CN109161766A - A kind of Biological magnesium alloy and preparation method thereof of the layer of consolidation containing amorphous - Google Patents
A kind of Biological magnesium alloy and preparation method thereof of the layer of consolidation containing amorphous Download PDFInfo
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- CN109161766A CN109161766A CN201811107808.4A CN201811107808A CN109161766A CN 109161766 A CN109161766 A CN 109161766A CN 201811107808 A CN201811107808 A CN 201811107808A CN 109161766 A CN109161766 A CN 109161766A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
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- 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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- 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
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- 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
- C22F3/00—Changing the physical structure of non-ferrous metals or alloys by special physical methods, e.g. treatment with neutrons
Abstract
The invention discloses a kind of Biological magnesium alloys and preparation method thereof of layer of consolidation containing amorphous, belong to Biological magnesium alloy design and amorphous manufacturing technology field.The Biological magnesium alloy successively includes substrate, heat affected layer, amorphous consolidation layer from the inside to surface.The magnesium alloy is with atomic percentage, including following component: magnesium 55-66%, zinc 28-35%, calcium 5-10%.Preparation method are as follows: by design component with high-purity magnesium ingot, zinc ingot metal, Mg-30Ca intermediate alloy is taken, the melting under protective atmosphere obtains Biological magnesium alloy block after pouring into mold.Remelting is carried out to Biological magnesium alloy block surface using laser melting process under protective atmosphere; obtain the Biological magnesium alloy of the layer of consolidation containing amorphous, the laser melting process parameter are as follows: laser power 400-600W, scanning speed 60-120mm/s; spot diameter is 3-5mm, overlapping rate 50%.Preparation method of the invention is simple and environmentally-friendly, and the Biological magnesium alloy of the gained layer of consolidation containing amorphous has excellent corrosion resistance.
Description
Technical field
The present invention relates to a kind of Biological magnesium alloys and preparation method thereof of layer of consolidation containing amorphous, belong to Biological magnesium alloy design
And manufacturing technology field.
Background technique
Due to its excellent mechanical compatibility, biocompatibility and degradability, becoming biology in recent years can drop magnesium alloy
The research hotspot of solution implantation Material Field.The intracorporal magnesium alloy materials of implantation biology slowly degrade in vivo and finally by new lifeves
Tissue replaces, and eliminates the puzzlement of second operation, alleviates the pain and medical burden of patient.But the chemical property of magnesium is extremely living
Sprinkle (- 2.36VSHE), and the oxidation film generated in corrosion process is loose porous (PBR=0.8), and magnesium and magnesium alloy is caused to exist
It is premature in human physiological environment containing chloride ion to lose its effect, while magnesium alloy degradation speed is too fast, leads to local pH
Value increases, and is unfavorable for the growth and stabilization of cambium.Therefore biological medical magnesium alloy degradation rate during human body is on active service
Too fast is a urgent problem to be solved.
The improvement of corrosion stability of magnesium alloy can be by adding alloying element or being surface-treated.Adding alloying element can be direct
The corrosion resistance for improving magnesium alloy materials, improves its corrosion potential, influences corrosion kinetics and erosion profile.But since implantation is given birth to
The intracorporal material of object is necessary for nontoxic element, therefore improving corrosion resistance using addition alloying element becomes more difficult.Traditional table
Face modification has the methods of chemical composition coating, plating, anodic oxidation, thermal spraying, and above method needs to add chemical reagent, be unfavorable for
It is environmentally protective.Laser remolten is that laser technology, the combined interleaving techniques of computer control system are related to physics, are changed
The fields such as, metal metallurgy smelting, it is easy to operate environmentally protective.Amorphous alloy is quenched and solidified by super, and atom comes not when alloy graining
And ordered arrangement crystallization, obtained solid alloy is longrange disorder structure, so that non crystalline structure be promoted to be formed.This amorphous alloy
It is with many unique performances, such as excellent magnetism, corrosion resistance, wearability, high intensity, high rigidity, block amorphous alloy
The new material of rising in recent years, to prepare bulk amorphous alloy to the corrosion resistance significant effect for improving Biological magnesium alloy.And it prepares
The approach of amorphous alloy has water quenching, copper mold casting, gets rid of band, directional solidification, powder metallurgic method etc., will limit contour alloy
Size shape is unfavorable for subsequent bio material clinical application.In existing technology, biological block is prepared using the method for laser
There is not been reported for the research of magnesium alloy amorphous coating.
Patent (CN 107164711A) discloses a kind of method that short-pulse laser improves Mg alloy surface corrosion resistance,
Remelted layer is obtained using short-pulse laser, however under conditions of the patent, remelted layer obtained and not formed amorphous consolidation
Layer, therefore corrosion resistance promotion is limited.
