CN108823469B - Sub-micron crystal superplasticity kirsite, preparation method and application - Google Patents
Sub-micron crystal superplasticity kirsite, preparation method and application Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229910000914 Mn alloy Inorganic materials 0.000 claims abstract description 74
- 239000011572 manganese Substances 0.000 claims abstract description 39
- 239000011701 zinc Substances 0.000 claims abstract description 37
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 29
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 27
- 238000001192 hot extrusion Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000003723 Smelting Methods 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 2
- 230000003746 surface roughness Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 description 10
- 238000009826 distribution Methods 0.000 description 6
- 238000005275 alloying Methods 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000012930 cell culture fluid Substances 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 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 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001887 electron backscatter diffraction Methods 0.000 description 2
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 241000973497 Siphonognathus argyrophanes Species 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000010621 bar drawing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/165—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon of zinc or cadmium or alloys based thereon
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Forging (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a kind of sub-micron crystal superplasticity kirsite, preparation method and application.The sub-micron crystal superplasticity kirsite includes: 0wt% < Mn≤5wt%, 95wt%≤Zn < 100wt%；And the crystallite dimension of the sub-micron crystal superplasticity kirsite is submicron order.The preparation method of the sub-micron crystal superplasticity kirsite includes: that pure zinc and pure manganese mixed smelting are obtained as cast condition manganese alloy；Obtained as cast condition manganese alloy is subjected to multi-pass hot extrusion, makes accumulative deflection >=90% of the as cast condition manganese alloy, to obtain sub-micron crystal superplasticity kirsite.Compared to the prior art, sub-micron crystal superplasticity kirsite of the invention, plasticity and excellent tenacity, elongation percentage is up to 150~450%, and preparation method is simple, convenient for operation, and sub-micron crystal superplasticity kirsite silk material can be prepared by further drawing process, expand the application range of kirsite.
Description
Technical field
The present invention relates to metal material processing technical fields, are specifically related to sub-micron crystal superplasticity kirsite, its preparation
Method and application.
Background technique
Metallic zinc be a kind of diamagnetism, the metal with close-packed hexagonal structure, zinc and kirsite building, household electrical appliance and
It has a wide range of applications in automobile and other industries, in recent years, kirsite is even more to become the potential biological medical degradable of a new generation
Metal.But, the crystal structure of zinc determines that the slip system of pure zinc is less, and plasticity is poor.Although can by addition alloying element
To improve its intensity and plasticity, but if as medical degradable metal, it is necessary to exclude the routine that aluminium, copper etc. are harmful to the human body
Alloying element.The intensity, plasticity and corrosion resistance of kirsite had both can be improved as a kind of common alloying element in manganese element,
It is a kind of biological friendly element again.The manganese alloy that manganese element is prepared as alloying element is while being applied to industry, also
It can be used as the option of biological medical degradable metal.
Existing manganese alloy mainly based on zinc-manganese binary, is aided with micro other elements, as cast condition manganese alloy is by rolling
The processing methods such as system, heat treatment improve its performance, but its crystallite dimension is relatively large, and the comprehensive performance of alloy cannot reach most
It is excellent.Manganese alloy has a wide range of applications, and is improved its performance by crystal grain refinement, can further expand its application range.
When crystal grain refinement to submicron-scale, the properties of material especially plasticity can be significantly improved.Sub-micron crystal superplasticity
The preparation of kirsite, which expands application range in industrial circle for kirsite, great meaning, is that aluminium closes in certain applications
The contenders of gold, magnesium alloy and copper alloy.
Summary of the invention
The main purpose of the present invention is to provide a kind of sub-micron crystal superplasticity kirsite, preparation method and application, with
Overcome deficiency in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment of the invention provides a kind of sub-micron crystal superplasticity kirsite, the sub-micron crystal superplasticity kirsite packet
The Mn of < containing 0wt%≤5wt% and 95wt%≤Zn < 100wt%；And the crystal grain ruler of the sub-micron crystal superplasticity kirsite
Very little is submicron order.
