CN107760945A - A kind of magnesium alloy with high corrosion drag and bioactivity and preparation method thereof - Google Patents

A kind of magnesium alloy with high corrosion drag and bioactivity and preparation method thereof Download PDF

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CN107760945A
CN107760945A CN201711011345.7A CN201711011345A CN107760945A CN 107760945 A CN107760945 A CN 107760945A CN 201711011345 A CN201711011345 A CN 201711011345A CN 107760945 A CN107760945 A CN 107760945A
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magnesium alloy
bioactivity
high corrosion
calcium silicates
powder
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CN107760945B (en
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帅词俊
高成德
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Central South University
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Abstract

The invention discloses a kind of magnesium alloy with high corrosion drag and bioactivity, the magnesium alloy is made up of Biological magnesium alloy matrix and the calcium silicates being evenly distributed in Biological magnesium alloy matrix, wherein, the mass percent of calcium silicates is 5 20%.Present invention additionally comprises a kind of method for preparing the magnesium alloy with high corrosion drag and bioactivity, comprise the following steps：(1) calcium silicates powder and Biological magnesium alloy powder are pressed into design proportion under protective atmosphere, ball milling obtains dispersed mixed-powder in ball mill；(2) using above-mentioned mixed-powder as raw material, under protective atmosphere, corrosion-resistant Biological magnesium alloy is prepared using selective laser fusing.Calcium silicates is successfully uniformly combined in Biological magnesium alloy matrix by the present invention, and the magnesium alloy being prepared has high corrosion resistance and bioactivity.