It is to use preset coating method and synchronous powder feeding system method at present to obtain Biological magnesium alloy amorphous consolidation layer, regardless of
Which kind of method requires to introduce other metallic elements, to form amorphous consolidation layer, however these metallic elements, such as Fe, Ni, Cu
Deng, the solid solubility in Mg is extremely limited, is distributed in Mg grain boundaries in netted, active cathode characteristic is shown in synthetic,
Alloy surface is promoted to form micro cell, it is totally unfavorable to the corrosion resistance of magnesium synthetic, while alloying element is in degradation process
It cannot be absorbed by the human body, there is certain toxicity.Therefore such methods are formed by the magnesium alloy of the layer of consolidation containing amorphous not
Suitable for as bio-medical material.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide one kind to have excellent anticorrosive performance, biofacies
The Biological magnesium alloy and preparation method thereof of the good layer of consolidation containing amorphous of capacitive.
To achieve the goals above, the invention provides the following technical scheme:
A kind of Biological magnesium alloy of the layer of consolidation containing amorphous of the present invention, the Biological magnesium alloy successively include base from the inside to surface
Material, heat affected layer, amorphous consolidation layer；The magnesium alloy is with atomic percentage, including following component:
Magnesium 55-66%, zinc 28-35%, calcium 5-10%.
Preferred scheme, the magnesium alloy is with atomic percentage, including following component:
Magnesium 60-66%, zinc 29-35%, calcium 5%.
As a further preference, the magnesium alloy is with atomic percentage, including following component:
Magnesium 60%, zinc 35%, calcium 5%.
Biological magnesium alloy provided in the present invention, wherein heat affected layer and amorphous consolidation layer are remelted layer, heat affecting
Layer is the part for failing to be formed non crystalline structure in remelted layer.
Preferred scheme, the amorphous consolidation layer with a thickness of 100-150 μm.
Technical solution of the present invention, provided is the magnesium-zinc-calcium alloy system for being capable of forming amorphous consolidation layer, and is had
There are good biocompatibility and corrosion resistance, is suitable for bio-medical material.
A kind of preparation method of the Biological magnesium alloy of the layer of consolidation containing amorphous of the present invention, by design component with take magnesium ingot, zinc ingot metal,
Mg-30Ca intermediate alloy carries out melting under protective atmosphere, and cast molding obtains Biological magnesium alloy block, carries out surface and locates in advance
Then reason carries out remelting to Biological magnesium alloy block surface using laser melting process under protective atmosphere, obtain molten containing amorphous
The Biological magnesium alloy of solidifying layer, the laser melting process parameter are as follows: laser power 400-600W, scanning speed 60-
120mm/s, spot diameter 3-5mm, overlapping rate 50%.
Preferred scheme, the magnesium ingot, zinc ingot metal purity >=99.99%, Mg-30Ca intermediate alloy in Ca element quality
Score is 29.74%.
In the present invention, it is the fiber laser device of 1024nm that laser melting process, which selects optical maser wavelength,.
In the present invention due to using melting method obtain Biological magnesium alloy block, only need to magnesium ingot,
The ingredient of zinc ingot metal and Mg-30Ca intermediate alloy is defined, and avoid using alloy powder carry out melting when it is pure for powder
The requirement of the parameters such as degree, partial size, therefore ball-milling technology process can be saved, it economizes on resources.It is also avoided simultaneously using alloyed powder
When end carries out smelting, due to powder volatilization, bring loss of material and ingredient change.
Preferred scheme, the fusion process are that melting container is first heated to 400-450 DEG C, and magnesium ingot is then added, and
Magnesium alloy covering agent is sprinkled on magnesium ingot surface；700-800 DEG C is then heated to, 10-15min is kept the temperature after magnesium ingot fusing, by furnace
Temperature is adjusted to 720-740 DEG C, and preheated spelter and Mg-30Ca intermediate alloy is then added, acquisition is stirred evenly after to be melted
Alloy melt then heats to 740-760 DEG C and is refined, and the old magnesium alloy covering agent on alloy melt surface is removed after refining,
One layer of magnesium alloy covering agent is sprinkled again on alloy melt surface, is cooled to 720-730 DEG C, stands 10-15min, removes alloy
The slag of melt liquid level is obtained to cast alloys melt；Protective atmosphere is continually fed into the fusion process.
In the present invention, old magnesium alloy covering agent, which refers to, is first heated to 400-450 DEG C for melting container, and magnesium is then added
Ingot, and the magnesium alloy covering agent sprinkled on magnesium ingot surface are referred to as old magnesium alloy covering agent after refining process.
The process of preferred scheme, the cast molding is that will pour to cast to cast alloys melt to preheat through 230-250 DEG C
Metal die in, up to Biological magnesium alloy block after molding.
