CN106148783A - Anticorrosive high-strength deformation nanometer Mg alloy and its preparation method and application - Google Patents
Anticorrosive high-strength deformation nanometer Mg alloy and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to anticorrosive high intensity deformation at room temperature nanometer Mg alloy and its preparation method and application.By particular category magnesium lithium alloy is carried out short route processing, producing to have and nanoscale richness lithium accumulation regions and the nanometer Mg alloy of nanoscale richness aluminum accumulation regions are distributed in rich magnesium matrix, wherein lithium atom percentage composition >=50 99% of nanoscale richness lithium accumulation regions, bulk averaged value scope are 100 8000 cubic nanometer and volumn concentration scope is 5 35%；Aluminum atomic percentage conc >=20 99% of nanoscale richness aluminum accumulation regions, bulk averaged value scope are 100 30000 cubic nanometer and volumn concentration scope is 0 25%.This nanometer Mg alloy at ambient temperature, is provided simultaneously with ultralight proportion, current of polarization in 0.1 mole of saline can as little as 3 μ A/cm2Corrosion resistance, 100 250 kilonewton meters/kilogram ratio surrender strong, reach as high as the elongation percentage of 60% and the excellent properties combination of good deformation performance, thus can be widely applied in mobile communication equipment, computer, photographing unit, the vehicles, Aero-Space and defence product.
Description
Technical field
The present invention relates to a kind of new metallic material and preparation method and application, especially relate to
A kind of anticorrosive, high intensity, deformation at room temperature performance nano-structure wrought magnesium alloy good, ultralight and
Its preparation method and application.
Background technology
The development of modern science and technology has important dependence and requirement to new metallic material,
Asking it lightweight, intensity is high, and anticorrosive, processability is good, it is easy to processing.Main
Have aluminum, magnesium, three kinds of light metals of titanium, its proportion be respectively 2.7,1.74 and 4.5 grams/vertical
Square centimetre, wherein magnesium is the lightest.Magnesium alloy, in these three alloy structure material, has relatively
Good specific strength and Castability, but, (1) is less because of its hexagonal lattice structure slip system,
Deformation at room temperature performance is low；(2) corrosion resistance is not up to the present because forming one layer of fine and close guarantor
Cuticula and poor, and do not have a kind of sacrificial anode material can be to its surface, as zinc-plated
Layer is the same to steel surface, protects.Therefore these two problems of magnesium alloy are restrictions all the time
Its wide variety of bottleneck.
By adding lithium to magnesium, form magnesium lithium alloy, it is possible to effectively solve magnesium alloy deformation at room temperature
The problem that performance is low.When lithium content is less than 5Wt.% (percentage by weight), magnesium lithium alloy is still
Keep the hexagonal lattice structure (referred to as α phase) of magnesium；After more than 5Wt.%, magnesium hexagonal crystal
Lattice crystal structure starts body-centered cubic structure (β phase) many to slip system, that deformation at room temperature performance is good
Change；After more than 10.5Wt.%, it is completely converted into body-centered cubic structure.So, to two
For unit's Mg-Li alloy, when lithium content less than 5Wt.%, for 5Wt.%-10.5Wt.% and
During more than 10.5Wt.%, it is respectively provided with single α phase, alpha+beta phase and single β phase constitution.
α phase amount Han lithium is less, has high rigidity and intensity (intensity is generally about equal to 3 times of Vickers hardnesses),
But deformation performance is poor, and β phase is just the opposite, has soft, low-intensity but high morphotropism
Energy.So, usual magnesium lithium alloy lithium content is the highest, and in tissue, β phase content is the highest, intensity
And hardness is the lowest, plastic deformation performance is the best.One or more other alloying elements join
After Mg-Li alloy, form ternary or polynary magnesium lithium alloy, the above-mentioned 5Wt.% of Li alloy can be caused
With the movement of the tissue critical line of 10.5Wt.% lithium content, and the shape that other phase is in the tissue
Become.These are tied due to body centred cubic crystal based on the magnesium lithium alloy of alpha+beta phase or β phase constitution
The existence of structure β phase, its deformation at room temperature performance only has the magnesium of hexagoinal lattice (α phase) to close relatively
Gold is greatly improved, and room temperature elongation percentage may be up to more than 80%.So, this kind of magnesium lithium alloy
Occur efficiently solving the problem that magnesium alloy deformation at room temperature performance is low, simultaneously as the ratio of lithium
Weight the lowest (0.534 gram/cc), also reduce further magnesium alloy proportion extremely
1.30-1.65g/cm3.Thus, the magnesium lithium alloy that alpha+beta phase or β phase constitution are main has super
Gently, high ratio modulus, excellent specific rigidity, heat conduction, conduct electricity, prominent absorption impact and damping
Performance, excellent capability of electromagnetic shielding, solderable performance, good machining property and cold
Deformation and processability.
