CN106811706B - A kind of effective ways of regulation and control Corrosion Behaviors of Magnesium Alloys rate - Google Patents

A kind of effective ways of regulation and control Corrosion Behaviors of Magnesium Alloys rate Download PDF

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CN106811706B
CN106811706B CN201510861755.5A CN201510861755A CN106811706B CN 106811706 B CN106811706 B CN 106811706B CN 201510861755 A CN201510861755 A CN 201510861755A CN 106811706 B CN106811706 B CN 106811706B
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magnesium alloy
rate
regulation
magnesium
corrosion
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CN106811706A (en
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许道奎
韩恩厚
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Institute of Metal Research of CAS
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Institute of Metal Research of CAS
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Abstract

The present invention relates to field of magnesium alloy, specially a kind of effective ways of regulation and control Corrosion Behaviors of Magnesium Alloys rate, prepared by Effective Regulation suitable for all kinds of wrought magnesium alloy corrosion rates and processing, meet in medical field magnesium alloy implant material in the biodegradation rate demand at different human body position.Under the conditions of 300~400 DEG C, the annealing of 0.5~2 hour is carried out to strong basis plane texture deformation states magnesium alloy, eliminates the residual stress brought by large deformation.Then, the cutting sampling of different orientation, the stringent component that sample surfaces is controlled to include crystallography crystal face and respectively shared ratio are carried out to alloy.The present invention can significantly regulate and control the corrosion resistance of magnesium alloy, solve the problems, such as regulation and control Corrosion Behaviors of Magnesium Alloys rate speed, reach requirement of the magnesium alloy in medical field difference biodegradation rate, so as to be obviously improved competitiveness of the magnesium alloy as human body implantation biomaterial.