As a further preference, in the refining process, be added refining agent, the additional amount of the refining agent be magnesium ingot,
1~1.5wt% of zinc ingot metal, Mg-30Ca gross mass.
Preferably in the refining process, refining agent is put into bell jar as further, bell jar immerses melt 2/3-
3/4 depths, agitation, makes alloy melt generate strong circulative convection, while constantly spreading refining agent in bath surface, molten to alloy
Until bright mirror surface is presented in body fluid face.
The refining agent being put into bell jar is first wrapped with paper.
In the present invention, the magnesium alloy covering it is known in the art that commercially available can be used in magnesium alloy covering agent, refining agent
Agent, refining agent.
Inventors have found that effectively being controlled the temperature of melting, addition programs through the invention, melting can be obtained
The uniform Biological magnesium alloy block of alloying component has metallic luster, and not oxidized.
In the present invention, fusion process is most important for that finally can obtain the Biological magnesium alloy of the layer of consolidation containing amorphous
, if the condition of fusion process cannot be controlled, on the one hand will lead to can not obtain qualified Biological magnesium alloy block, Yi Kai
It splits.On the other hand, Biological magnesium alloy block uneven components, so that can not successfully be obtained in post laser melting process
Layer is coagulated in amorphous remelting.
Preferred scheme, the protective gas are high purity argon, and the purity of the high purity argon is more than or equal to
99.99%.
Preferred scheme, the preprocessing process are that Biological magnesium alloy block successively uses 400-600-800-1000 mesh
Sand paper is polished, and polishing, which is placed in acetone, carries out ultrasonic cleaning, in Biological magnesium alloy block surface black after drying
Marking pen is smeared uniform.
Since the light absorptive of magnesium alloy is not strong, so smearing uniformly in magnesium alloy block surface black marking pen to improve
Absorptance.
Preferred scheme, the laser power are 400-500W, scanning speed 90-120mm/s.
As a further preference, the laser power is 500W, scanning speed 90mm/s.
Principle and advantage:
Technical solution of the present invention, what inventor initiated is obtained by the way of laser remolten on magnesium-zinc-calcium alloy block
Amorphous consolidation layer was obtained, the characteristics of using laser, keeps it molten to quite high temperature in the local location heat build-up of Mg alloy surface
Change, is then act through the heat absorption and its conduction fuel factor of colder metallic matrix, molten metal surface is made quickly to be quenched solidification, from
And form amorphous layer.
For magnesium base alloy, the complexity for forming amorphous structure has very big difference, such as alloy system Mg-
Cu-Y, just with the very strong ability for forming amorphous, a large amount of research at present is all to concentrate on this kind of alloy, but due to its component
For biological alloy, biodegrade can occur after implanting, generated excess Cu element and Y element are for disease
The cell Proliferation and tissue repair of trouble have certain inhibiting effect.However for Mg-Zn-Ca alloy system of the invention, but belong to
In the weaker alloy system of formation amorphous ability, therefore up to the present there are no pass through laser remolten about Mg-Zn-Ca alloy
Method formed amorphous consolidation layer report.
The present invention through a large number of experiments, is on the one hand precisely controlled the alloy composition ratio of Mg-Zn-Ca, on the other hand logical
The process for crossing control melting first melts out the magnesium alloy block for suitably forming amorphous consolidation layer, then by effectively controlling laser
The selection of technological parameter in reflow process, is finally obtained the magnesium alloy with amorphous consolidation layer, and present invention gained magnesium alloy is non-
Up to 100-150 μm, the corrosion resistance of Biological magnesium alloy significantly improves the thickness of brilliant consolidation layer, with regard to charge transfer resistance RPNumber
5-6 times is improved relative to untreated Mg-Zn-Ca alloy for value.
Preparation method of the invention is simple, due to not having to add other metal components, it is ensured that gained is molten containing amorphous
The Biological magnesium alloy of solidifying layer is the biodegradable material with good biocompatibility and appropriate degradation rate.
Detailed description of the invention
Microscopic appearance figure is organized in Biological magnesium alloy surface longitudinal section combined area under different scanning speed in Fig. 1 embodiment 1,
In: (a) master alloy；(b)500W,60mm/s；(c)500W,90mm/s；(d)500W,120mm/s；
Fig. 2 is Biological magnesium alloy surface remelting area ladder when laser power is 500W, scanning speed is 60mm/s in embodiment 1
Spend tissue microscopic appearance figure, in which: (a) gradient layer, (b) amorphous layer, (c) heat affected layer, (d) substrate；
Fig. 3 is Biological magnesium alloy surface remelting area ladder when laser power is 500W, scanning speed is 90mm/s in embodiment 1
Spend tissue microscopic appearance figure, in which: (a) gradient layer, (b) amorphous layer, (c) heat affected layer, (d) substrate；
Fig. 4 is Biological magnesium alloy surface remelting area when laser power is 500W, scanning speed is 120mm/s in embodiment 1
Gradient structure microscopic appearance figure, in which: (a) gradient layer, (b) amorphous layer, (c) heat affected layer, (d) substrate；
Fig. 5 is the electrochemical tests test result of gained Biological magnesium alloy under different scanning speed in embodiment 1,
In: (a) master alloy；(b)500W,60mm/s；(c)500W,90mm/s；(d)500W,120mm/s；
Fig. 6 is the electrochemical impedance spectroscopy test result of gained Biological magnesium alloy under different scanning speed in embodiment 1,
In: (a) master alloy；(b)500W,60mm/s；(c)500W,90mm/s；(d)500W,120mm/s.
