pipe volumes of 5-25%
Sample, be put into internal diameter for 8-16mm；In a diameter of 0.4-0.8mm of lower end circular open glass tube, quartz glass tube is filled
It is fitted on high vacuum single roller rotation quenching equipment；Low vacuum is first taken out in advance with mechanical pump to below 5Pa, then with molecular pump pumping high vacuum extremely
1.0×10-3After below Pa, reversely charging high-purity argon gas, the draught head in control pipe with intracavitary is 0.04-0.10MPa, with 800-
1000r/min speed rotates Zhou Changwei 50cm copper rods, by foundry alloy sensing heating into 700-720 DEG C of alloy melt,
Alloy melt is ejected into the copper roller surface of rotation at a high speed, moment coagulation forming using draught head, you can obtain alloy and quench state Mg-
Zn-Nd-Ca-Sm alloys；
（4）Resistance furnace is warming up to 200-220 DEG C, step（3）Obtained Mg-Zn-Nd-Ca-Sm magnesium alloys are placed in resistance furnace,
Insulation 3-6h is made annealing treatment；Sample after annealing is put into 300-350 DEG C of resistance furnace and carries out solution treated, during insulation
Between be 12-13h, the type of cooling is 50-80 DEG C of quenching-in water；Gu carrying out natrual ageing after the completion of molten, aging time is 4-7
My god, obtain the Mg-Zn-Nd-Ca-Sm magnesium alloys of heat treatment state.
Further, step（1）Described Mg-Ca intermediate alloys are made up of the component of following mass percent：21.50-
22.50%Ca, impurity is less than 0.03%, and surplus is Mg.
Further, step（1）Described Mg-Nd intermediate alloys are made up of the component of following mass percent：22.00-
23.00%Nd, impurity is less than 0.03%, and surplus is Mg.
Further, step（1）Described Mg-Sm intermediate alloys, are made up of the component of following mass percent：26.00-
27.00%Sm, impurity is less than 0.05%, and surplus is Mg.
Further, step（2）The female ingot second of the described Mg-Zn-Nd-Ca-Sm cast alloy crystal boundary that hands down uniformly divides
Cloth is on the matrix of alloy, and crystal grain is tiny and equiax crystal occurs, and average grain size is 8 ~ 9 μm.
Above-mentioned even corrosion resistant Biological magnesium alloy can be applied in terms of bone Biological magnesium alloy.
Heretofore described second is mutually made up of five kinds of elements of Mg, Zn, Nd, Ca, Sm；The present invention heat treatment be
Magnesium alloy local corrosion is solved, improves the effective way of alloy corrosion speed.It can be made by appropriate heat treatment in alloy
The uniform a small amount of distribution of second phase in the base, reduces matrix and the galvanic corrosion of the second phase in degradation process and acted on, and
Uniform the second a small amount of phase can effectively reduce Cl-Caused local corrosion, then turns to homogeneous corrosion, improves magnesium alloy
Corrosion resistance.
Beneficial effects of the present invention：
（1）Zn, Nd, Ca, Sm element that the present invention chooses can be excreted with body metabolism process within the specific limits, with very
Good biocompatibility；
（2）The present invention changes the microstructure of magnesium alloy, as cast condition Mg-Zn- by controlling the reaction condition in preparation method
The crystal boundary that hands down of the second of Nd-Ca-Sm alloy casting state alloys is evenly distributed on the matrix of alloy, and crystal grain is tiny and occurs isometric
Crystalline substance, microstructure is uniform so that the increasing number of crystal boundary, slow down the corrosion rate of alloy；Sprayed by high vacuum rapid solidification
After penetrating and being heat-treated, on crystal boundary second it is mutually most of be all fused to admittedly in matrix, small part even dispersion is distributed on matrix,
The quantity in the cathode activity site of alloy surface is reduced, alloy is changed from spot corrosion to homogeneous corrosion.
(3) Biological magnesium alloy microstructure prepared by the present invention is uniform, and the second distributed mutually is uniform on crystal boundary, in corrosion process
Alloy is not susceptible to local corrosion, and the etch pit of alloy surface is few and shallow after corrosion test, and forms of corrosion is homogeneous corrosion,
Enough macrostructures for preferably preserving military service alloy, are retained the globality of alloy, farthest retain alloy
Globality, corrosion resistance is significantly enhanced；Magnesium alloy is solved as implantation material, under arms during because degradation rate
Alloy globality caused by too fast is lost, and makes the problem of alloy original paper prematurely fails.