Generally, magnesium lithium alloy in the world is mainly ternary and multicomponent alloy, its preparation method and
Process route is: (1) chooses Mg, Li and the former material such as other alloying element and melting fusing
Material, after carrying out melting or fusing in the electric furnace of protective atmosphere or slag, (2) are cast into
The ingot of variously-shaped size, (3) ingot, after high temperature homogenizing annealing processes, directly passes through
The various thermal processing methods such as extruding, hot rolling, forging make bar, wire rod, sheet material, band,
Tubing and various section bar.
Prepare through above-mentioned technical process, the ternary containing 7-16Wt.% lithium and multicomponent alloy type
Material, be organized as alpha+beta phase or β phase be main tissue, generally its mean grain size size for
In 50-300 micrometer range, Vickers hardness scope in 50-75HV, quenched after, wherein
Some particular category alloy, hardness can reach more than 100HV, but through natural or artificial
After timeliness, hardness can progressively fall back to the front state that quenches.
At present, this two classes alpha+beta phase common or β phase constitution are main ternary and polynary magnesium lithium
Alloy, although solve the problem that magnesium alloy deformation at room temperature performance is low, but, due to the change of lithium
Learn activity high, cause original corrosion resistance to deteriorate further with regard to poor Magnesium Anti-Corrosion,
Not only it is to say, current magnesium lithium alloy does not solves the problem of magnesium alloy corrosion resistance difference, instead
Cause it more to deteriorate, become the conjunction that in current all magnesium alloys, corrosion resistance classification is worst
Gold, intensity reduces the most further simultaneously.Such as, typical LA141 magnesium lithium in magnesium lithium alloy
Alloy tensile strength when room temperature is 132-166MPa, yield strength is 106-158MPa
And elongation percentage is 11%-24%.
So, up to the present, be not documented have simultaneously anticorrosive, high
Intensity, the appearance of the wrought magnesium alloy that deformation at room temperature performance is good.Thus develop this kind of magnesium alloy,
It is classified as one of most important target of international Mei Ye association, is world today's magnesium alloy manufacturing industry and section
The worldwide technological puzzle that the worker that grinds is in the urgent need to address.
Summary of the invention
The present invention is by containing 7-16Wt.% lithium, and after quenching, Vickers hardness can increase to 100
The ternary of more than HV and polynary magnesium lithium alloy material, be processed further processing, in its group
Knitting the tissue having obtained nano scaled elemental accumulation regions the rarest in metal material, this tissue is composed
Give the performance that this magnesium alloy is unusual: there is improved corrosion performance, high intensity, room simultaneously
The excellent properties combination that warm deformation performance is good.Therefore invented this anticorrosive high-strength deformation to receive
Rice magnesium alloy, and its preparation method and application.The present invention has successfully hewed out a brand-new way
Footpath, solves and has at present that corrosion resistance is good, intensity is high and room temperature becomes the most simultaneously
This worldwide technological puzzle of magnesium alloy that shape performance is good.
The present invention solves the technical scheme that above-mentioned technical problem used:
By to containing 7-16Wt.% lithium, and after quenching, Vickers hardness can increase to 100HV
Above ternary and polynary magnesium lithium alloy bar, sheet material, band, wire rod, tubing or section bar
Semi-finished product, according to preparation method of the invention below, prepare nano scaled elemental in its tissue
Accumulation regions, forms nano-structure, and the nano-structure of this uniqueness gives the superiority that this alloy is unique
Can combine, thus prepare described anticorrosive high-strength nano wrought magnesium alloy.
