CN110064750A - A kind of Biological magnesium alloy and preparation method thereof containing abundant LPSO structure - Google Patents
A kind of Biological magnesium alloy and preparation method thereof containing abundant LPSO structure Download PDFInfo
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- CN110064750A CN110064750A CN201910287598.XA CN201910287598A CN110064750A CN 110064750 A CN110064750 A CN 110064750A CN 201910287598 A CN201910287598 A CN 201910287598A CN 110064750 A CN110064750 A CN 110064750A
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 27
- 239000000956 alloy Substances 0.000 claims abstract description 27
- 239000011572 manganese Substances 0.000 claims abstract description 24
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 24
- 238000005516 engineering process Methods 0.000 claims abstract description 11
- 230000001681 protective effect Effects 0.000 claims abstract description 10
- 238000005275 alloying Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 31
- 238000000498 ball milling Methods 0.000 claims description 24
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 20
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 20
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 claims description 17
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 9
- 238000010309 melting process Methods 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- 238000000149 argon plasma sintering Methods 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- 238000003723 Smelting Methods 0.000 claims description 4
- 238000013461 design Methods 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000012890 simulated body fluid Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 2
- 229910052737 gold Inorganic materials 0.000 claims 2
- 239000010931 gold Substances 0.000 claims 2
- FDDDWPXMCZXWBM-UHFFFAOYSA-N [Ge].[Zn].[Mg] Chemical compound [Ge].[Zn].[Mg] FDDDWPXMCZXWBM-UHFFFAOYSA-N 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 30
- 230000015556 catabolic process Effects 0.000 abstract description 29
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 abstract description 6
- 239000011777 magnesium Substances 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 5
- 238000004781 supercooling Methods 0.000 abstract description 2
- 239000000155 melt Substances 0.000 abstract 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 210000000988 bone and bone Anatomy 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007943 implant Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910000927 Ge alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 231100000734 genotoxic potential Toxicity 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
- B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/32—Process control of the atmosphere, e.g. composition or pressure in a building chamber
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/36—Process control of energy beam parameters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- 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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0408—Light metal alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
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Abstract
The invention discloses a kind of Biological magnesium alloys and preparation method thereof containing abundant LPSO structure, the Biological magnesium alloy melts (SLM) technology alloying manganese by selective laser and obtains into the magnesium alloy with long period stacking order (LPSO) structure, on the one hand, magnesium alloy stacking fault energy is reduced using manganese element, intermetallic compound is reduced while increasing LPSO number of structures and is precipitated；On the other hand, increase alloy degree of supercooling using manganese element, refined crystal grain and LPSO structure, obtain having and enrich magnesium alloy that is tiny and being uniformly distributed LPSO structure.LPSO structure is formed by parallel lamellar full of matrix, fine and close catabolite is formed by preferential degradation, plays a protective role to magnesium matrix, and then the degradation drag of magnesium alloy greatly improved.
Description
Technical field
The present invention relates to a kind of Biological magnesium alloys and preparation method thereof containing abundant LPSO structure, belong to biomaterial design
And preparation technical field.
Background technique
Biological magnesium alloy has good degradability, biocompatibility, bioactivity and biological safety, meanwhile,
Also there is high specific stiffness, specific strength, density, Young's modulus and people's bone are close, and stress-shielding effect can be effectively reduced.Therefore, raw
Object magnesium alloy is considered as a kind of novel degradable medical metal material with development potential, in treatment fracture and bone defect side
Face has potential advantage.But magnesium alloy degrades too fast in human body environment as bone implant material, implantation material is caused to exist
Bone tissue just loses its mechanical integrity before not yet repairing completely；Meanwhile magnesium alloy implantation material influences during fast degradation
The pH of implant site is balanced, and is generated a large amount of hydrogen and formed hydrogen capsule, influences bone growth, these all limit magnesium alloy conduct
The clinical application of bone implant material.The degradation drag for how improving Biological magnesium alloy, makes the speed of its degradation rate Yu internal skeletonization
Degree matches, and becomes problem in the urgent need to address.
In recent years, long period stacking order (LPSO) structure has received widespread attention in terms of improving metal degradation behavior.
LPSO structure is a kind of unstable second phase for being distributed in intra-die, it can form product under fluid environment with preferential degradation
Film, thus play a protective role to matrix, and they are distributed in intra-die in parallel lamellar, this directional distribution
It can inhibit extension of the degradation process between adjacent grain.For this purpose, researcher adds rare earth element (gadolinium, yttrium, dysprosium etc.)