（4）The present invention is simple to operate, just with popularization and application.
Brief description of the drawings
(a) in Fig. 1, (b) are respectively the back scattering of Mg-Zn-Nd-Ca-Sm magnesium alloys prepared by comparative example 2 and embodiment 3
Electron scanning electron microscope；
Fig. 2 is the erosion profile figure that the alloy of embodiment 3 is obtained after weight-loss corrosion；
Fig. 3 is each embodiment and the weight-loss corrosion test result of comparative example magnesium alloy；
Fig. 4 is the electrochemical corrosion test polarization curve of each embodiment and comparative example magnesium alloy.
Embodiment
The present invention is described in further detail with reference to the accompanying drawings and detailed description.
High vacuum single roller used revolves the model for system of quenching in the embodiment of the present invention：The types of HVDS- II.
The percentage composition of embodiment 1-4 magnesium alloy nominal composition each elements is listed in table 1.
The embodiment 1-4 magnesium alloy nominal compositions of table 1（wt%）
Embodiment 1
（1）The quality of each metal is weighed by the composition proportion of embodiment 1 in table 1, in CO2+SF6 Under mixed gas protected, by height
Pure magnesium ingot is placed in graphite-clay crucible and is heated to 700 DEG C, and Mg-Ca intermediate alloys are sequentially added after high-purity magnesium ingot melts,
Mg-Nd intermediate alloys and Mg-Sm intermediate alloys, are warming up to 750 DEG C, and pure zinc ingot, 10 minutes are added after raw material are completely melt
Afterwards, the waste residue of molten surface is removed, and is stirred, 733 DEG C of insulations is then cooled to and stands 30 minutes；
(2) alloy melt for being incubated standing is cooled to 710 DEG C, in SF6And CO2Under mixed gas protected, it is cast to and is preheated to
In 405 DEG C of mould, the female ingot of Mg-Zn-Nd-Ca-Sm cast alloy is made, wherein described SF6And CO2Volume ratio is 1:130；
（3）By step（2）The female ingot of the Mg-Zn-Nd-Ca-Sm cast alloy of preparation cuts into fritter, takes the examination of 5% quartzy pipe volume
Sample, is put into internal diameter for 8mm, in a diameter of 0.4mm of lower end circular open glass tube, quartz glass tube is assembled into high vacuum list
Roller revolves quenching equipment, low vacuum is first taken out in advance with mechanical pump to 4Pa, then with molecular pump pumping high vacuum to 0.8 × 10-3Pa, reversely charging is high
After pure argon, interior and intracavitary the draught head of control pipe is 0.04-0.10MPa；Zhou Changwei 50cm copper rods are made with 800r/min speed
Rotate, by foundry alloy sensing heating into 700 DEG C of alloy melt, alloy melt is ejected into using draught head and rotated at a high speed
Copper roller surface, moment coagulation forming, you can obtain alloy and quench state Mg-Zn-Nd-Ca-Sm alloys；
（4）Resistance furnace is warming up to 200 DEG C, step（3）Obtained Mg-Zn-Nd-Ca-Sm magnesium alloys are placed in resistance furnace, insulation
6h is made annealing treatment；Sample after annealing is put into 300 DEG C of resistance furnace and carries out solution treated, soaking time is 13h, cold
But mode is 50 DEG C of quenching-in water；Gu carrying out natrual ageing after the completion of molten, aging time is 7 days, obtains the Mg- of heat treatment state
Zn-Nd-Ca-Sm magnesium alloys.
In the embodiment：Step（1）Described Mg-Ca intermediate alloys constitute 21.50% by the component of following mass percent
Ca, impurity is less than 0.03%, and surplus is Mg；Step（1）Described Mg-Nd intermediate alloys by following mass percent component group
Into：23.00%Nd, impurity is less than 0.03%, and surplus is Mg；Step（1）Described Mg-Sm intermediate alloys, by following quality percentage
The component composition of ratio：26.00%Sm, impurity is less than 0.05%, and surplus is Mg.
After weight-loss corrosion is tested, the corrosion depth of alloy is 4.18mm/a.