Description

A kind of magnesium alloy with high corrosion drag and bioactivity and preparation method thereof
Technical field
The invention belongs to Biological magnesium alloy preparing technical field, more particularly to one kind, and there is high corrosion drag and biology to live Magnesium alloy of property and preparation method thereof.
Background technology
Biological magnesium alloy is because of its biodegradability and high specific strength (the ratio between intensity and density), in bone tissue engineer The fields such as support, orthopaedics fixture obtain increasing concern.Compared with other medical materials, the machine of magnesium and magnesium alloy Tool performance can effectively alleviate stress-shielding effect as orthopedic implanting material, promote the growth of bone and be cured closer to nature bone Close；Importantly, can voluntarily be degraded while bone uptake, metabolism can be progressively absorbed by organisms.However, biological magnesium closes The shortcomings that gold is maximum is to be degraded in body fluid too fast, causes to lose mechanical integrity before defect Bone Defect Repari；Fast erosion simultaneously Caused a large amount of hydrogen and pH value rise can also hinder wound healing.In addition, although some researchs show that magnesium alloy can pass through Release can stimulate the magnesium ion of marrow stromal cell to strengthen osteanagenesis, and in early stage in vivo studies, it is observed that planting Enter and gap between thing and bone tissue be present.Therefore, how to improve the corrosion resistance of Biological magnesium alloy and further improve it Bioactivity, it is its problem in the urgent need to address as biodegradation material.
In recent years, the silicate bioceramic based on calcium silicates receives increasing because of excellent bioactivity Concern.In vivo assess can gradually be degraded in verified calcium silicates Ceramic implants, do not cause locally or systemically toxicity, Inflammation or foreign body reaction.Research has shown that the Si ions discharged in calcium silicates degradation process can be by promoting human mesenchyme dry thin Adhesion, propagation and the differentiation of born of the same parents and Gegenbaur's cell carry out promoting bone growing.In addition, calcium silicates ceramics can in degradation process shape Into electronegative silanol base, the forming core for apatite provides target spot and promotes it in the deposition of alloy surface, so as to improve alloy Corrosion resistance.These features allow enhancing phase of the calcium silicates as magnesium and magnesium alloy, are particularly improving corrosion resistance Huge potentiality have been shown with terms of bioactivity.
Because the existing study limitation of Biological magnesium alloy is prepared in using powder metallurgy, the common process such as melting-casting, Powder metallurgy process is carried out under the fusing point less than parent metal, and meeting residual porosity, makes its sintered density inside alloy Deficiency, and the setting time of casting method is long and wetability between ceramic particle and metallic matrix is poor, ceramic particle easily goes out Existing agglomeration.Therefore, it is a huge challenge to be effectively combined in Biological magnesium alloy using calcium silicates as the second phase.
The content of the invention
One kind is provided it is an object of the invention to overcome the deficiencies in the prior art has high corrosion drag and bioactivity Magnesium alloy and preparation method thereof.
A kind of magnesium alloy with high corrosion drag and bioactivity, the magnesium alloy is by Biological magnesium alloy matrix and uniformly The calcium silicates being distributed in Biological magnesium alloy matrix is formed, wherein, the mass percent of calcium silicates is 5-20%, is preferably 8- 12%th, it is more preferably 10%.
The particle size of the calcium silicates is 1~10 μm.
A kind of method for preparing the magnesium alloy with high corrosion drag and bioactivity, comprises the following steps：
(1) calcium silicates powder and Biological magnesium alloy powder are pressed into design proportion under protective atmosphere, the ball milling in ball mill Obtain dispersed mixed-powder；Wherein, drum's speed of rotation is 300~400rad/min, and ratio of grinding media to material is 16~24:1, ball Consume time as 3~5 hours；
(2) using above-mentioned mixed-powder as raw material, under protective atmosphere, H is controlled2O and O2Concentration is less than 30ppm, utilizes Selective laser fusing prepares corrosion-resistant Biological magnesium alloy；In preparation process, to control laser power be 75-110W, sweep speed is 200-260mm/min, spot diameter are 45-105 μm, sweep span is 30~100 μm, powdering thickness is 100~220 μm.
Further, drum's speed of rotation 320-380rad/min；Ball-milling Time is 3.5-4.5 hours；Ratio of grinding media to material is 18 ~22:1；Laser power is 82-98W；Sweep speed is 225-235mm/min；Spot diameter is 55-95 μm, and sweep span is 52-70μm；Powdering thickness is 130-170 μm.
Specifically, drum's speed of rotation is 350rad/min；Ratio of grinding media to material is 20:1；Ball-milling Time is 4 hours；Laser power For 90W；Sweep speed is 220mm/min；Spot diameter is 80 μm；Sweep span is 60 μm；Powdering thickness is 150 μm.
Further, abrading-ball is that diameter is respectively 5~10mm stainless steel balls.
Further, described Biological magnesium alloy powder is Mg-Zn series alloy powders, is preferably Mg-3Zn alloy powders.
Further, the particle diameter of the calcium silicates powder is 1~10 μm.
Further, the particle diameter of the Biological magnesium alloy powder is 50~100 μm.
Further, protective atmosphere is SF in step (1)6And CO2Gas atmosphere.
Further, protective atmosphere is the high-purity argon gas atmosphere of purity 99.999% in step (2).
Principle and advantage
The present invention, which has attempted that calcium silicate particle is combined in Biological magnesium alloy matrix using SLM technologies first, to be had There are the overall magnesium alloy materials of high corrosion drag and bioactivity.Calcium silicate particle is uniformly distributed as the second phase in the present invention In magnesium alloy substrate, the work(of its high corrosion drag and bioactivity with the sustaining degradation of Biological magnesium alloy, can be played Energy.
The present invention by the control to calcium silicate particle particle diameter, with reference to high speed ball milling and specific sintering process, realize The reunion for being uniformly distributed while avoiding calcium silicates as far as possible of calcium silicates and grow up, this is realizes its high corrosion drag Necessary condition is provided with bioactive functions.Association of the present invention in raw material particle size, high speed ball milling and SLM sintering process Under same-action, calcium silicates is evenly distributed in magnesium alloy substrate, so as to mutually strengthen the mechanical property of matrix as dispersion-strengtherning. In addition, by controlling the size of calcium silicates and content to control the degradation rate of magnesium alloy, this is the material designed by the present invention Material is used as implant, has more favorable advantage.