The embodiment of the invention also provides a kind of preparation methods of sub-micron crystal superplasticity kirsite, comprising the following steps:
(1) melting after mixing pure zinc with pure manganese obtains as cast condition manganese alloy；
(2) the obtained as cast condition manganese alloy of step (1) is subjected to multi-pass hot extrusion, makes the accumulative of the as cast condition manganese alloy
Deflection >=90%, to obtain sub-micron crystal superplasticity kirsite.
The embodiment of the invention also provides a kind of preparation methods of sub-micron crystal superplasticity kirsite silk material, including following step
It is rapid:
(1) by pure zinc and pure manganese mixed smelting, as cast condition manganese alloy is obtained；
(2) the obtained as cast condition manganese alloy of step (1) is subjected to multi-pass hot extrusion, makes the accumulative of the as cast condition manganese alloy
Deflection is more than or equal to 95%, to obtain sub-micron crystal superplasticity Zinc alloy bar；
(3) drawing is carried out to the obtained sub-micron crystal superplasticity Zinc alloy bar of step (2), obtains sub-micron crystal superplasticity zinc
Alloy wire.
The embodiment of the invention also provides the sub-micron crystal superplasticity kirsite or sub-micron crystal superplasticity saxonia metal wires
Material is preparing the purposes in medical metal stand material.
Compared with prior art, the beneficial effect comprise that
(1) sub-micron crystal superplasticity kirsite provided in an embodiment of the present invention has sub-micron crystal structure, contains alloy
Element manganese (Mn), the content of manganese play rush in the range of being greater than 0wt% and being less than or equal to 5wt% in kirsite system
Into the effect of refinement crystal grain, the plasticity of kirsite can be improved, can express room temperature superplasticity；
(2) sub-micron crystal superplasticity kirsite provided in an embodiment of the present invention improves the disadvantage of kirsite toughness deficiency,
Elongation percentage has reached superplastic standard, and the elongation percentage of such kirsite can reach 150~450%, has expanded kirsite in work
Application range in industry production.The sub-micron crystal superplasticity kirsite or sub-micron crystal superplasticity kirsite silk material performance of preparation are excellent
It is good, it can be used for various kirsite silk material purposes, the intravascular stent that future can be used in medical metal；
(3) sub-micron crystal superplasticity kirsite or sub-micron crystal superplasticity kirsite silk material provided in an embodiment of the present invention
Preparation method so that kirsite crystal grain refinement reaches superplasticity property to submicron order, and is prepared by controlling preparation process
Method is simple, convenient for operation.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The some embodiments recorded in invention, for those of ordinary skill in the art, without creative efforts,
It is also possible to obtain other drawings based on these drawings.
Fig. 1 is the shape appearance figure of Zn-Mn alloy prepared by the embodiment of the present invention 1；
Fig. 2 is Zn-Mn alloy grain size distribution prepared by the embodiment of the present invention 1；
Fig. 3 is the stress-strain diagram of Zn-Mn alloy prepared by the embodiment of the present invention 1；
Fig. 4 is the cellular morphology picture of Zn-Mn alloy cytotoxicity experiment prepared by the embodiment of the present invention 1；
Fig. 5 is Zn-Mn alloy grain size distribution prepared by the embodiment of the present invention 2；
Fig. 6 is Zn-Mn alloy grain size distribution prepared by the embodiment of the present invention 3；
Fig. 7 is Zn-Mn alloy wire prepared by the embodiment of the present invention 4.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution.The technical solution, its implementation process and principle etc. will be further explained as follows.
Sub-micron crystal superplasticity kirsite provided in an embodiment of the present invention, the sub-micron crystal superplasticity kirsite include
0wt% < Mn≤5wt% and 95wt%≤Zn < 100wt%；And the crystal grain ruler of the sub-micron crystal superplasticity kirsite
Very little is 0.1 μm~0.95 μm, reaches submicron order.