Embodiment 2
（1）The quality of each metal is weighed by the composition proportion of embodiment in table 1, in CO2+SF6 , will be high-purity under mixed gas protected
Magnesium ingot is placed in graphite-clay crucible and is heated to 710 DEG C, and Mg-Ca intermediate alloys, Mg- are sequentially added after high-purity magnesium ingot melts
Nd intermediate alloys and Mg-Sm intermediate alloys, are warming up to 740 DEG C, and pure zinc ingot is added after raw material are completely melt, after 12 minutes,
The waste residue of molten surface is removed, and is stirred, 737 DEG C of insulations is then cooled to and stands 25 minutes；
(2) alloy melt for being incubated standing is cooled to 715 DEG C, in SF6And CO2Under mixed gas protected, it is cast to and is preheated to
In 395 DEG C of mould, the female ingot of Mg-Zn-Nd-Ca-Sm cast alloy is made, wherein described SF6And CO2Volume ratio is 1:130；
（3）By step（2）The female ingot of the Mg-Zn-Nd-Ca-Sm cast alloy of preparation cuts into fritter, takes 25% quartzy pipe volume
Sample, is put into internal diameter for 16mm；In a diameter of 0.4mm of lower end circular open glass tube, quartz glass tube is assembled to Gao Zhen
Empty list roller rotation quenching equipment；Low vacuum is first taken out in advance with mechanical pump to 4.8, then with molecular pump pumping high vacuum to 0.9 × 10-3Pa, instead
Fill after high-purity argon gas, the draught head in control pipe with intracavitary is 0.10MPa, makes Zhou Changwei 50cm copper rods with 1000r/min speed
Rotate, by foundry alloy sensing heating into 720 DEG C of alloy melt, alloy melt is ejected into using draught head and rotated at a high speed
Copper roller surface, moment coagulation forming, you can obtain alloy and quench state Mg-Zn-Nd-Ca-Sm alloys；
（4）Resistance furnace is warming up to 220 DEG C, step（3）Obtained Mg-Zn-Nd-Ca-Sm magnesium alloys are placed in resistance furnace, insulation
3h is made annealing treatment；Sample after annealing is put into 350 DEG C of resistance furnace and carries out solution treated, soaking time is 12h, cold
But mode is 80 DEG C of quenching-in water；Gu carrying out natrual ageing after the completion of molten, aging time is 4 days, obtains the Mg- of heat treatment state
Zn-Nd-Ca-Sm magnesium alloys.
In the embodiment：Step（1）Described Mg-Ca intermediate alloys constitute 22.50% by the component of following mass percent
Ca, impurity is less than 0.03%, and surplus is Mg；Step（1）Described Mg-Nd intermediate alloys by following mass percent component group
Into：22.00%Nd, impurity is less than 0.03%, and surplus is Mg；Step（1）Described Mg-Sm intermediate alloys, by following quality percentage
The component composition of ratio：27.00%Sm, impurity is less than 0.05%, and surplus is Mg.
After weight-loss corrosion is tested, the corrosion depth of alloy is 2.45mm/a.
Embodiment 3
（1）The quality of each metal is weighed by the composition proportion of embodiment in table 1, in CO2+SF6 , will be high-purity under mixed gas protected
Magnesium ingot is placed in graphite-clay crucible and is heated to 705 DEG C, and Mg-Ca intermediate alloys, Mg- are sequentially added after high-purity magnesium ingot melts
Nd intermediate alloys and Mg-Sm intermediate alloys, are warming up to 745 DEG C, and pure zinc ingot is added after raw material are completely melt, after 11 minutes,
The waste residue of molten surface is removed, and is stirred, 735 DEG C of insulations is then cooled to and stands 28 minutes；
(2) alloy melt for being incubated standing is cooled to 712 DEG C, in SF6And CO2Under mixed gas protected, it is cast to and is preheated to
In 400 DEG C of mould, the female ingot of Mg-Zn-Nd-Ca-Sm cast alloy is made, wherein described SF6And CO2Volume ratio is 1:130；
（3）By step（2）The female ingot of the Mg-Zn-Nd-Ca-Sm cast alloy of preparation cuts into fritter, takes 15% quartzy pipe volume
Sample, is put into internal diameter for 12mm；In a diameter of 0.6mm of lower end circular open glass tube, quartz glass tube is assembled to Gao Zhen
Empty list roller rotation quenching equipment；Low vacuum is first taken out in advance with mechanical pump to 4.5, then with molecular pump pumping high vacuum to 0.95 × 10-3P, instead
Fill after high-purity argon gas, interior and intracavitary the draught head of control pipe is 0.06MPa；Turn Zhou Changwei 50cm copper rod with 900r/min speed
Move up, by foundry alloy sensing heating into 710 DEG C of alloy melt, alloy melt is ejected into rotation at a high speed using draught head
Copper roller surface, moment coagulation forming, you can obtain alloy and quench state Mg-Zn-Nd-Ca-Sm alloys；
（4）Resistance furnace is warming up to 210 DEG C, step（3）Obtained Mg-Zn-Nd-Ca-Sm magnesium alloys are placed in resistance furnace, insulation
4h is made annealing treatment；Sample after annealing is put into 320 DEG C of resistance furnace and carries out solution treated, soaking time is 12.5h,
The type of cooling is 65 DEG C of quenching-in water；Gu carrying out natrual ageing after the completion of molten, aging time is 6 days, obtains heat treatment state
Mg-Zn-Nd-Ca-Sm magnesium alloys.