The preparation method of described anticorrosive high-strength nano wrought magnesium alloy, it is characterised in that
This preparation method step is as follows:
(1) choose above-mentioned containing 7-16Wt.% lithium and quenching after Vickers hardness can increase to 100HV
Above ternary and polynary magnesium lithium alloy bar, sheet material, band, wire rod, tubing or section bar
Semi-finished product；
(2) above-mentioned semi-finished product are heated to more than 200-450 DEG C, are incubated more than 1-100 minute
Time, carry out Quenching Treatment, obtain more than Vickers hardness 100HV and in 0.1 molar salt
Standard potentiodynamic polarization electric current in water is 3-12 μ A/cm2Quenching structure material；
(3) above-mentioned quenching structure material being carried out nature or artificial aging, aging temp can be
More than room temperature to 200 DEG C, aging time was from more than 1 minute to 10000 hour；After timeliness
Tissue, relative to quenching structure, the composition according to aging temp, time and alloy is different,
Vickers hardness reduce more than 1-50HV and in 0.1 mole of saline potentiodynamic polarization electric current liter
High 0.1-10 μ A/cm2Above；
(4) material after above-mentioned timeliness is carried out deformation process, processing mode for rolling, forging,
Swage, extrude, drawing, roll-in, punching press, one of which or several in deep draw and reaming,
When deflection is more than more than 2-20%, obtains described anticorrosive high-strength nano deformed Mg and close
Gold, possesses following nano-structure；
(5) this nano-structure be characterized as being distributed in rich magnesium matrix nanoscale richness lithium accumulation regions,
Nanoscale richness aluminum accumulation regions and other element nanometer accumulation regions, its tissue signature is: (a)
Described nanoscale richness lithium accumulation regions is defined as lithium atom percentage composition >=50 in this alloy structure
The region of At.%, the lithium atom percentage composition in this region is by the 50At.% on its surface progressively
Bring up to the 50-99.99At.% at center；B the nanoscale richness aluminum accumulation regions described in () is defined as
The region of aluminum atomic percentage conc >=20At.% in this alloy structure, the aluminum atom in this region
Percentage composition is brought up to the 20-99At.% at center by the 20At.% on surface；C () is according to one-tenth
Dividing different with processing technique, this alloy also can be containing elements such as nanoscale zinc-rich, Fu Yin, copper-rich
Accumulation regions, every kind of enriched element atom content >=20 in its each nanoscale accumulation regions
At.%, and brought up to 20-90At.% successively to center by surface, every kind of nanoscale accumulation regions,
Bulk averaged value scope is 100-125000 cubic nanometer, accounts for all materials and amasss content range and is
0-10%；Rich magnesium matrix described in (d) be defined as above-mentioned various element nanoscale accumulation regions and
Beyond other phase composition, the magnesium atom content region more than 50At.%.This nanostructured is composed
Give the following performance of described anticorrosive high-strength nano wrought magnesium alloy.
(6) there is the described anticorrosive high-strength nano wrought magnesium alloy of above-mentioned nano-structure feature,
Its performance characteristic is, is provided simultaneously with improved corrosion, high intensity and high deformation at ambient temperature
Performance: the standard potentiodynamic polarization electric current 3-12 μ A/cm in 0.1 mole of saline2, when it
When being exposed to surrounding, its surface and the oxygen in surrounding, carbon dioxide, moisture etc.
React, Li that form a kind of densification, that be insoluble in water2CO3Protecting film, as at aluminum
The Al that surface is formed2O3Film protection aluminum, and the Cr of stainless steel surfaces2O3Film protection rustless steel is the same,
Giving this alloy improved corrosion performance, protection alloy is from corrosion further；Meanwhile, nano junction
Structure give this magnesium alloy high than yield strength reach 100-250 kilonewton meter/kilogram, and body-centered
The rich lithium accumulation regions of cubic structure, imparts the high deformation performance of this magnesium alloy, and elongation percentage is the highest
Up to 60%.
Here it is the preparation method of described anticorrosive high-strength nano wrought magnesium alloy, and gained
Nano-structure and this nano-structure give the excellent properties combination of this alloy.
(7) due to described anticorrosive high-strength nano wrought magnesium alloy, there is anti-corruption ultralight, high
The excellent properties combination of erosion, high intensity and high deformation performance, thus can be applicable to manufacture ultralight magnesium
Alloyed components, is applied in following product:
Electronic apparatus class, such as mobile communication equipment, computer, photographing unit,
The vehicles, such as automobile, train, bicycle and civil aircraft,
Aero-Space, such as satellite, airship, space shuttle, moonfall device and rocket,
And defence product, if any people and unmanned military aircraft, guided missile, aerial bomb,
Big gun is penetrated or scatterable mine and submarine mine, radar, tank composite armour, automatic rifle
The artillery equipments such as sighting device, magazine and gun stock.
Can effectively alleviate these products weight, improve its payload, increase its intensity and rigidity,
Reduce vibration, absorb impact and effectively reduce the external environment condition electromagnetic interference to product.