Description

A kind of effective ways of regulation and control Corrosion Behaviors of Magnesium Alloys rate
Technical field
The present invention relates to field of magnesium alloy, specially a kind of effective ways of regulation and control Corrosion Behaviors of Magnesium Alloys rate, suitable for each Prepared by the Effective Regulation of class wrought magnesium alloy corrosion rate and processing, meet in medical field magnesium alloy implant material in different people The biodegradation rate demand of body region.
Background technology
Due to magnesium and magnesium alloy with good biocompatibility and degradability and with people's bone with comparable springform The features such as amount, can be used as ideal medical field biology to be implanted into candidate material.In addition, element magnesium is in human-body biological metabolic process Required essential elements.In general, the intake of the daily magnesium of normal adult is 300-400mg.Wherein, extra Mg2+It can be with It is absorbed by the body or is discharged by urine internal.As it can be seen that the product that implantation material made of magnesium alloy is degraded in human body will not Side effect is generated to human body.Simultaneously as the self degradation of magnesium alloy, takes out implantation piece so second operation need not be carried out, It significantly reduces cost and reduces the pain of patient.Although magnesium and magnesium alloy have above advantages, they are too fast Degradation rate significantly limit its application in medical field.In addition, the hydrogen meeting generated due to the biodegradation of magnesium Occur to assemble and bubble hydrogen is generated near implant, human cell tissue can be made to occur to detach and eventually lead to the hair of caries disease It is raw.In order to improve the corrosion resistance of magnesium alloy, researcher has carried out magnesium alloy a large amount of alloying experimental studies.Although exploitation The corrosive nature of new multicomponent magnesium alloy materials gone out meets biodegradable requirement, but the certain alloys member included Element such as heavy metal element can be harmful.Therefore, it is necessary under the premise of alloy compositions are not changed, selection has had life at present The magnesium alloy materials of object medical prospect promote their corrosion-resistant behavior, to meet magnesium alloy biomaterials to varying degrees The demand of different degradation rates.
Invention content
The purpose of the present invention is to provide a kind of effective ways of regulation and control Corrosion Behaviors of Magnesium Alloys rate, solve magnesium alloy and are using The problems such as corrosion rate is too fast and uncontrollable in field.
The technical scheme is that:
It is a kind of regulate and control Corrosion Behaviors of Magnesium Alloys rate effective ways, carry out under the conditions of 300~400 DEG C going for 0.5~2 hour Stress annealing processing, makes magnesium alloy obtain strong basis plane texture.
The effective ways of the regulation and control Corrosion Behaviors of Magnesium Alloys rate, magnesium alloy are all kinds of wrought magnesium alloys.
The effective ways of the regulation and control Corrosion Behaviors of Magnesium Alloys rate, Corrosion Behaviors of Magnesium Alloys rate is adjustable.
The effective ways of the regulation and control Corrosion Behaviors of Magnesium Alloys rate, under room temperature, magnesium alloy is 0.1M in molar concentration NaCl solution in, corrosion potential Ecorr=-1.75~-1.55VSCE, corrosion electric current density icorr=2~500 μ A/cm2, lose Weight rate is 0.2~9.5mg/cm2/day。
The effective ways of the regulation and control Corrosion Behaviors of Magnesium Alloys rate, before stress relief annealing process, carry out magnesium alloy Deformation processing keeps the temperature 3~5 hours at 300~500 DEG C, and hot extrusion molding is carried out to alloy, and extrusion ratio is 4~6:1.
The effective ways of the regulation and control Corrosion Behaviors of Magnesium Alloys rate, it is stringent that sample surfaces is controlled to include crystallography crystal face Component and respectively shared ratio, in particular to:(0002) the crystal grain quantity of basal plane orientation and (10-10) and (11-20) cylinder The ratio being orientated between crystal grain quantity summation, proportional region is more than 15 or less than 0.08.
The present invention design philosophy be:
The present invention by reasonable selection with medical prospect magnesium alloy materials, to alloy carry out large deformation plastic processing and Stress relief annealing makes alloy generate strong basal plane texture.Using wire cutting sampling technique, choose comprising different crystal face score Orientation sample.Since the corrosion resistance of basal plane is best, there is the corrosion resistance of sample surfaces that basal plane orientation is concentrated most It is good.In view of microcell galvanic corrosion can occur between basal plane and cylinder orientation crystal grain, by certain score cylinder orientation crystal grain and more The corrosion resistance of the specimen surface of base planar orientation crystal grain composition is worst.Finally, magnesium alloy different crystal face corrosion potential is utilized Between existing difference, by controlling the crystallography face component and relative area score that sample surfaces include, reached to alloy The control of corrosion rate.
Advantages of the present invention and advantageous effect are:
1st, the present invention obtains the biodegradation rate of alloy by magnesium alloy materials of the selection with very strong medical prospect Control greatly improves their potentiality as implantation material.
2nd, magnesium alloy of the invention has universality, and the development for high anti-corrosion industrial magnesium alloy provides reference, opens up The engineering field of magnesium alloy possible application is opened up.
3rd, the equipment used in the present invention is simple, and cost is relatively low, and processing technology is simple, convenient.
Description of the drawings
Fig. 1 (a)-Fig. 1 (c) chooses the sampling of wrought magnesium alloy AZ31 and Microstructure Information (embodiment 1, embodiment 2 and reality Apply example 3).Wherein, Fig. 1 (a) is the sampling direction of embodiment 1, embodiment 2 and embodiment 3;Fig. 1 (b) is orientated sample for embodiment 3 The heterogeneous microstructure of product;Fig. 1 (c) is (0002), (11-20) and (10-10) pole figure.
The collecting gas result (embodiment 1, embodiment 2 and embodiment 3) of Fig. 2 different orientation magnesium alloys AZ31.
Specific embodiment