Specific embodiment
Below in conjunction with attached drawing to the preferred embodiment of the present invention, the invention will be further described.
In embodiments of the present invention, magnesium alloy covering agent used, refining agent purchase have in Jiaozuo City inflammation space non-ferrous metal
Limit company.
Embodiment 1
The present embodiment is shown in the identical situation of other process conditions, laser power 500W, and scanning speed is respectively
The Biological magnesium alloy of the layer of consolidation containing amorphous obtained by 60mm/s, 90mm/s, 120mm/s in the case of 3 kinds.
The ratio for being 60:35:5 in atomic ratio prepares magnesium ingot, zinc ingot metal and the mass content that purity is 99.99%
29.73% Mg-30Ca intermediate alloy.After first cast steel crucible is put into shaft furnace and is warming up to 400 DEG C, it is added in crucible
Pure magnesium, and one layer of magnesium alloy covering agent is sprinkled on MAG block surface.700 DEG C are warming up to, keeps the temperature 10min after MAG block is completely melt,
Furnace temperature is adjusted to 720 DEG C, pure spelter and Mg-30Ca intermediate alloy after 200 DEG C of preheatings is added, after alloy is completely melt
It is stirred evenly with stirring spoon.Melt is risen to 740 DEG C later and is refined (refining agent dosage is the 1% of total charging weight).Essence
It is good to refine agent paper bag, is put into bell jar, bell jar immerses 2/3 depths of melt, and carrying out slowly agitation makes melt generate strong circulation
Convection current, while refining agent constantly is spread in bath surface, until bright mirror surface is presented to liquid level.After refining, remove sidewall of crucible and
Flux on bath surface, then sprinkle one layer of new coverture.Furnace temperature is down to 720 DEG C, standing is taken off on liquid level after ten minutes
Slag.Taking-up is preheated to 250 DEG C of metal die before casting, and magnesium liquid is poured smoothly into mold.In entire fusion process
In, it is all constantly passed through high-purity argon gas into crucible and carries out melt protecting.
By above procedure melting obtain ingredient uniformly, the Biological magnesium alloy block with metallic luster, use wire cutting
Machine-cut makees five samples under same parameters at the sample having a size of 30 × 20 × 8mm size.
(2) sample cut is successively successively polished on the dry sand paper of 400-600-800-1000 mesh, removes metal watch
Surface oxidation film carries out acetone ultrasonic wave and goes oil processing after polishing.Since magnesium alloy light absorptive is not strong, therefore need to be by its surface black
Marking pen smear as absorbed layer, so as to improve the absorptance of Biological magnesium alloy.
(3) on the laser work platform that sample is put into optical fiber laser after carrying out the above pretreatment, setting laser parameter and
It is displaced program.Parameter setting is as follows: control laser power is 500W, and scanning speed is respectively 60mm/s, 90mm/s, 120mm/s,
Control spot diameter is 3mm, overlapping rate 50%.It is passed through startup program after the argon gas that purity is 99.99% is protected, finally
Remelted layer is obtained on Biological magnesium alloy surface.
(4) magnesium alloy after processing is completed is taken out from workbench, it is subjected to simple cleaning treatment with alcohol, is blown
It is dry.