In some more specifically embodiments, the sub-micron crystal superplasticity kirsite include 0wt% < Mn≤
5wt%, surplus Zn.
Manganese (Mn) element plays the role of promoting refinement crystal grain in kirsite system, can improve the plasticity of kirsite.
When the content of Mn is greater than 5%, Mn is for promoting the effect of refinement crystal grain that will weaken, while the addition of a large amount of Mn is unfavorable for protecting
Hold the intensity of kirsite.When the content of Mn is 0~5% but when in the range of not including 0, promote the effect of kirsite crystal grain refinement
It will be almost the same.
In some embodiments, the Mn content in the sub-micron crystal superplasticity kirsite is greater than 0wt% and to be less than
Or it is equal to 1wt%.
In some embodiments, the crystallite dimension of the sub-micron crystal superplasticity kirsite is 0.1 μm~0.95 μm.
The preparation method of sub-micron crystal superplasticity kirsite provided in an embodiment of the present invention, comprising the following steps:
(1) melting after mixing pure zinc with pure manganese obtains as cast condition manganese alloy；
(2) the obtained as cast condition manganese alloy of step (1) is subjected to multi-pass hot extrusion, makes the accumulative of the as cast condition manganese alloy
Deflection >=90%, to obtain sub-micron crystal superplasticity kirsite.
In some embodiments, the step (1) specifically includes: pure zinc being mixed with pure manganese, at 650~700 DEG C
It after 10~30min of melting, is poured into mold in 600~650 DEG C, obtains as cast condition manganese alloy bar stock after being cooled to room temperature.
In some embodiments, the mass ratio of the pure zinc and pure manganese be 19: 1~9999: 1, preferably 99: 1~
9999∶1。
In some specific embodiments, the original of the sub-micron crystal superplasticity kirsite is mixed according to metering proportion
Material, and the raw material after 10~30min of melting, is poured into mold in 600~650 DEG C, is cooled at 650~700 DEG C
As cast condition manganese alloy is obtained after room temperature.
According to the fusing point of ingredient each in kirsite, the smelting temperature of kirsite is controlled into the melting between 650~700 DEG C
10~30min, pouring temperature not only can make each component of kirsite sufficiently dissolve each other at 600~650 DEG C, but also can reduce scaling loss,
Obtain the best as-cast structure of performance.
In some embodiments, the step (2) specifically includes: the obtained as cast condition manganese alloy turning of step (1) is gone
It descales, then multi-pass hot extrusion is carried out to the as cast condition manganese alloy.
In some embodiments, ingot casting heating temperature is 200~300 DEG C in the multi-pass hot extrusion, soaking time
It is 2~3 hours, mould heating-up temperature is 220~240 DEG C.
In some embodiments, the multi-pass hot extrusion is 10~30 passages.
In some embodiments, the deflection of every a time hot extrusion is 4%~95%.
In some embodiments, through multi-pass hot extrusion, make the accumulative deflection > 95% of the as cast condition manganese alloy.
Suitable extruding temperature is conducive to the progress of extrusion process, can also have an impact to the microstructure of material, passage
The variation of deflection can significantly affect crystallite dimension, so that the properties to material have an impact.
In some preferred embodiments, the as cast condition manganese alloy is squeezed, the extruding temperature be 230~
280 DEG C, squeezing passage is 20~30, accumulative deflection >=95% of as cast condition manganese alloy.
The embodiment of the invention provides a kind of sub-micron crystal superplasticity kirsites prepared by the method.
The preparation method of sub-micron crystal superplasticity kirsite silk material provided in an embodiment of the present invention, comprising the following steps:
(1) by pure zinc and pure manganese mixed smelting, as cast condition manganese alloy is obtained；
(2) the obtained as cast condition manganese alloy of step (1) is subjected to multi-pass hot extrusion, makes the accumulative of the as cast condition manganese alloy
Deflection >=95%, to obtain sub-micron crystal superplasticity Zinc alloy bar；
(3) drawing is carried out to the obtained sub-micron crystal superplasticity Zinc alloy bar of step (2), obtains sub-micron crystal superplasticity zinc
Alloy wire.