With reference to specific embodiments and the drawings, the present invention will be further described, it should be noted that the embodiment provided It is for illustrating the present invention rather than limitation of the present invention, protection scope of the present invention is not limited to the specific of following implementation Embodiment.
Embodiment 1
I), alloy is chosen
Using commercial AZ31 wrought magnesium alloys bar, chemical composition (mass percentage) is:3%Al, 1%Zn, Remaining is Mg;
II), deformation processing
4 hours are kept the temperature at 400 DEG C, hot extrusion molding, extrusion ratio 5 are carried out to alloy:1.
III), stress relief annealing
1 hour is kept the temperature at 400 DEG C to As-extruded alloy, stress relief annealing is carried out, to eliminate residual stress to alloy corrosion Anisotropic influence.
V), microstructure characterizes
Its preparation process of the sample of structure observation is as follows:Using No. 1000 silicon carbide silicon carbide paper flattened surfaces;Then it adopts It is mechanically polished with oil base diamond paste;EBSD analysis results show that the texture of alloy is typical basal plane texture, corresponding to scheme Spectrum and (0002), (11-20) and (10-10) pole figure are shown in attached drawing 1, and the texture for showing alloy is typical basal plane fiber texture degree.This implementation In example, the stringent component that sample surfaces is controlled include crystallography crystal face and it is respective shared by ratio, in particular to:(0002) base Ratio between the crystal grain quantity of planar orientation and (10-10) and (11-20) cylinder orientation crystal grain quantity summation, preferred proportion model It is more than 15 or less than 0.08 (its value is generally higher than 8 or less than 0.5, the present embodiment 0.04) to enclose, and makes the corruption of alloy surface It is minimum to lose rate.
IV), sample position and corrosive nature test
The sample that size is 5mm (length) × 5mm (width) × 3mm (thickness) is cut using wire cutting, sample surfaces are perpendicular to crowded The axis of pressure bar material, the specific schematic diagram that is orientated are shown in attached drawing 1.With resin carry out it is cold inlay, surface is processed by shot blasting;Then, Sample is put into the NaCl solution (physiological saline) that molar concentration is 0.1M at ambient temperature and impregnate and electrochemistry reality It tests.Hydrogen collection experiment is carried out under open circuit potential, specific hydrogen is precipitated curve and sees attached drawing 2.It, will with banister brush after experiment The corrosion product removal of specimen surface, the weight that it is claimed to lose calculate weight loss rate.The sample surfaces for exposing 5mm × 5mm are opened The measurement of dynamic potential polarization curve is opened up, determines the corresponding parameters of electrochemical corrosion of alloy, rate of weight loss 1.5mg/ cm2/ day, corrosion potential Ecorr=-1.65VSCE, corrosion current icorr=20 μ A/cm2
Embodiment 2
Part same as Example 1 is:
I), alloy is chosen
II), deformation processing
III), stress relief annealing
V), microstructure characterizes
Difference from Example 1 is:
IV), sample position and corrosive nature test
The sample that size is 5mm (length) × 5mm (width) × 3mm (thickness), sample surfaces and extruded rod are cut using wire cutting The axis of material is shown in attached drawing 1 into 45 degree of angles, the specific schematic diagram that is orientated.With resin carry out it is cold inlay, surface is processed by shot blasting;So Afterwards, sample is put into the NaCl solution that molar concentration is 0.1M at ambient temperature and is impregnated and electrochemistry experiment.It is opening Hydrogen collection experiment is carried out under the current potential of road, specific hydrogen is precipitated curve and sees attached drawing 2.As it can be seen that embodiment 2 is orientated the liberation of hydrogen speed of sample Rate is most fast.After experiment, the corrosion product of specimen surface is removed with banister brush, the weight that it is claimed to lose calculates weightless speed Rate.The sample surfaces for exposing 5mm × 5mm are carried out with the measurement of dynamic potential polarization curve, determines that the corresponding electrochemistry of alloy is rotten Lose parameter, rate of weight loss 4.5mg/cm2/ day, corrosion potential Ecorr=-1.72VSCE, corrosion current icorr=100 μ A/cm2
Embodiment 3
Part same as Example 1 is:
I), alloy is chosen
II), deformation processing
III), stress relief annealing
V), microstructure characterizes
Difference from Example 1 is:
IV), sample position and corrosive nature test
The sample that size is 5mm (length) × 5mm (width) × 3mm (thickness) is cut using wire cutting, sample surfaces, which are in, to be squeezed The central core of bar and parallel with the axis of extruded bars, the specific schematic diagram that is orientated are shown in attached drawing 1.With resin carry out it is cold inlay, it is right Surface is processed by shot blasting;Then, sample is put into the NaCl solution that molar concentration is 0.1M at ambient temperature and soaked Bubble and electrochemistry experiment.Hydrogen collection experiment is carried out under open circuit potential, specific hydrogen is precipitated curve and sees attached drawing 2.As it can be seen that implement The liberation of hydrogen rate that example 3 is orientated sample is most slow.After experiment, the corrosion product of specimen surface is removed with banister brush, claims its damage The weight of mistake calculates weight loss rate.The sample surfaces for exposing 5mm × 5mm are carried out with the measurement of dynamic potential polarization curve, is determined The corresponding parameters of electrochemical corrosion of alloy, rate of weight loss 0.4mg/cm2/ day, corrosion potential Ecorr=-1.60VSCE, Corrosion current icorr=5 μ A/cm2
Embodiment the result shows that, the present invention using can significantly improve or reduce magnesium alloy biodegradation rate processing And treatment process, under the conditions of 300~400 DEG C, strong basis plane texture deformation states magnesium alloy is carried out at the annealing of 0.5~2 hour Reason, eliminates the residual stress brought by large deformation.Then, the cutting sampling of different orientation is carried out to alloy, strictly controls sample Surface includes the component of crystallography crystal face and respectively shared ratio.The present invention can significantly regulate and control the corrosion resistance of magnesium alloy Can, it solves the problems, such as that Corrosion Behaviors of Magnesium Alloys rate speed can be regulated and controled, reaches magnesium alloy in medical field difference biodegradation rate Requirement, so as to be obviously improved magnesium alloy as human body implantation biomaterial competitiveness.