In the embodiment：Step（1）Described Mg-Ca intermediate alloys constitute 23.0% by the component of following mass percent
Ca, impurity is less than 0.03%, and surplus is Mg；Step（1）Described Mg-Nd intermediate alloys by following mass percent component group
Into：22.50%Nd, impurity is less than 0.03%, and surplus is Mg；Step（1）Described Mg-Sm intermediate alloys, by following quality percentage
The component composition of ratio：26.50%Sm, impurity is less than 0.05%, and surplus is Mg.
For after weight-loss corrosion is tested, the corrosion depth of alloy is 0.57 mm/a.
Embodiment 4
（1）The quality of each metal is weighed by the composition proportion of embodiment in table 1, in CO2+SF6 , will be high-purity under mixed gas protected
Magnesium ingot is placed in graphite-clay crucible and is heated to 705 DEG C, and Mg-Ca intermediate alloys, Mg- are sequentially added after high-purity magnesium ingot melts
Nd intermediate alloys and Mg-Sm intermediate alloys, are warming up to 745 DEG C, and pure zinc ingot is added after raw material are completely melt, after 11 minutes,
The waste residue of molten surface is removed, and is stirred, 735 DEG C of insulations is then cooled to and stands 25 minutes；
(2) alloy melt for being incubated standing is cooled to 715 DEG C, in SF6And CO2Under mixed gas protected, it is cast to and is preheated to
In 398 DEG C of mould, the female ingot of Mg-Zn-Nd-Ca-Sm cast alloy is made, wherein described SF6And CO2Volume ratio is 1:130；
（3）By step（2）The female ingot of the Mg-Zn-Nd-Ca-Sm cast alloy of preparation cuts into fritter, takes 18% quartzy pipe volume
Sample, is put into internal diameter for 10mm；In a diameter of 0.6mm of lower end circular open glass tube, quartz glass tube is assembled to Gao Zhen
Empty list roller rotation quenching equipment；Low vacuum is first taken out in advance with mechanical pump to 4.5, then with molecular pump pumping high vacuum to 0.85 × 10-3P, instead
Fill after high-purity argon gas, interior and intracavitary the draught head of control pipe is 0.06MPa；Turn Zhou Changwei 50cm copper rod with 900r/min speed
Move up, by foundry alloy sensing heating into 710 DEG C of alloy melt, alloy melt is ejected into rotation at a high speed using draught head
Copper roller surface, moment coagulation forming, you can obtain alloy and quench state Mg-Zn-Nd-Ca-Sm alloys；
（4）Resistance furnace is warming up to 210 DEG C, step（3）Obtained Mg-Zn-Nd-Ca-Sm magnesium alloys are placed in resistance furnace, insulation
4h is made annealing treatment；Sample after annealing is put into 320 DEG C of resistance furnace and carries out solution treated, soaking time is 12.5h,
The type of cooling is 65 DEG C of quenching-in water；Gu carrying out natrual ageing after the completion of molten, aging time is 6 days, obtains heat treatment state
Mg-Zn-Nd-Ca-Sm magnesium alloys.
In the embodiment：Step（1）Described Mg-Ca intermediate alloys constitute 23.2% by the component of following mass percent
Ca, impurity is less than 0.03%, and surplus is Mg；Step（1）Described Mg-Nd intermediate alloys by following mass percent component group
Into：22.80%Nd, impurity is less than 0.03%, and surplus is Mg；Step（1）Described Mg-Sm intermediate alloys, by following quality percentage
The component composition of ratio：26.50%Sm, impurity is less than 0.05%, and surplus is Mg.