Into magnesium-zinc alloy, improve the degradation drag of magnesium alloy to obtain LPSO structure.Research finds the forming amount of LPSO structure
It is positively correlated with the additive amount of these rare earth elements, but the presence of the rare earth element of high-content is accompanied by between a large amount of metals in alloy
Compound, which is precipitated, causes galvanic corrosion, and the degradation drag of magnesium alloy is still difficult to meet Bone Defect Repari requirement, it is often more important that, largely
Release there may be genotoxic potential harm to human body in rare earth element body.
Summary of the invention
For using rare earth element to be added in the magnesium alloy of the magnesium alloy structure obtained containing LPSO in the prior art, deposit
It is low in LPSO structural content, it degrades the problems such as too fast, the object of the present invention is to provide a kind of containing abundant LPSO structure
Biological magnesium alloy and preparation method thereof.
To achieve the goals above, the present invention adopts the following technical scheme that,
A kind of Biological magnesium alloy containing abundant LPSO structure of the present invention, the Biological magnesium alloy are melted by selective laser
(SLM) technology alloying manganese is obtained into the magnesium alloy of the structure containing LPSO, mass fraction of the manganese in Biological magnesium alloy
0.2-0.5wt%.
The present invention initiate by selective laser smelting technology alloying manganese element into the magnesium alloy with LPSO structure,
It is found surprisingly that, on the one hand by the addition of manganese element, LPSO quantity can be increased while reducing intermetallic compound precipitation, it is another
Aspect, manganese element can Refining Mg Alloy matrix grain and LPSO structure crystal grain simultaneously, can by collective effect of both above
Improve the degradation drag for greatly improving magnesium alloy.Inventor attempted a large amount of other elements, does not play and increases LPSO structure
Effect, preferably addition manganese element, just achieve unexpected effect.
Inventors have found that the performance to the Biological magnesium alloy obtained containing abundant LPSO structure of the mass fraction of manganese has
Having a great impact, manganese content is very few, and it is limited to the promotion of LPSO content in alloy, thus have for the promotion for drag of degrading
Limit, manganese content is excessive, and more than its solid solubility limit in Biological magnesium alloy, manganese element can be precipitated with manganese simple substance particle, increases electricity
Thermogalvanic corrision is unfavorable for the raising of degradation drag.
A kind of Biological magnesium alloy containing abundant LPSO structure of the present invention, the Biological magnesium alloy are melted by selective laser
(SLM) technology alloying manganese, gadolinium are obtained into magnesium-zinc alloy, mass fraction 0.2- of the manganese in Biological magnesium alloy
0.5wt%, mass fraction 10-20wt% of the gadolinium in Biological magnesium alloy.
Preferred scheme, mass fraction 10wt% of the gadolinium in Biological magnesium alloy.
Inventors have found that optimal synergy can be played with manganese element when rare earth element is selected from gadolinium.
Preferred scheme, the magnesium-zinc alloy are Mg-3Zn-0.5Zr (ZK30).
Inventors have found that when magnesium-zinc alloy is ZK30, the addition of germanium improvement achieved is best.
Preferred scheme, mass fraction 0.35-0.5wt% of the manganese in Biological magnesium alloy.
As a further preference, mass fraction 0.5wt% of the manganese in Biological magnesium alloy.
Preferred scheme, corrosion rate of the Biological magnesium alloy in simulated body fluid are 0.15~0.4mm/year.
As a further preference, corrosion rate of the Biological magnesium alloy in simulated body fluid is 0.19~0.34mm/
year。
A kind of preparation method of the Biological magnesium alloy containing abundant LPSO structure of the present invention wraps following steps living:
Step 1
By design component with manganese powder end, gadolinium powder, magnesium-zinc alloy powder is taken, ball milling is carried out under protective atmosphere and is mixed
Powder, the revolving speed of the ball milling are 200-600rad/min, Ball-milling Time 4-8h,
Step 2
It is that raw material obtains magnesium zinc using selective laser melting process under protective atmosphere by mixed-powder obtained by step 1
Germanium alloy；
During the laser sintering process, control laser power is 50-90W, sweep speed 200-400mm/s, control
Spot diameter processed is 60-100 μm.
Preferred scheme, the partial size at the manganese powder end are 2-8 μm.
Preferred scheme, the partial size of the gadolinium powder are 5-10 μm.
Preferred scheme, the magnesium-zinc alloy powder are ZK30 powder, and partial size is 30-60 μm.