Steamed bun peak is observed by X-ray diffractometer detection, this Biological magnesium alloy of explanation after laser treatment generates
Amorphous coating, Fig. 1 are that microscopic appearance is organized in Biological magnesium alloy surface longitudinal section combined area under different scanning speed in embodiment 1
Figure.Fig. 2,3,4 are respectively had the pattern of the sample surfaces difference heat affected layer under the processing of same laser technical parameters
Body surface sign, Fig. 2 are Biological magnesium alloy surface remelting area ladder when laser power is 500W, scanning speed is 60mm/s in embodiment 1
Tissue microscopic appearance figure is spent, Fig. 3 is Biological magnesium alloy table when laser power is 500W, scanning speed is 90mm/s in embodiment 1
Face reflow zone gradient structure microscopic appearance figure, Fig. 4 are raw when laser power is 500W, scanning speed is 120mm/s in embodiment 1
Object Mg alloy surface reflow zone gradient structure microscopic appearance figure,.By can be seen that Fig. 1 to 4, laser power be 500W, sweep
Retouch speed be 90mm/s when, the amorphous consolidation layer of formation is most thick and best, the surface after laser treatment there are about with a thickness of
300-350 μm of laser remolten layer, remelted layer show the microcosmic microscopic structure different from matrix, can form thickness in metal surface
The amorphous layer that up to 100-150 μm of degree.It is more fine and close that remelted layer compares tissue with substrate, and different zones microscopic structure is not
Together.After polishing, polishing, cleaning, corrode 10-15s with 1% nitric acid alcohol, can be seen that substrate is held from erosion profile figure
It is also easy to produce spot corrosion, so that the metal in part spot corrosion region falls off to form hole.Carry out swashing for corrosion test together with substrate
Light remelted layer, due to forming amorphous consolidation layer, corrosion resisting property increases and not formed corrosion hole, corrosion product are few.
Fig. 5 be the Biological magnesium alloy use SBF solution as the polarization curve of corrosive liquid, it can thus be concluded that: by laser
Metal phase after remelting significantly improves master alloy corrosion resisting property, be 500W by laser power, scanning speed be 90mm/s with
Master alloy compares it is found that the corrosion current density of this Biological magnesium alloy reduces an order of magnitude, and corrosion potential is shuffled
0.343V.By for the dynamics and thermodynamics corroded, corrosion resistance is significantly improved.
Fig. 6 is that the Biological magnesium alloy is using the SBF solution can be obtained as the impedance spectra of corrosive liquid by Fig. 6: biology magnesium conjunction
Gold all shows as single appearance impedance before and after Laser Experiments, and metal has shown dispersion effect.Data are precisely intended with software
After conjunction, table 1 is obtained.As known from Table 1, its charge transfer resistance of magnesium alloy of the present embodiment 1 after laser remolten RPIt is significant to increase
Greatly, charge transfer resistance increase the nearly Biological magnesium alloy amorphous alloy six times, formed after laser machining show it is excellent resistance to
Corrosive nature.
In 1 embodiment 1 of table under different scanning speed gained Biological magnesium alloy electrochemical impedance spectroscopy fitting result
Embodiment 2
(1) ratio for being 66:29:5 in atomic ratio prepares magnesium ingot, zinc ingot metal and the mass content that purity is 99.99%
29.73% Mg-30Ca intermediate alloy.After first cast steel crucible is put into shaft furnace and is warming up to 400 DEG C, it is added in crucible
Pure magnesium, and one layer of magnesium alloy covering agent is sprinkled on MAG block surface.700 DEG C are warming up to, keeps the temperature 10min after MAG block is completely melt,
Furnace temperature is adjusted to 720 DEG C, pure spelter and Mg-30Ca intermediate alloy after 200 DEG C of preheatings is added, after alloy is completely melt
It is stirred evenly with stirring spoon.Melt is risen to 740 DEG C later and is refined (refining agent dosage is the 1% of total charging weight).Essence
It is good to refine agent paper bag, is put into bell jar, bell jar immerses 2/3 depths of melt, and carrying out slowly agitation makes melt generate strong circulation
Convection current, while refining agent constantly is spread in bath surface, until bright mirror surface is presented to liquid level.After refining, remove sidewall of crucible and
Flux on bath surface, then sprinkle one layer of new coverture.Furnace temperature is down to 720 DEG C, standing is taken off on liquid level after ten minutes
Slag.Taking-up is preheated to 250 DEG C of metal die before casting, and magnesium liquid is poured smoothly into mold.In entire fusion process
In, it is all constantly passed through high-purity argon gas into crucible and carries out melt protecting.
By above procedure melting obtain ingredient uniformly, the Biological magnesium alloy block with metallic luster, use wire cutting
Machine-cut is at the sample having a size of 30 × 20 × 8mm size.
(2) sample cut is successively polished on the dry sand paper of 400-600-800-1000 mesh, removes metal surface oxygen
Change film, acetone ultrasonic cleaning is carried out after polishing and goes oil processing.Since magnesium alloy light absorptive is not strong, therefore its surface need to be sticked black
Coloring agent band is as absorbed layer, so as to improve the light absorptive of Biological magnesium alloy.
(3) on the laser work platform that sample is put into optical fiber laser after carrying out the above pretreatment, setting laser parameter and
It is displaced program.Parameter setting is as follows: control laser power is 600W, and scanning speed 90mm/s, control spot diameter is 3mm,
Overlapping rate is 50%.Startup program after the argon gas that purity is 99.99% is protected is opened, is finally weighed on Biological magnesium alloy surface
Crucible zone.