After weight-loss corrosion is tested, the corrosion depth of alloy is 2.37 mm/a.
Comparative example 1
（1）The quality of each metal is weighed according to the composition proportion of embodiment 3, in CO2+SF6 Under mixed gas protected, by high purity magnesium
Ingot is placed in graphite-clay crucible and is heated to 705 DEG C, and Mg-Ca intermediate alloys, Mg-Nd are sequentially added after high-purity magnesium ingot melts
Intermediate alloy and Mg-Sm intermediate alloys, are warming up to 745 DEG C, and pure zinc ingot is added after raw material are completely melt, after 11 minutes, is removed
The waste residue of molten surface is removed, and is stirred, 735 DEG C of insulations is then cooled to and stands 28 minutes；
(2) alloy melt for being incubated standing is cooled to 712 DEG C, in SF6And CO2Under mixed gas protected, it is cast to and is preheated to
In 400 DEG C of mould, the female ingot of Mg-Zn-Nd-Ca-Sm cast alloy is made, wherein described SF6And CO2Volume ratio is 1:130；
（3）Resistance furnace is warming up to 210 DEG C, step（2）Obtained Mg-Zn-Nd-Ca-Sm magnesium alloys are placed in resistance furnace, insulation
4h is made annealing treatment；Sample after annealing is put into 320 DEG C of resistance furnace and carries out solution treated, soaking time is 12.5h,
The type of cooling is 65 DEG C of quenching-in water；Gu carrying out natrual ageing after the completion of molten, aging time is 6 days, obtains heat treatment state
Mg-Zn-Nd-Ca-Sm magnesium alloys.
In the embodiment：Step（1）Described Mg-Ca intermediate alloys constitute 23.0% by the component of following mass percent
Ca, impurity is less than 0.03%, and surplus is Mg；Step（1）Described Mg-Nd intermediate alloys by following mass percent component group
Into：22.50%Nd, impurity is less than 0.03%, and surplus is Mg；Step（1）Described Mg-Sm intermediate alloys, by following quality percentage
The component composition of ratio：26.50%Sm, impurity is less than 0.05%, and surplus is Mg.
After weight-loss corrosion is tested, the corrosion depth of alloy is 4.26mm/a.
Comparative example 2
The quality of each metal is weighed according to the proportioning of Zn, Nd, Ca, Sm each element in embodiment 3, graphite-clay crucible is placed in
Resistance furnace is together warming up to 500 DEG C, in SF6And CO2Under mixed gas protected, by high-purity magnesium ingot, Mg-Ca, Mg-Nd, Mg-Sm
Between alloy be put into graphite-clay crucible, be warming up to 740-750 DEG C, pure zinc ingot, 10 minutes added after raw material are completely melt
Afterwards, the waste residue of molten surface is removed, and is stirred, 30 minutes are stood, in SF6And CO2Under mixed gas protected, casting forming,
The female ingot of Mg-Zn-Nd-Ca-Sm cast alloy is made.
After weight-loss corrosion is tested, the corrosion depth of alloy is 5.92 mm/a.
Performance test
First, Morphology analysis
The microscopic appearance of the cast alloy of comparative example 2 and the heat treatment state alloy of embodiment 3 is detected using ESEM, sees attached
Shown in Fig. 1, a figures from accompanying drawing 1 and are evenly distributed, are in partly as can be seen that the crystallite dimension of the cast alloy of comparative example 2 is tiny
Equiax crystal is evenly distributed, and average grain size is at 8~9 μm.After Overheating Treatment, as shown in b figures in accompanying drawing 1, the alloy of embodiment 3
The second of grain boundaries is mutually most of to be solidly soluted into matrix, makes the galvanic corrosion produced by alloy substrate and the second phase factor potential difference
Effect reduce, and then make alloy tend to homogeneous corrosion.
The microscopic appearance that the alloy of embodiment 3 is carried out after SBF weight-loss corrosions is detected, as shown in accompanying drawing 2, from figure
As can be seen that the corrosion process of alloy is corroded along crystal boundary to intra-die, etch pit is not found, therefore, after processing
The Corrosion Types of alloy are homogeneous corrosion.