In some embodiments, the step (1) specifically includes: pure zinc being mixed with pure manganese, at 650~700 DEG C
It after 10~30min of melting, is poured into mold in 600~650 DEG C, obtains as cast condition manganese alloy bar stock after being cooled to room temperature.
In some embodiments, the mass ratio of the pure zinc and pure manganese be 19: 1~9999: 1, preferably 99: 1~
9999∶1。
In some embodiments, the step (2) specifically includes: the obtained as cast condition manganese alloy turning of step (1) is gone
It descales, then multi-pass hot extrusion is carried out to the as cast condition manganese alloy.
Further, after scale removal, the as cast condition manganese alloy diameter of rod difference≤0.1mm.
Further, after scale removal, surface roughness Ra≤1.4 μm of the as cast condition manganese alloy.
In some embodiments, ingot casting heating temperature is 200~300 DEG C in the multi-pass hot extrusion, soaking time
It is 2~3 hours, mould heating-up temperature is 220~240 DEG C.
In some embodiments, the multi-pass hot extrusion is 10~30 passages.
In some embodiments, the deflection of every a time hot extrusion is 4%~95%.
In some embodiments, the step (3) specifically includes: pass deformation≤5% of the drawing, drawing
Accumulative deflection >=20%.
In some embodiments, aligning and/or polishing treatment are carried out to obtained as cast condition manganese alloy silk material.
Specifically, after the drawing of sub-micron crystal superplasticity Zinc alloy bar, add up deflection >=20% compared with initial drawing,
Room temperature aligning then is carried out to the sub-micron crystal superplasticity kirsite silk material of acquisition.
The embodiment of the invention also provides the sub-micron crystal superplasticity kirsite silk materials prepared by the method.
The embodiment of the invention also provides the sub-micron crystal superplasticity kirsite or the sub-micron crystal superplasticity
Kirsite silk material is preparing the purposes in medical metal stand material.
In some specific embodiments, the sub-micron crystal superplasticity kirsite silk material can be used for various saxonia metal wires
Material purposes, the intravascular stent that future can be used in medical metal.
To make the objectives, technical solutions, and advantages of the present invention more comprehensible, by the following examples and in conjunction with attached drawing
The technical solution that present invention be described in more detail.However, selected embodiment is merely to illustrate the present invention, without limiting this hair
Bright range.
Percentage composition used in following embodiments is unless otherwise specified mass percentage, and raw material is pure zinc
(99.99wt.%) and pure manganese (99.99wt.%).
Embodiment 1:
The present embodiment mixes pure zinc and pure manganese according to mass ratio using pure zinc, pure manganese as raw material for 99.9:0.1, and will
Mixed raw material melting 20min at 650 DEG C, and poured into mold in 620 DEG C, diameter 60mm is obtained after being cooled to room temperature
Manganese alloy ingot, and cut off zinc-containing alloy ingot casting both ends and crust, obtains the manganese alloy ingot of diameter 50mm, then to obtaining
The manganese alloy ingot obtained carries out hot extrusion, and the ingot casting heating temperature is 220 DEG C, keeps the temperature 2 hours, mould heating-up temperature 230
DEG C, it is squeezed using 20 passages, first time pass deformation is 95%, and remaining pass deformation is 4%~20%, is squeezed to diameter
4mm (accumulative deflection is 99%), it is final to obtain the sub-micron crystal superplasticity manganese alloy that diameter is 4mm.
The microscopic appearance that rodlike manganese alloy is observed using EBSD obtains Fig. 1, and manganese alloy crystallite dimension is very in Fig. 1
It is tiny.Fig. 2 is the grain size distribution that EBSD is measured, and average grain size is 0.38 μm, has reached submicron order.