The present invention is after high speed ball milling, and using the SLM techniques of special parameter, the high cooldown rate of SLM techniques can make Biological magnesium alloy quickly solidifies, and so as to reduce component segregation, obtains the uniform microstructure of composition.Due to composition uniformly just not That degradation rate is inconsistent be present to occur, (when not having coating or uneven components, the degraded easily occurred is fast The inconsistent phenomenon of rate).
The present invention is when prepared by material, by the dosage of calcium silicates powder, rotational speed of ball-mill and time and selective laser The technological parameter of fusing carries out strictly controlling the problem grown up to overcome silicic acid calcium phase easily to reunite.Using different quality containing Comparative example experiment, which is carried out, with the calcium silicates powder of different-grain diameter finds that excessive calcium silicates powder can be sent out in magnesium alloy substrate It is raw to reunite, hole is formed in matrix, is unfavorable for improving the degraded drag and compressive strength of Biological magnesium alloy.Calcium silicate particle chi Very little smaller, the surface area of particle is bigger, and surface energy is bigger, and the situation of particle agglomeration is also more serious, causes the degraded of alloy Drag and mechanical property are deteriorated.Calcium silicate particle is oversized, can be excessive due to interfacial area finite sum enhancing grain spacing, Its fracture mechanism is closed with magnesium matrix and calcium silicates interfacial detachment based on calcium silicate particle cleavatge of crystals, is unfavorable for alloy mechanical property The raising of energy.Rotational speed of ball-mill and Ball-milling Time can influence the distributing homogeneity of reinforcement calcium silicate particle.When rotational speed of ball-mill or when Between not within the scope of the present invention when, or the formal distribution that calcium silicate particle can be caused to reunite between matrix powder gap, Abrading-ball can be attached to mill tube inwall, cause mixing efficiency low.
In summary, the parameter such as calcium silicate particle size, milling parameters and SLM technological parameters in the present invention Selection be not random value, but the wisdom crystallization of creative work is tested, pays many times by inventor, each Under the synergy of technological parameter, the calcium silicates of addition can be used as the second phase to exist and be evenly distributed on magnesium alloy substrate, And then obtain the Biological magnesium alloy integral material with high corrosion drag and bioactivity.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
Calcium silicates powder and Mg-3Zn alloy powders are used as raw material, by 10:90 mass ratio weighs 1g calcium silicates powder (1~10 μm of particle diameter) and 9g Mg-3Zn magnesium alloy powders (50~100 μm), in SF6And CO2Under the protection of gas, in ball mill In with the rad/min of rotating speed 350, ratio of grinding media to material 20:Dispersed magnesium alloy/calcium silicates mixed-powder is obtained after 1, ball milling 4h. It is in the protection of 99.999% high-purity argon gas, 80 μm of spot diameter, laser power 90W, sweep speed 220mm/min, sweep span 60 μm, under the process conditions of 150 μm of powdering thickness, prepare the compound Mg-3Zn alloys of calcium silicates.
Test finds that calcium silicates does not react in SLM forming processes with magnesium alloy substrate, and is uniformly dispersed in In alloy substrate (size is about 1~10 μm).Compared to Mg-3Zn alloys, the compound Mg-3Zn of the calcium silicates of mass percent 10% Alloy surface forms more apatite, and bioactivity greatly improves.Weight loss experiments result shows, composite quality hundred Divide than after 10% calcium silicates, the corrosion rate of Mg-3Zn alloys is reduced to 0.2mm/year by 1.5mm/year, and corrosion resistance is big Width improves.Meanwhile compression performance test result shows that the compressive strength of the Mg-3Zn alloys after composite calcium silicate is carried by 150MPa Height arrives 220MPa.
Embodiment 2
Calcium silicates powder and Mg-3Zn alloy powders are used as raw material, by 15:85 mass ratio weighs 1.5g calcium silicate powders End and 8.5g Mg-3Zn magnesium alloy powders, in SF6And CO2Under the protection of gas, with rotating speed 350r/min, ball material in ball mill Than 20:Dispersed magnesium alloy/calcium silicates mixed-powder is obtained after 1, ball milling 4h.99.999% high-purity argon gas protect, 80 μm of spot diameter, laser power 95W, sweep speed 240mm/min, sweep span are 70 μm, the work of 160 μm of powdering thickness Under the conditions of skill, the compound Mg-3Zn alloys of calcium silicates are prepared.
Weight loss experiments and compression performance test result show, after the calcium silicates of composite quality percentage 15%, Mg-3Zn The corrosion rate of alloy is reduced to 0.6mm/year, while compressive strength brings up to 202MPa.
In the technology of the present invention development process, following scheme (such as comparative example 1, comparative example 2, comparative example 3) is have also been attempted, But the performance of products obtained therefrom is much worse than embodiment.
Comparative example 1
Other conditions are consistent with embodiment 1, and difference is, weigh 7.5g Mg-3Zn alloy powders and 2.5g silicon Sour calcium powder, test find that calcium silicate particle is reunited in alloy substrate.The corrosion rate of prepared Biological magnesium alloy For 1.8mm/year, compressive strength 144MPa.
Comparative example 2
Other conditions are consistent with embodiment 1, and difference is, during ball milling, the rotating speed of ball mill is 200rad/min Ball milling 2h.Detect the performance of its products obtained therefrom, the corrosion rate of prepared Biological magnesium alloy is 1.2mm/year, compressive strength For 161MPa.
Comparative example 3
Other conditions are consistent with embodiment 1, and difference is, SLM controls laser power as 65W, scanning when sintering Speed is 180mm/min, spot diameter is 200 μm；Detect the performance of its products obtained therefrom, the corrosion of prepared Biological magnesium alloy Speed is 2mm/year, compressive strength 120MPa.