2nd, corrosive nature is tested
1. weight-loss corrosion is tested
Weight-loss corrosion is carried out to alloy as corrosive liquid using simulated body fluid, corrosion test refers to the reality of ASTM-G31 metals
Test room immersion corrosion standard.Test is carried out in FX303-O constant incubators：It it is 37 DEG C by temperature setting, after sample is polished
Suspension is soaked in the simulated body fluid configured（Solution is by deionized water and the material composition being listed in Table 2 below）, soak time is
24h, 72h, 120h, 192h, 201h, 504h, a corrosive liquid is changed during immersion every 24h.Sample is taken out after the completion of immersion
It is placed in chromic acid silver nitrate solution（200g/LCrO3 + 10g/LAgNO3）Middle cleaning, calculates the quality damage before and after sample weight-loss corrosion
Lose, draw the weight-loss corrosion speed of alloy.Accompanying drawing 3 is each composition embodiment and comparative example 1, the weightlessness of comparative example 2 in corresponding table 1
Corrosion rate test result.
The nonaqueous component of the simulated body fluid of table 2（g/L）
From the test result of accompanying drawing 3 and according to the density and corroded area of each alloy, each embodiment and comparative example alloy are calculated
Corrosion depth, result of calculation is shown in Table 3.
The various embodiments of the present invention of table 3 and comparative example corrosion depth
It can be drawn by the result of Fig. 3 and table 3, the corrosion rate of embodiment 3 is minimum, and corrosion depth is minimum, reaches 0.57
Mm/a, corrosion resistance is preferably, secondly embodiment 4, embodiment 2, embodiment 1, comparative example 1, comparative example 2.
2. electrochemical corrosion is tested
Electrochemical corrosion test is carried out to the alloy of each embodiment and comparative example, experiment uses LK2005A type electrochemical workstations,
Using three-electrode system, test sample is working electrode, and saturated calomel electrode is reference electrode, and platinum electrode is to electrode, electrolysis
Liquid is the SBF simulated body fluids configured according to table 2.Test and start after OCP is stable, first carry out cathodic scan, carrying out
Anodic scan, potential scanning speed is 5 mV/s, and electric potential scanning interval is -2.5V ~ -0.5V, and sensitivity is 10mV.Implement to each
Example and comparative example are carried out after electrochemical corrosion test, and the polarization curve of each sample is as shown in Figure 4.After being fitted to polarization curve
The corrosion potential and corrosion current density for calculating alloy are as shown in table 4.
Table 4 is the fitting result to alloy polarization curve
It can be obtained with reference to Fig. 4 and table 4, the corrosion potential of embodiment 3 is -1.34V, and corrosion current density is 0.38 mA/cm2。
The corrosion resisting property of the electrochemical corrosion of each embodiment and comparative example alloy is respectively from high to low：Embodiment 3, embodiment 4, implementation
Example 2, embodiment 1, comparative example 1, comparative example 2.It is consistent with the result of weight-loss corrosion, therefore, it is determined that the technique of embodiment 3 is optimal
Scheme.
Summary result, embodiment 3 quenches through overwinding, be heat-treated after the magnesium alloy for preparing, corrosion resistance can be obtained best
Meet the alloy of bone Biological magnesium alloy standard.
The magnesium alloy preparation technology and handling process that the present invention is provided are simple, and preparation cost is low, and the magnesium alloy of preparation has
Excellent corrosion resistance, the characteristics of overcoming magnesium alloy spot corrosion makes it still be able to after military service longer period of time more complete
Its structural intergrity of whole holding, and the good biocompatibility of alloy, catabolite do not react with human body, are expected in life
Thing medical domain is applied.
Claims (9)
1. a kind of even corrosion resistant Biological magnesium alloy, it is characterised in that the Biological magnesium alloy is made up of Mg, Zn, Nd, Ca, Sm；
The mass percent component of wherein each element is：Zn 5.0-7.0%, Nd 0.2-1.5%, Ca 0.1-2.0%, Sm 0.1-1.0%,
Surplus is Mg and inevitable impurity element.
2. a kind of even corrosion resistant Biological magnesium alloy according to claim 1, it is characterised in that in the Biological magnesium alloy
The mass percent component of each element is Zn 6.1%, Nd 0.4%, Ca 0.9%, Sm 0.3%, and remaining is magnesium and trace impurity
Element；It is Mg by the chemical formula of atomic percentage96.92Zn2.38Nd0.07Ca0.57Sm0.05。
3. a kind of even corrosion resistant Biological magnesium alloy according to claim 1, it is characterised in that the even corrosion resistant life
The forms of corrosion of thing magnesium alloy is general corrosion.