According to ASTM-E8-04 extension test standard, rodlike manganese alloy is prepared into stretching sample.And it is polished to sample is stretched
Later, it is cleaned by ultrasonic 5min respectively in acetone, absolute ethanol and deionized water, then, using universal material mechanics machine
Tension test is carried out at room temperature, and tensile speed 1mm/min, obtained stress-strain diagram is as shown in figure 3, tensile strength reaches
To 122MPa, elongation percentage reaches 275%.
The present embodiment also tests the biocompatibility of rodlike manganese alloy, specifically:
Leaching liquor is prepared according to ISO 10993-5:2009 standard, extraction medium is that cell culture fluid (contains 12.5% serum
Incomplete DMEM culture medium (containing dual anti-)).Extraction ratio is the ratio of surface area of sample and leaching liquor volume, is 2: 3.Extraction
Condition is in 37 DEG C of 5%CO2It is extracted 24 hours in constant incubator.
The preparation method of leaching liquor: first use deionized water ultrasonic the sub-micron crystal superplasticity manganese alloy that diameter is 4mm
Cleaning moves into Biohazard Safety Equipment after drying, and soaking disinfection 24 hours, are then placed on filter paper for manganese alloy in 75% alcohol
Upper ultraviolet-sterilization 2 hours.After sterilizing, manganese alloy is put into centrifuge tube, quantitative cell culture fluid is added, by centrifuge tube
Mouth sealing, moves into 37 DEG C of 5%CO2It is placed 24 hours in insulating box.
After L-929 cell (the American Type Culture Collection committee, Chinese Academy of Sciences cell bank) recovery, passage, with 0.5%
Trypsase makes cell fall off from culture bottle, and the cell to fall off is configured to 10 with DMEM cell culture fluid4The cell of a/mL
Suspension.96 well culture plates are taken, every hole is added the cell suspending liquid of 100 μ L, is placed in 5%CO2Culture 24 hours in constant incubator
(37±2℃).To cell it is adherent after, absorb original fluid, 100 μ L leaching liquors are added in every hole.In 5%CO2Constant incubator
After culture 72 hours, cellular morphology (as shown in Figure 4) is obtained using high intension imager.The result shows that cell morphology is rendered as
The shuttle shape of health stretching, extension converges growth, illustrates that sub-micron crystal superplasticity manganese alloy has excellent cell compatibility.
Embodiment 2
The present embodiment mixes pure zinc and pure manganese according to mass ratio using pure zinc, pure manganese as raw material for 98.5: 1.5, and will
Mixed raw material melting 30min at 660 DEG C, and poured into mold in 620 DEG C, diameter 60mm is obtained after being cooled to room temperature
Manganese alloy ingot, turning as cast condition manganese alloy bar stock surface to diameter 50mm, completely removes oxide skin, carries out to the kirsite
It squeezing, the ingot casting heating temperature is 230 DEG C, keeps the temperature 2 hours, and mould heating-up temperature is 220 DEG C, it is squeezed using 25 passages, the
Pass deformation is 85%, and remaining pass deformation is 5%~20%, and (adding up deflection is for extruding to diameter 4.5mm
99%) manganese alloy that average grain size is 0.42 μm, is obtained, grain size distribution is as shown in Figure 5.
Embodiment 3
The present embodiment is that 95:5 mixes pure zinc and pure manganese, and will mix according to mass ratio using pure zinc, pure manganese as raw material
The melting 30min at 690 DEG C of raw material afterwards, and poured into mold in 640 DEG C, diameter 60mm zinc-manganese is obtained after being cooled to room temperature
Alloy pig, turning as cast condition manganese alloy bar stock surface to diameter 50mm, completely removes oxide skin, squeezes to the kirsite
Pressure, the ingot casting heating temperature are 240 DEG C, keep the temperature 3 hours, and mould heating-up temperature is 225 DEG C, are squeezed using 13 passages, first
Secondary pass deformation is 85%, and remaining pass deformation is 4%~20%, and (adding up deflection is for extruding to diameter 6.4mm
98%) manganese alloy that crystallite dimension is 0.92 μm, is obtained, grain size distribution is as shown in Figure 6.