Preferred scheme, in the step 1, the revolving speed of the ball milling is 300-500rad/min, Ball-milling Time 5-
7h。
As a further preference, in the step 1, the revolving speed of the ball milling is 400rad/min, and Ball-milling Time is
6h。
Preferred scheme, in the step 2, during the laser sintering process, control laser power is 60-80W,
Sweep speed is 250-350mm/s, and control spot diameter is 70-90 μm.
As a further preference, in the step 2, during the laser sintering process, control laser power is
80W, sweep speed 300mm/s, control spot diameter are 80 μm.
Principle and advantage:
The present invention attempts the preparation using selective laser smelting technology alloying manganese into the magnesium alloy of the structure containing LPSO for the first time
Obtain a kind of Biological magnesium alloy containing abundant LPSO structure.The addition of appropriate manganese element, on the one hand, due to its unique atom half
Diameter, manganese element can reduce magnesium alloy stacking fault energy, and intermetallic compound is reduced while increasing LPSO number of structures and is precipitated；It is another
Aspect increases alloy degree of supercooling using manganese element, has refined crystal grain and LPSO structure, obtains having and enriches tiny and be uniformly distributed
The magnesium alloy of LPSO structure, LPSO structure preferential degradation forms fine and close catabolite in alloy, plays protection to magnesium matrix and makees
With, and then the degradation drag of magnesium alloy greatly improved.Manganese content is very few, and it is less that LPSO content is formed in alloy；Manganese content mistake
More, more than its solid solubility limit in the magnesium alloy, manganese element can be precipitated with manganese simple substance particle, increased galvanic corrosion, be unfavorable for
The raising for drag of degrading.
In the present invention, manganese powder end and magnesium alloy powder pass through the optimization to ball-milling technology and parameter by ball milling mixing
Selection, avoids the reunion at manganese powder end and promotes its dispersion.And when ball-milling technology and parameter be not in the range of the present invention chooses
When, more serious manganese agglomeration occurs, LPSO structure distribution is uneven in the alloy of preparation, is degrading the degradability of alloy
Energy.
Selective laser smelting technology has the characteristics that quickly to solidify, and is applied to the preparation of LPSO structure magnesium alloy, energy
It is enough to form more tiny magnesium alloy crystal grain and LPSO structure, while the precipitation of intermetallic compound is avoided, in addition, increasing manganese member
The solid solubility of element in the magnesium alloy, improving manganese element reduces the effect of magnesium alloy stacking fault energy, is more advantageous to magnesium alloy stacking fault energy
It reduces, more LPSO phases is formed, to further increase the degradation drag of magnesium alloy.
In selective laser during melting process, laser power has large effect to the performance of material, in laser power
When too low, there is hole inside institute's alloyage, reduces the degradation drag of alloy；When laser power is excessively high, alloy magnesium elements
It is easy scaling loss, manganese element content is opposite to be improved, and with the precipitation of simple substance particle form, is unfavorable for degradation drag and is improved.
In conclusion the parameters such as the selection of selective laser melting process and manganese element, manganese element content in the present invention
Selection is not random value, but the crystallization tested, made the creative labor many times by inventor, the present invention pass through to manganese
Constituent content control cooperates under the synergistic effect of peculiar selective laser melting process parameter, and a kind of regulation LPSO structure is prepared
The method for improving magnesium alloy degradation drag is expected to be applied to bio-medical field.
Detailed description of the invention
The alloy microstructure of Biological magnesium alloy of the gained containing abundant LPSO structure in Fig. 1 embodiment 1.
The alloy microstructure of Biological magnesium alloy of the gained containing abundant LPSO structure in Fig. 2 embodiment 2.
The alloy microstructure of the Biological magnesium alloy of gained structure containing LPSO in Fig. 3 comparative example 1.
Specific embodiment
It below will the present invention is further illustrated by specific embodiment.
Embodiment 1
It is last (5 μm of average grain diameter) to weigh 0.05g manganese powder, 8.95g magnesium-zinc alloy powder (ZK30 powder, 50 μm of average grain diameter)
With 1.0g gadolinium powder (8 μm of average grain diameter), the two is placed in ball mill, ball milling obtains evenly dispersed mix under protective atmosphere
Powder is closed, drum's speed of rotation is 400 revs/min, Ball-milling Time 6 hours.Using above-mentioned mixed-powder as raw material, pass through selective laser
Melting process prepares the Biological magnesium alloy of the structure containing LPSO, in preparation process, controls laser power 80W, scanning speed 300mm/
80 μm of min, spot diameter.