(4) magnesium alloy after processing is completed is taken out from workbench, it is subjected to simple cleaning treatment with alcohol, is blown
It is dry.
The middle remelted layer of the resulting Biological magnesium alloy of the present embodiment 2 with a thickness of 580-800 μm, X-ray detection is not found
Steamed bun peak, while in scanning electron microscope in observation pattern, alloying component is finer and close after laser treatment, but is 600W in power
It is and not formed complete amorphous coating.It is only the integrated structure of amorphous and crystalline state, through detecting, charge transfer resistance RPFor
1563, after laser treatment, alloying component more uniformization, corrosion resisting property improves old friend, but compares embodiment 1
In had complete coating corrosion resistance improve it is limited.
Embodiment 3
(1) ratio for being 60:35:5 in atomic ratio prepares magnesium ingot, zinc ingot metal and the mass content that purity is 99.99%
29.73% Mg-30Ca intermediate alloy.After first cast steel crucible is put into shaft furnace and is warming up to 450 DEG C, it is added in crucible
Pure magnesium, and one layer of magnesium alloy covering agent is sprinkled on MAG block surface.800 DEG C are warming up to, keeps the temperature 10min after MAG block is completely melt,
Furnace temperature is adjusted to 740 DEG C, pure spelter and Mg-30Ca intermediate alloy after 200 DEG C of preheatings is added, after alloy is completely melt
It is stirred evenly with stirring spoon.Melt is risen to 760 DEG C later and is refined (refining agent dosage is the 1.5% of total charging weight).
Refining agent paper bag is good, is put into bell jar, and bell jar immerses 2/3 depths of melt, and carrying out slowly agitation makes melt generate strong follow
Ring convection current, while refining agent constantly is spread in bath surface, until bright mirror surface is presented to liquid level.After refining, sidewall of crucible is removed
With the flux on bath surface, then one layer of new coverture is sprinkled.Furnace temperature is down to 720 DEG C, standing takes liquid level off after ten minutes
On slag.Taking-up is preheated to 250 DEG C of metal die before casting, and magnesium liquid is poured smoothly into mold.In entire melting
Cheng Zhong is constantly passed through high-purity argon gas into crucible and carries out melt protecting.
By above procedure melting obtain ingredient uniformly, the Biological magnesium alloy block with metallic luster, use wire cutting
Machine-cut is at the sample having a size of 30 × 20 × 8mm size.
(2) sample cut is successively successively polished on the dry sand paper of 400-600-800-1000 mesh, removes metal watch
Surface oxidation film carries out acetone ultrasonic wave and goes oil processing after polishing.Since magnesium alloy light absorptive is not strong, therefore need to be by its surface black
Marking pen smear as absorbed layer, so as to improve the absorptance of Biological magnesium alloy.
(3) on the laser work platform that sample is put into fiber laser device after pre-processing more than carrying out, laser parameter is set
And displacement program.Parameter setting is as follows: control laser power is 400W, scanning speed 120mm/s, and control spot diameter is
5mm, overlapping rate 50%.It is passed through startup program after the argon gas that purity is 99.99% is protected, is finally obtained on Biological magnesium alloy surface
Obtain remelted layer.
(4) magnesium alloy after processing is completed is taken out from workbench, it is subjected to simple cleaning treatment with alcohol, is blown
It is dry.
The middle remelted layer of the resulting Biological magnesium alloy of the present embodiment 3 with a thickness of 260-300 μm, wherein amorphous consolidation layer
With a thickness of 50-80 μm.Through detecting, charge transfer resistance RPIt is 3045.Corrosion resistance improves.
Comparative example 1
Other conditions are identical as the condition of embodiment 1, be only magnesium alloy composition not within the scope of the invention, wherein scanning
Speed is 90mm/s, and magnesium ingot, zinc ingot metal and the mass fraction that purity is 99.99% by the ratio for being 67:28:5 in atomic ratio are
29.73% Mg-30Ca alloy carries out melting.
This comparative example 1 Biological magnesium alloy middle remelted layer with a thickness of 350-400 μm, X-ray diffractometer detects not
It was found that steamed bun peak, while pattern is observed in scanning electron microscope, alloying component is finer and close after laser treatment, but under this ingredient
By laser treatment, and not formed amorphous coating.Through detecting, charge transfer resistance RPIt is 1362, old friend passes through laser treatment
Afterwards, alloying component more uniformization, corrosion resisting property improve less.
Comparative example 2
Other conditions are identical as the condition of embodiment 1, be only magnesium alloy composition not within the scope of the invention, wherein scanning
Speed is 90mm/s, and magnesium ingot, zinc ingot metal and the mass fraction that purity is 99.99% by the ratio for being 54:41:5 in atomic ratio are
29.73% Mg-30Ca alloy carries out melting.