4. the preparation method of the even corrosion resistant Biological magnesium alloy described in a kind of any one of claim 1-3, it is characterised in that adopt
Use following steps：
（1）Each raw material are weighed by formula, in CO2+SF6Under mixed gas protected, high-purity magnesium ingot is placed in graphite-clay crucible
700-710 DEG C is inside heated to, Mg-Ca intermediate alloys, Mg-Nd intermediate alloys and Mg-Sm are sequentially added after high-purity magnesium ingot melts
Intermediate alloy, is warming up to 740-750 DEG C, and pure zinc ingot is added after raw material are completely melt, after 10-12 minutes, removes liquation table
The waste residue in face, and stir, then it is cooled to 735 ± 2 DEG C of insulations and stands 25-30 minutes；
(2) alloy melt for being incubated standing is cooled to 710-715 DEG C, in SF6And CO2Under mixed gas protected, preheating is cast to
Into 395-405 DEG C of mould, the female ingot of Mg-Zn-Nd-Ca-Sm cast alloy is made, wherein described SF6And CO2Volume ratio is
1:130；
（3）By step（2）The female ingot of the Mg-Zn-Nd-Ca-Sm cast alloy of preparation cuts into fritter, takes the quartzy pipe volumes of 5-25%
Sample, be put into internal diameter for 8-16mm；In a diameter of 0.4-0.8mm of lower end circular open glass tube, quartz glass tube is filled
It is fitted on high vacuum single roller rotation quenching equipment；Low vacuum is first taken out in advance with mechanical pump to below 5Pa, then with molecular pump pumping high vacuum extremely
1.0×10-3After below Pa, reversely charging high-purity argon gas, interior and intracavitary the draught head of control pipe is 0.04-0.10MPa；With 800-
1000r/min speed rotates Zhou Changwei 50cm copper rods, by foundry alloy sensing heating into 700-720 DEG C of alloy melt,
Alloy melt is ejected into the copper roller surface of rotation at a high speed, moment coagulation forming using draught head, you can obtain alloy and quench state Mg-
Zn-Nd-Ca-Sm alloys；
（4）Resistance furnace is warming up to 200-220 DEG C, step（3）Obtained Mg-Zn-Nd-Ca-Sm magnesium alloys are placed in resistance furnace,
Insulation 3-6h is made annealing treatment；Sample after annealing is put into 300-350 DEG C of resistance furnace and carries out solution treated, during insulation
Between be 12-13h, the type of cooling is 50-80 DEG C of quenching-in water；Gu carrying out natrual ageing after the completion of molten, aging time is 4-7
My god, obtain the Mg-Zn-Nd-Ca-Sm magnesium alloys of heat treatment state.
5. preparation method according to claim 4, it is characterised in that step（1）Described Mg-Ca intermediate alloys are by following
The component composition of mass percent：21.50-22.50%Ca, impurity is less than 0.03%, and surplus is Mg.
6. preparation method according to claim 4, it is characterised in that step（1）Described Mg-Nd intermediate alloys are by following
The component composition of mass percent：22.00-23.00%Nd, impurity is less than 0.03%, and surplus is Mg.
7. preparation method according to claim 4, it is characterised in that step（1）Described Mg-Sm intermediate alloys, by with
The component composition of lower mass percent：26.00-27.00%Sm, impurity is less than 0.05%, and surplus is Mg.
8. preparation method according to claim 4, it is characterised in that step（2）Described Mg-Zn-Nd-Ca-Sm as cast conditions
Alloy mother's ingot second crystal boundary that hands down is evenly distributed on the matrix of alloy, and crystal grain is tiny and equiax crystal occurs, average crystal grain chi
Very little is 8 ~ 9 μm.
9. a kind of application of the uniform corrosion resistance Biological magnesium alloy described in any one of claim 1-3, it is characterised in that, it is described
Magnesium alloy can be applied in terms of bone Biological magnesium alloy.
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| CN114921700A (en) * | 2022-05-25 | 2022-08-19 | 中南大学 | Biodegradable Mg-Zn-Ca-Re alloy |
| CN115679173A (en) * | 2022-10-25 | 2023-02-03 | 中国科学院金属研究所 | Stress corrosion resistant magnesium alloy applied to biomedical material field, and preparation method and application thereof |
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