Test is found, forms tiny crystal grain and tiny LPSO phase in prepared alloy, and be uniformly filled in entire crystal grain
Inside, while there is no intermetallic compound that (Fig. 1) is precipitated in alloy.After alloying manganese, magnesium alloy degradation rate is from 0.61mm/
Year is reduced to 0.19mm/year.
The magnesium alloy that the fast trip of present invention degradation is 0.61mm/year refers to, compared with Example 1, only first without addition manganese
Element has LPSO structure magnesium alloy containing gadolinium.
Embodiment 2
It is last (5 μm of average grain diameter) to weigh 0.02g manganese powder, 8.98g magnesium-zinc alloy powder (ZK30 powder, 50 μm of average grain diameter)
With 1.0g gadolinium powder (8 μm of average grain diameter), the two is placed in ball mill, ball milling obtains uniformly mixed mix under protective atmosphere
Powder is closed, drum's speed of rotation is 400 revs/min, Ball-milling Time 6 hours.Using above-mentioned mixed-powder as raw material, pass through selective laser
Melting process prepares the Biological magnesium alloy of the structure containing LPSO, in preparation process, controls laser power 80W, scanning speed 300mm/
80 μm of min, spot diameter.
Test discovery forms more LPSO structures but simultaneously compared to the magnesium alloy for being not added with manganese element in prepared alloy
The entire intra-die of underfill, while (Fig. 2) is precipitated in a small amount of intermetallic compound, the degradation rate of alloy is 0.25mm/
year。
Embodiment 3
It is last (5 μm of average grain diameter) to weigh 0.05g manganese powder, 8.95g magnesium-zinc alloy powder (ZK30 powder, 50 μm of average grain diameter)
With 1.0g gadolinium powder (8 μm of average grain diameter), the two is placed in ball mill, ball milling obtains evenly dispersed mix under protective atmosphere
Powder is closed, drum's speed of rotation is 300 revs/min, Ball-milling Time 5 hours.Using above-mentioned mixed-powder as raw material, pass through selective laser
The medical magnesium alloy of fusing preparation structure containing LPSO；In preparation process, control laser power 80W, scanning speed 300mm/min,
80 μm of spot diameter.
Test discovery, forms LPSO structure abundant in prepared alloy, compared to the magnesium alloy for being not added with manganese element,
Degradation rate is reduced to 0.34mm/year from from 0.61mm/year.
Embodiment 4
It is last (5 μm of average grain diameter) to weigh 0.05g manganese powder, 8.95g magnesium-zinc alloy powder (ZK30 powder, 50 μm of average grain diameter)
With 1.0g gadolinium powder (8 μm of average grain diameter), the two is placed in ball mill, ball milling obtains evenly dispersed mix under protective atmosphere
Powder is closed, drum's speed of rotation is 400 revs/min, Ball-milling Time 6 hours.Using above-mentioned mixed-powder as raw material, pass through selective laser
Melting process prepares the Biological magnesium alloy of the structure containing LPSO, in preparation process, controls laser power 50W, scanning speed 300mm/
80 μm of min, spot diameter.
Test is found, is formed LPSO phase abundant in prepared alloy, and be full of entire intra-die, is formed tiny crystalline substance
Grain and tiny LPSO phase, LPSO is evenly distributed disperse in intra-die, while not having intermetallic compound precipitation in alloy.Drop
Solution rate is 0.22mm/year.
In the technology of the present invention development process, following scheme has also been attempted, but the performance of products obtained therefrom is much worse than implementation
Example.
Comparative example 1
Other conditions are consistent with embodiment 1, the difference is that: weigh 0.08g manganese powder end, 8.92g magnesium-zinc alloy powder
End and 1.0g gadolinium powder.Test is found, LPSO Xiang Bingyou simple substance manganese distribution of particles is formed in prepared alloy in intra-die (figure
3), degradation rate is increased to 0.48mm/year.
Comparative example 2
Other conditions are consistent with embodiment 1, the difference is that: in preparation process, control laser power 40W, scanning
80 μm of speed 300mm/min, spot diameter.Test discovery, the consistency of prepared alloy is lower, this be laser energy density not
Caused by magnesium-zinc alloy powder, gadolinium powder and manganese powder end can be made to be completely melt, degradation rate is increased to 0.61mm/year.
Comparative example 3
Other conditions are consistent with embodiment 1, the difference is that: in preparation process, control laser power 90W, scanning
40 μm of speed 600mm/min, spot diameter.Test finds there is the precipitation of simple substance manganese particle in prepared alloy, this is because power
Excessively high magnesium evaporation, causes the relative amount of manganese in alloy to improve, is precipitated in simple substance, degradation rate is increased to 0.57mm/year.