This comparative example 2 Biological magnesium alloy middle remelted layer with a thickness of 250-300 μm, X-ray diffractometer detects not
It was found that steamed bun peak, while pattern is observed in scanning electron microscope, alloying component is finer and close after laser treatment, but under this ingredient
By laser treatment, and not formed amorphous coating.Through detecting, charge transfer resistance RPIt is 1456.
Comparative example 3
Other conditions are same as Example 1, be only refining temperature be 950 DEG C.
As a result fail to obtain the uniform Biological magnesium alloy block of alloying component, the magnesium alloy block of formation has the cracking of a bit
Defect, be not easy it is blocking, cause it is subsequent also fail to obtain amorphous again coagulate layer.
Comparative example 4
Other conditions are same as Example 3, are only to be warming up to 800 DEG C, 10min is kept the temperature after MAG block is completely melt, not into
Trip temperature adjustment, the pure spelter and Mg-30Ca intermediate alloy being directly added into after 200 DEG C of preheatings.
As a result gained magnesium alloy does not obtain qualified magnesium alloy block, in post laser reflow process in fusion process
In, amorphous is not obtained coagulates layer again.
Comparative example 5
Other conditions are identical as the condition of embodiment 1, and only in laser remolten technical process, wherein scanning speed is 150mm/
s。
It since scanning speed is too fast, can be seen that from the macro morphology of sample, modification of surface morphology is not fairly obvious, process
After scanning electron microscopic observation, there was only 50 μm or so in alloy surface laser remolten layer, after the test of corrosion resisting property, the results showed that
It is unobvious with matrix master alloy corrosion resisting property difference.Therefore in the case where power is 500W, scanning speed 150mm/s can not be formed
While amorphous consolidation layer, too fast due to sweeping speed, the remelted layer of formation is imperfect, and corrosion resisting property improves unobvious.
Claims (10)
1. a kind of Biological magnesium alloy of the layer of consolidation containing amorphous, it is characterised in that: the Biological magnesium alloy successively includes from the inside to surface
Substrate, heat affected layer, amorphous consolidation layer；The magnesium alloy is with atomic percentage, including following component:
Magnesium 55-66%, zinc 28-35%, calcium 5-10%.
2. a kind of Biological magnesium alloy of layer of consolidation containing amorphous according to claim 1, it is characterised in that: the magnesium alloy with
Atomic percentage, including following component:
Magnesium 60-66%, zinc 29-35%, calcium 5%.
3. a kind of Biological magnesium alloy of the layer of consolidation containing amorphous described in any one according to claim 1~2, it is characterised in that:
The amorphous consolidation layer with a thickness of 100-150 μm.
4. the method for preparing a kind of Biological magnesium alloy of layer of consolidation containing amorphous as described in claims 1 to 3 any one, special
Sign is: by design component with magnesium ingot, zinc ingot metal, Mg-30Ca intermediate alloy, the melting under protective atmosphere is taken, cast molding is obtained
Biological magnesium alloy block carries out surface preparation, then uses laser melting process to Biological magnesium alloy block under protective atmosphere
Body surface face carries out remelting, obtains the Biological magnesium alloy of the layer of consolidation containing amorphous, the laser melting process parameter are as follows: laser power is
400-600W, scanning speed 60-120mm/s, spot diameter 3-5mm, overlapping rate 50%.
5. a kind of preparation method of the Biological magnesium alloy of layer of consolidation containing amorphous according to claim 4, it is characterised in that: institute
The mass fraction for stating Ca element in purity >=99.99%, Mg-30Ca intermediate alloy of magnesium ingot, zinc ingot metal is 29.74%；
The protective gas is high purity argon, purity >=99.99% of the high purity argon.
6. a kind of preparation method of the Biological magnesium alloy of layer of consolidation containing amorphous according to claim 4, which is characterized in that institute
State fusion process are as follows: melting container is first heated to 400-450 DEG C, magnesium ingot is then added, and sprinkle magnesium alloy on magnesium ingot surface
Coverture；700-800 DEG C is then heated to, 10-15min is kept the temperature after magnesium ingot fusing, furnace temperature is adjusted to 720-740 DEG C, so
Preheated spelter and Mg-30Ca intermediate alloy are added afterwards, acquisition alloy melt is stirred evenly after to be melted, is then heated to
740-760 DEG C is refined, and the old magnesium alloy covering agent on alloy melt surface is removed after refining, is spread again on alloy melt surface
Upper one layer of magnesium alloy covering agent, is cooled to 720-730 DEG C, stands 10-15min, remove alloy melt liquid level slag obtain to
Cast alloys melt；Protective atmosphere is continually fed into the fusion process.