Embodiment 4
The present embodiment mixes pure zinc and pure manganese according to mass ratio using pure zinc, pure manganese as raw material for 99.55: 0.45, and
By mixed raw material at 680 DEG C melting 25min, and poured into mold in 630 DEG C, obtain diameter after being cooled to room temperature
60mm manganese alloy ingot, turning as cast condition manganese alloy bar stock surface to diameter 50mm, completely removes oxide skin, to the kirsite
It is squeezed, the ingot casting heating temperature is 240 DEG C, keeps the temperature 2.5 hours, and mould heating-up temperature is 220 DEG C, is squeezed using 25 passages
Pressure, first time pass deformation are 80%, and remaining pass deformation is 4%~20%, are squeezed to diameter 5mm (accumulative deflection
For 99%), the kirsite silk material for being then 3.7mm by bar drawing to diameter.Obtained round silk material is aligned, is thrown
Light is to get sub-micron crystal superplasticity kirsite silk material is arrived, as shown in Figure 7.
In addition, inventor also utilize it is corresponding in the alternate embodiments 1-4 such as above listed other process conditions
Process conditions have carried out corresponding test, the content of required verifying and close with embodiment 1-4 product.So herein not to each
The verifying content of a embodiment is explained one by one, and only illustrates the excellent place of the present patent application using Examples 1 to 4 as representative.
It should be appreciated that above-described is only some embodiments of the present invention, it is noted that for the common of this field
For technical staff, under the premise of not departing from concept of the invention, other modification and improvement can also be made, these are all
It belongs to the scope of protection of the present invention.
Claims (27)
1. a kind of sub-micron crystal superplasticity kirsite, it is characterised in that: the sub-micron crystal superplasticity kirsite includes 0wt% <
Mn≤5wt% and 95wt%≤Zn < 100wt%；And the crystallite dimension of the sub-micron crystal superplasticity kirsite is submicron order.
2. sub-micron crystal superplasticity kirsite according to claim 1, it is characterised in that: the sub-micron crystal superplasticity zinc
Alloy includes 0wt% < Mn≤1wt%.
3. sub-micron crystal superplasticity kirsite according to claim 1, it is characterised in that: the sub-micron crystal superplasticity zinc
The crystallite dimension of alloy is 0.1 μm ~ 0.95 μm.
4. a kind of preparation method of sub-micron crystal superplasticity kirsite, which comprises the following steps:
(1) melting after mixing pure zinc with pure manganese obtains as cast condition manganese alloy；
(2) the obtained as cast condition manganese alloy of step (1) is subjected to multi-pass hot extrusion, makes the accumulative deformation of the as cast condition manganese alloy
Amount >=90%, to obtain sub-micron crystal superplasticity kirsite.
5. the preparation method according to claim 4, which is characterized in that the step (1) specifically includes: by pure zinc and pure manganese
Mixing, at 650 ~ 700 DEG C after 10 ~ 30min of melting, pours into mold in 600 ~ 650 DEG C, obtains as cast condition after being cooled to room temperature
Manganese alloy bar stock.
6. the preparation method according to claim 4, it is characterised in that: in step (1), the mass ratio of the pure zinc and pure manganese
For 19:1 ~ 9999:1.
7. preparation method according to claim 6, it is characterised in that: in step (1), the mass ratio of the pure zinc and pure manganese
For 99:1 ~ 9999:1.
8. the preparation method according to claim 4, it is characterised in that: in step (2), ingot casting in the multi-pass hot extrusion
Heating temperature is 200 ~ 300 DEG C, and soaking time is 2 ~ 3 hours, and mould heating-up temperature is 220 ~ 240 DEG C.