Comparative example 4
Other conditions are consistent with embodiment 1, the difference is that: drum's speed of rotation is 150 revs/min, Ball-milling Time 2
Hour.Test finds that the LPSO phase formed in magnesium alloy is unevenly distributed, and degradation surface is uneven and etch pit occurs.
Comparative example 5
Other conditions are consistent with embodiment 1, the difference is that: manganese element is replaced with into elemental lithium, as a result, it has been found that, magnesium
The LPSO phase structure formed in alloy is reduced, and intermetallic compound phase increases, and degradation rate is increased to 0.55mm/year.
Comparative example 6
Other conditions are consistent with embodiment 1, the difference is that: manganese element is replaced with into zr element, as a result, it has been found that, magnesium
The LPSO phase structure formed in alloy is reduced, and intermetallic compound phase increases, and degradation rate is increased to 0.68mm/year.
Comparative example 7
Other conditions are consistent with embodiment 1, the difference is that: rare-earth element gadolinium is substituted for rare-earth element cerium, is tied
There is not LPSO structure mutually to be formed in fruit discovery magnesium alloy, can be only formed intermetallic compound phase, magnesium alloy degradation rate is
0.55mm/year。
Comparative example 8
Other conditions are consistent with embodiment 1, the difference is that: rare-earth element gadolinium is substituted for rare-earth elements of lanthanum, is tied
There is not LPSO structure mutually to be formed in fruit discovery magnesium alloy, can be only formed intermetallic compound phase, magnesium alloy degradation rate is
1.22mm/year。
Claims (10)
1. a kind of Biological magnesium alloy containing abundant LPSO structure, it is characterised in that: the Biological magnesium alloy is molten by selective laser
Change technology alloying manganese is obtained into the magnesium alloy of the structure containing LPSO, mass fraction 0.2- of the manganese in Biological magnesium alloy
0.5wt%.
2. a kind of Biological magnesium alloy containing abundant LPSO structure according to claim 1, it is characterised in that: the biology magnesium
Alloy is obtained by selective laser smelting technology alloying manganese, gadolinium into magnesium-zinc alloy, matter of the manganese in Biological magnesium alloy
Measure score 0.2-0.5wt%, mass fraction 10-20wt% of the gadolinium in Biological magnesium alloy.
3. a kind of Biological magnesium alloy containing abundant LPSO structure according to claim 2, it is characterised in that: the magnesium zinc closes
Gold is ZK30 alloy.
4. a kind of Biological magnesium alloy containing abundant LPSO structure according to claim 1 or 2, it is characterised in that: the manganese
Mass fraction 0.35-0.5wt% in Biological magnesium alloy.
5. a kind of Biological magnesium alloy containing abundant LPSO structure according to claim 1 or 2, it is characterised in that: the life
Corrosion rate of the object magnesium alloy in simulated body fluid is 0.15~0.4mm/year.
6. preparing a kind of preparation side of Biological magnesium alloy containing abundant LPSO structure as described in claim 1-5 any one
Method, which is characterized in that wrap following steps living:
Step 1
By design component with manganese powder end, gadolinium powder, magnesium-zinc alloy powder is taken, ball milling is carried out under protective atmosphere and obtains mixed powder
End, the revolving speed of the ball milling are 200-600rad/min, Ball-milling Time 4-8h,
Step 2
It is raw material by mixed-powder obtained by step 1, under protective atmosphere, magnesium zinc germanium is obtained using selective laser melting process and is closed
Gold；
During the laser sintering process, control laser power is 50-90W, sweep speed 200-400mm/s, controls light
Spot diameter is 60-100 μm.
7. a kind of preparation method of Biological magnesium alloy containing abundant LPSO structure according to claim 6, which is characterized in that
The partial size at the manganese powder end is 2-8 μm, and the partial size of the gadolinium powder is 5-10 μm.
8. a kind of preparation method of Biological magnesium alloy containing abundant LPSO structure according to claim 6, which is characterized in that
The magnesium-zinc alloy powder is ZK30 powder, and partial size is 30-60 μm.
9. a kind of preparation method of Biological magnesium alloy containing abundant LPSO structure according to claim 6: it is characterized in that,
In the step 1, the revolving speed of the ball milling is 300-500rad/min, Ball-milling Time 5-7h.
10. a kind of preparation method of Biological magnesium alloy containing abundant LPSO structure according to claim 6: its feature exists
In in the step 2, during the laser sintering process, control laser power is 60-80W, sweep speed 250-
350mm/s, control spot diameter are 70-90 μm.
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