7. a kind of preparation method of the Biological magnesium alloy of layer of consolidation containing amorphous according to claim 6, which is characterized in that institute
State in refining process, be added refining agent, the additional amount of the refining agent be magnesium ingot, zinc ingot metal, Mg-30Ca gross mass 1~
1.5wt%；
In the refining process, refining agent is put into bell jar, bell jar immerses the depths melt 2/3-3/4, agitation, while constantly existing
Bath surface spreads refining agent, until bright mirror surface is presented to alloy melt liquid level.
8. a kind of preparation method of the Biological magnesium alloy of layer of consolidation containing amorphous according to claim 4, which is characterized in that institute
The process for stating cast molding is to cast from pouring to cast alloys melt in the metal die through 230 DEG C of -250 DEG C of preheatings, after molding
Up to Biological magnesium alloy block.
9. a kind of preparation method of the Biological magnesium alloy of layer of consolidation containing amorphous according to claim 4, which is characterized in that
The preprocessing process is that Biological magnesium alloy block successively uses 400-600-800-1000 mesh sand paper to polish, after polishing
It is placed in acetone and carries out ultrasonic cleaning, smeared uniformly after dry in Biological magnesium alloy block surface black marking pen.
10. a kind of preparation method of the Biological magnesium alloy of layer of consolidation containing amorphous according to claim 4, which is characterized in that
The laser power is 400-500W, scanning speed 90-120mm/s.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111468722A (en) * | 2020-04-01 | 2020-07-31 | 长沙新材料产业研究院有限公司 | Novel substrate, method and application for verifying 3D printing metal powder |
| CN112575209A (en) * | 2020-11-11 | 2021-03-30 | 西北工业大学 | Amorphous preparation method based on crystalline phase-amorphous phase conversion |
| CN112981201A (en) * | 2019-12-17 | 2021-06-18 | 财团法人金属工业研究发展中心 | Magnesium-zinc-calcium alloy and magnesium-zinc-calcium alloy powder |
| CN113265599A (en) * | 2021-05-17 | 2021-08-17 | 扬州大学 | Mg-Zn amorphous/nanocrystalline composite structure medical material and preparation method thereof |
| CN113388792A (en) * | 2021-06-29 | 2021-09-14 | 江西理工大学 | Biomedical amorphous magnesium alloy powder, composite material and preparation process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191168A (en) * | 2006-11-23 | 2008-06-04 | 北京有色金属研究总院 | Magnesium alloy and preparation method thereof |
| CN104018100A (en) * | 2014-05-29 | 2014-09-03 | 北京航空航天大学 | Biomedical degradable magnesium-based bulk amorphous alloy and preparation method thereof |
| CA2942184A1 (en) * | 2014-04-18 | 2015-10-22 | Terves Inc. | Galvanically-active in situ formed particles for controlled rate dissolving tools |
| CN107815618A (en) * | 2017-10-26 | 2018-03-20 | 中南大学 | A kind of amorphous Biological magnesium alloy and preparation method thereof |
-
2018
- 2018-09-21 CN CN201811107808.4A patent/CN109161766B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191168A (en) * | 2006-11-23 | 2008-06-04 | 北京有色金属研究总院 | Magnesium alloy and preparation method thereof |
| CA2942184A1 (en) * | 2014-04-18 | 2015-10-22 | Terves Inc. | Galvanically-active in situ formed particles for controlled rate dissolving tools |
| CN104018100A (en) * | 2014-05-29 | 2014-09-03 | 北京航空航天大学 | Biomedical degradable magnesium-based bulk amorphous alloy and preparation method thereof |
| CN107815618A (en) * | 2017-10-26 | 2018-03-20 | 中南大学 | A kind of amorphous Biological magnesium alloy and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112981201A (en) * | 2019-12-17 | 2021-06-18 | 财团法人金属工业研究发展中心 | Magnesium-zinc-calcium alloy and magnesium-zinc-calcium alloy powder |
| CN111468722A (en) * | 2020-04-01 | 2020-07-31 | 长沙新材料产业研究院有限公司 | Novel substrate, method and application for verifying 3D printing metal powder |
| CN112575209A (en) * | 2020-11-11 | 2021-03-30 | 西北工业大学 | Amorphous preparation method based on crystalline phase-amorphous phase conversion |
| CN113265599A (en) * | 2021-05-17 | 2021-08-17 | 扬州大学 | Mg-Zn amorphous/nanocrystalline composite structure medical material and preparation method thereof |
| CN113265599B (en) * | 2021-05-17 | 2022-08-26 | 扬州大学 | Mg-Zn amorphous/nanocrystalline composite structure medical material and preparation method thereof |
| CN113388792A (en) * | 2021-06-29 | 2021-09-14 | 江西理工大学 | Biomedical amorphous magnesium alloy powder, composite material and preparation process |
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