Claims (10)

  1. A kind of 1. magnesium alloy with high corrosion drag and bioactivity, it is characterised in that：The magnesium alloy is by Biological magnesium alloy base Body and the calcium silicates being evenly distributed in Biological magnesium alloy matrix are formed, wherein, the mass percent of calcium silicates is 5-20%.
  2. 2. the magnesium alloy according to claim 1 with high corrosion drag and bioactivity, it is characterised in that：Calcium silicates Mass percent is 8-12%.
  3. 3. the magnesium alloy according to claim 2 with high corrosion drag and bioactivity, it is characterised in that：Calcium silicates Mass percent is 10%.
  4. 4. the magnesium alloy with high corrosion drag and bioactivity according to claim any one of 1-3, it is characterised in that： The particle size of the calcium silicates is 1~10 μm.
  5. 5. a kind of method for preparing the magnesium alloy with high corrosion drag and bioactivity described in claim any one of 1-4, It is characterised in that it includes following steps：
    (1) calcium silicates powder and Biological magnesium alloy powder are pressed into design proportion under protective atmosphere, ball milling obtains in ball mill Dispersed mixed-powder；Drum's speed of rotation is 300~400rad/min, and ratio of grinding media to material is 16~24:1, Ball-milling Time be 3~ 5 hours；
    (2) using above-mentioned mixed-powder as raw material, under protective atmosphere, H is controlled2O and O2Concentration is less than 30ppm, is selected using laser Area's fusing prepares corrosion-resistant Biological magnesium alloy；In preparation process, to control laser power be 75-110W, sweep speed 200- 260mm/min, spot diameter are 45-105 μm, sweep span is 30~100 μm, powdering thickness is 100~220 μm.
  6. 6. the method according to claim 5 for preparing the magnesium alloy with high corrosion drag and bioactivity, its feature exist In：
    Drum's speed of rotation is 320-380rad/min；
    Ball-milling Time is 3.5-4.5 hours；
    Ratio of grinding media to material is 18~22:1；
    Laser power is 82-98W；
    Sweep speed is 225-235mm/min；
    Spot diameter is 55-95 μm；
    Sweep span is 52-70 μm；
    Powdering thickness is 130-170 μm.
  7. 7. the method according to claim 6 for preparing the magnesium alloy with high corrosion drag and bioactivity, its feature exist In：
    Drum's speed of rotation is 350rad/min；
    Ratio of grinding media to material is 20:1；
    Ball-milling Time is 4 hours；
    Laser power is 90W；
    Sweep speed is 220mm/min；
    Spot diameter is 80 μm；
    Sweep span is 60 μm；
    Powdering thickness is 150 μm.
  8. 8. the method for magnesium alloy of the preparation with high corrosion drag and bioactivity according to claim any one of 5-7, It is characterized in that：The particle diameter of the calcium silicates powder is 1~10 μm；The particle diameter of the Biological magnesium alloy powder is 50~100 μm.
  9. 9. the method according to claim 8 for preparing the magnesium alloy with high corrosion drag and bioactivity, its feature exist In：Described Biological magnesium alloy powder is Mg-3Zn alloy powders.
  10. 10. the method according to claim 8 for preparing the magnesium alloy with high corrosion drag and bioactivity, its feature exist In：Protective atmosphere is SF in step (1)6And CO2Gas atmosphere；Protective atmosphere is the high-purity argon of purity 99.999% in step (2) Gas atmosphere.
CN201711011345.7A 2017-10-26 2017-10-26 A kind of magnesium alloy and preparation method thereof with high corrosion drag and bioactivity Expired - Fee Related CN107760945B (en)

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Cited By (5)

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CN111888519A (en) * 2020-08-13 2020-11-06 江西理工大学 Strontium-containing mesoporous bioglass-magnesium composite material and preparation method and application thereof
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CN113880120A (en) * 2021-11-22 2022-01-04 无锡市泽镁新材料科技有限公司 Preparation method of silicon steel-grade magnesium oxide and silicon steel-grade magnesium oxide protective film
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