Claims (4)

1. a kind of effective ways of regulation and control Corrosion Behaviors of Magnesium Alloys rate, it is characterised in that:Under the conditions of 300~400 DEG C carry out 0.5~ The stress relief annealing process of 2 hours makes magnesium alloy obtain strong basis plane texture;
Before stress relief annealing process, deformation processing is carried out to magnesium alloy, keeps the temperature 3~5 hours at 300~500 DEG C, pairing Gold carries out hot extrusion molding, and extrusion ratio is 4~6:1;
After annealing, the cutting sampling of different orientation is carried out to alloy, it is stringent that sample surfaces is controlled to include crystallography crystal face Component and respectively shared ratio, in particular to:(0002) the crystal grain quantity of basal plane orientation and (10-10) and (11-20) column Ratio between planar orientation crystal grain quantity summation, proportional region are more than 15 or less than 0.08.
2. the effective ways of regulation and control Corrosion Behaviors of Magnesium Alloys rate described in accordance with the claim 1, it is characterised in that:Magnesium alloy is all kinds of Wrought magnesium alloy.
3. the effective ways of regulation and control Corrosion Behaviors of Magnesium Alloys rate described in accordance with the claim 1, it is characterised in that:Corrosion Behaviors of Magnesium Alloys speed Rate is adjustable.
4. the effective ways of regulation and control Corrosion Behaviors of Magnesium Alloys rate described in accordance with the claim 1, it is characterised in that:Under room temperature, In the NaCl solution that magnesium alloy is 0.1M in molar concentration, corrosion potential Ecorr=-1.75~-1.55VSCE, corrosion electric current density For icorr=2~500 μ A/cm2, weight loss rate is 0.2~9.5mg/cm2/day。
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CN107607242A (en) * 2017-09-22 2018-01-19 上海实达精密不锈钢有限公司 A kind of residual stress detection method of cold rolled precision metal sheet band

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001140049A (en) * 1999-11-12 2001-05-22 Fukui Megane Kogyo Kk Spectacles frame member using magnesium alloy and method of manufacture
CN103380223A (en) * 2011-02-24 2013-10-30 住友电气工业株式会社 Magnesium alloy and manufacturing method for same
CN103394545A (en) * 2013-07-30 2013-11-20 上海交通大学 Precise machining method for capillary tube for biodegradable magnesium alloy intravascular stent
CN103598927A (en) * 2013-10-17 2014-02-26 上海交通大学 Degradable magnesium alloy nerve conduit for nerve defect repair and preparation method of nerve conduit

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001140049A (en) * 1999-11-12 2001-05-22 Fukui Megane Kogyo Kk Spectacles frame member using magnesium alloy and method of manufacture
CN103380223A (en) * 2011-02-24 2013-10-30 住友电气工业株式会社 Magnesium alloy and manufacturing method for same
CN103394545A (en) * 2013-07-30 2013-11-20 上海交通大学 Precise machining method for capillary tube for biodegradable magnesium alloy intravascular stent
CN103598927A (en) * 2013-10-17 2014-02-26 上海交通大学 Degradable magnesium alloy nerve conduit for nerve defect repair and preparation method of nerve conduit
CN104055599A (en) * 2013-10-17 2014-09-24 上海交通大学 Degradable magnesium alloy nerve conduit for nerve defect repair and preparing method of degradable magnesium alloy nerve conduit

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