The technological progress using the technique scheme present invention to obtain is:
The present invention is by increasing to 100 to containing Vickers hardness after 7-16Wt.% lithium and quenching
The ternary of more than HV and polynary magnesium lithium alloy semi-finished product are processed further processing, and obtain
There is excellent corrosion protection energy, be provided simultaneously with the good nanometer Mg of high intensity, deformation at room temperature performance and close
Gold, its preparation method and application, successfully solve and have high corrosion resistance the most simultaneously
This worldwide technological puzzle of magnesium alloy that energy, high intensity and deformation at room temperature performance are good.
Why the magnesium-alloy material that the inventive method produces, can solve the problem that this global problem,
Giving the credit to (a) selects present invention particular category magnesium alloy as defined in above-mentioned paragraph half to become
Product material, (b) is produced with preparation method described in the invention, (c), upper
State the special nano-structure described in detail in paragraph: in rich magnesium matrix, nano level richness is distributed
Lithium accumulation regions, nanoscale richness aluminum accumulation regions and other element nanometer accumulation regions.
Generally, it is referred to as nano-structure material containing tissue size less than the material of 100 nanometers, should
Material because of its tissue size significantly less than common micro level organization material, thus in performance ten
Divide and be different from a micron organization material.For micron organization material, its corrosion resistance, intensity
Performance and deformation at room temperature performance are conflicting, these those relations disappeared long, be extremely difficult to all this
A little performance indications are simultaneously in optimum state.So, the special nano-structure of this alloy, beat
Break this restriction of micron organization material, imparted this magnesium alloy and be so different from usual micron
The excellent properties combination of unique improved corrosion, high intensity and deformation at room temperature performance of level magnesium alloy.
This Magnesium Anti-Corrosion galvanic electricity pressure current of polarization in 0.1 mole of saline is
3-12μA/cm2, the least corrosion resistance of this electric current is the best, so, this conjunction in most cases
The anticorrosive electric current of gold is between 1 μ A/cm of fine aluminium2The 10 μ A/cm with pure magnesium2Centre, and fine aluminium
There is respectively in aluminium alloy and magnesium alloy best corrosion resistance with pure magnesium.It is to say,
The original specific magnesium lithium alloy that corrosion resistance is worst in all magnesium alloys, according to condition requirement,
Through the art of this patent processed, after forming nano-structure, its corrosion resistance significantly surmounts pure
Magnesium and other classification magnesium alloy, become the magnesium alloy that corrosion resistance is best.Atmospheric environment around
In, this alloy surface reacts with the oxygen in air and environment, moisture and carbon dioxide etc.,
Form one layer of fine and close Li being insoluble in water2CO3Protecting film.This layer of protecting film, closes just as aluminum
The Al that gold and stainless steel surfaces are formed2O3And Cr2O3Protecting film is the same, protects its alloy bulk
From corrosion further, give this alloy improved corrosion performance.Meanwhile, nano-structure also gives
This magnesium alloy 100-250 kilonewton meter/kilogram ratio yield strength, reach as high as 60%
Elongation percentage and good deformation at room temperature performance.
So, this magnesium alloy has the most excellent combining properties, obtains weight in field of magnesium alloy
Quantum jump, give the credit to for meet this patent particular requirement containing 7-16Wt.% lithium and quenching
Rear Vickers hardness can increase to the ternary of more than 100HV and complex magnesium alloy bar, sheet material,
The semi-finished product of wire rod, tubing or section bar, according to the processing method of this patent, add further
Unique nano-structure obtained by work, defines described anticorrosive high-strength deformation nanometer Mg
Alloy.
Owing to described anticorrosive high-strength nano wrought magnesium alloy has ultralight, improved corrosion, height
The excellent properties combination of intensity and high deformation performance, thus can be applicable to manufacture ultralight magnesium alloy zero
Parts, are applied in following product:
Electronic apparatus class, such as mobile communication equipment, computer, photographing unit,
The vehicles, such as automobile, train, bicycle and civil aircraft,
Aero-Space, such as satellite, airship, space shuttle, moonfall device and rocket,
And defence product, if any people and unmanned military aircraft, guided missile, aerial bomb,
Big gun is penetrated or scatterable mine and submarine mine, radar, tank composite armour, automatic rifle
The artillery equipments such as sighting device, magazine and gun stock.
Can effectively alleviate these products weight, improve its payload, increase its intensity and rigidity,
Reduce vibration, absorb impact and effectively reduce the external environment condition electromagnetic interference to product.