9. the preparation method according to claim 4, it is characterised in that: in step (2), the multi-pass hot extrusion be 10 ~
30 passages.
10. the preparation method according to claim 4, it is characterised in that: in step (2), the deformation of every a time hot extrusion
Amount is 4% ~ 95%.
11. the preparation method according to claim 4, it is characterised in that: in step (2), through multi-pass hot extrusion, make described
The accumulative deflection > 95% of as cast condition manganese alloy.
12. the preparation method according to claim 4, which is characterized in that the step (2) specifically includes: by step (1) institute
As cast condition manganese alloy turning scale removal is obtained, then multi-pass hot extrusion is carried out to the as cast condition manganese alloy.
13. the sub-micron crystal superplasticity kirsite prepared by any one of claim 4-12 the method.
14. a kind of preparation method of sub-micron crystal superplasticity kirsite silk material, which comprises the following steps:
(1) by pure zinc and pure manganese mixed smelting, as cast condition manganese alloy is obtained；
(2) the obtained as cast condition manganese alloy of step (1) is subjected to multi-pass hot extrusion, makes the accumulative deformation of the as cast condition manganese alloy
Amount >=95%, to obtain sub-micron crystal superplasticity Zinc alloy bar；
(3) drawing is carried out to the obtained sub-micron crystal superplasticity Zinc alloy bar of step (2), obtains sub-micron crystal superplasticity kirsite
Silk material.
15. preparation method according to claim 14, which is characterized in that the step (1) specifically includes: by pure zinc with it is pure
Manganese mixing, at 650 ~ 700 DEG C after 10 ~ 30min of melting, pours into mold in 600 ~ 650 DEG C, is cast after being cooled to room temperature
State manganese alloy bar stock.
16. preparation method according to claim 14, it is characterised in that: in step (1), the quality of the pure zinc and pure manganese
Than for 19:1 ~ 9999:1.
17. preparation method according to claim 16, it is characterised in that: in step (1), the quality of the pure zinc and pure manganese
Than for 99:1 ~ 9999:1.
18. preparation method according to claim 14, which is characterized in that the step (2) specifically includes: by step (1)
Obtained as cast condition manganese alloy turning scale removal, then multi-pass hot extrusion is carried out to the as cast condition manganese alloy.
19. preparation method according to claim 18, which is characterized in that the step (2) specifically includes: scale removal
Afterwards, diameter of rod difference≤0.1mm of the as cast condition manganese alloy.
20. preparation method according to claim 18, which is characterized in that the step (2) specifically includes: scale removal
Afterwards, surface roughness Ra≤1.4 μm of the as cast condition manganese alloy.
21. preparation method according to claim 14, it is characterised in that: in the step (2), the multi-pass hot extrusion
Middle ingot casting heating temperature is 200 ~ 300 DEG C, and soaking time is 2 ~ 3 hours, and mould heating-up temperature is 220 ~ 240 DEG C.
22. preparation method according to claim 14, it is characterised in that: in the step (2), the multi-pass hot extrusion
For 10 ~ 30 passages.
23. preparation method according to claim 14, it is characterised in that: in the step (2), every a time hot extrusion
Deflection is 4% ~ 95%.
24. preparation method according to claim 14, which is characterized in that the step (3) specifically includes: the drawing
Pass deformation≤5%, accumulative deflection >=20% of drawing.
25. preparation method according to claim 14, it is characterised in that further include: to obtained as cast condition manganese alloy silk material into
Row aligning and/or polishing treatment.
26. the sub-micron crystal superplasticity kirsite silk material prepared by any one of claim 14-25 the method.
27. Asia described in sub-micron crystal superplasticity kirsite described in any one of claim 1,2,3,13 or claim 26
Micron crystalline superplastic kirsite silk material is preparing the purposes in medical metal stand material.
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| CN109735744B (en) * | 2019-01-28 | 2020-05-26 | 东北大学 | Zinc-based alloy bar/plate with room-temperature superplasticity and preparation method thereof |
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