Accompanying drawing explanation
Fig. 1 is this anticorrosive high-strength deformation nanometer Mg alloy three-dimensional in 40x40x70 nanometer
Atom distribution in space and organization charts thereof；
Fig. 2 is this anticorrosive high-strength deformation nanometer Mg alloy atom in bigger three dimensions
Distribution and organization charts thereof；
Fig. 3 present this anticorrosive high-strength deformation nanometer Mg alloy and existing commercial titanium alloy,
Aluminium alloy and existing magnesium alloy performance comparison in specific strength and elongation percentage performance space；
Fig. 4 presents this anticorrosive high-strength deformation nanometer Mg alloy and existing industrial magnesium alloys,
In ratio yield strength and elongation percentage performance space, and in ratio yield strength and represent corrosion resistance
Performance comparison in the performance space of the current of polarization of energy；
Fig. 5 is this anticorrosive high-strength deformation nanometer Mg alloy and existing best corrosion resistance row
For the experimental result contrast in corrosion resistance is tested of the pure magnesium alloy, and be better than the anti-corruption of pure magnesium
The Corrosion resistance mechanism of erosion performance.
In figure 1 above, 1-richness magnesium matrix, 2-richness lithium accumulation regions, 3-richness aluminum accumulation regions.
Wherein, Fig. 1, three-dimensional atom probe reconstruct figure discloses this magnesium alloy at one
Tissue in 40x40x70 nanometer three-dimensional spatial area and atom scattergram.(1-a) illustrate
The rich lithium accumulation regions (dark particulate matter) being positioned in rich magnesium matrix (loose sand shape region) and rich aluminum
The appearance and size of accumulation regions (lighter colored particles thing), and spatial distribution.Rich lithium accumulation regions and rich aluminum
Accumulation regions, be respectively defined as by atomic percentage conc be 50At.% lithium, 20At.% aluminum etc.
Content interface, area encompassed.(1-b) can be seen that lithium atom percentage composition from left to right
From equal size interface and the center of rich magnesium matrix 50At.% in rich lithium accumulation regions, increase successively
The distribution situation added.(1-c) illustrate aluminum atomic percentage conc from left to right from rich magnesium matrix to
The distribution shape that in rich aluminum accumulation regions, the equal size interface of 20At.% and center, accumulation regions increase successively
Condition.
Fig. 2, three-dimensional atom probe reconstruct figure discloses: the rich lithium accumulation regions in (A) this alloy
Size, pattern and the spatial distribution state of (dark particulate matter).Rich lithium accumulation regions be defined as by
Atomic percentage conc is the equal size interface area encompassed of 50At.% lithium；(B) show
Rich lithium accumulation regions (dark particulate matter) and the rich magnesium matrix at place thereof in figure (A) (dissipate
Sand-like region, is defined as beyond all elements accumulation regions and other phase constitution, magnesium atom content
Region more than 50At.%) tissue；Figure (C) illustrates in figure (B), central part
In a diameter of 10 nm cylinder shape regions that rectangular bar is indicated, magnesium and lithium atom are along body length
The scattergram in degree direction, discloses magnesium and lithium atom distribution shape in rich magnesium matrix and rich lithium accumulation regions
Condition.
Fig. 3 be this nanometer Mg alloy with existing commercial titanium alloy, aluminium alloy and magnesium alloy at ratio by force
Degree and elongation percentage performance space in performance comparison；The specific strength of usual material and elongation percentage,
As shown in other alloy in this figure, it is that this rises that relation dropped.This contrast has disclosed Ben Na
Rice magnesium alloy, compared with industrial aluminum, magnesium, titanium alloy, has high specific strength, with high-elongation
Combine with the excellent properties of high deformation performance.
Fig. 4-a shows this alloy and existing industrial magnesium alloys, than yield strength-elongation percentage
Performance comparison in performance space.Generally ratio yield strength and two performances of elongation percentage of material refer to
Mark, as shown in other magnesium alloy in this figure, is that this rises that relation dropped.This contrast discloses
This alloy, compared with current existing industrial magnesium alloys, has the highest ratio yield strength simultaneously and prolongs
Stretch the excellent properties combination of rate.
Fig. 4-b shows that the existing industrial magnesium alloys of this alloy and other is than yield strength-polarization electricity
Performance comparison in stream performance space, demonstrates that this alloy, compared with industrial magnesium alloys, has simultaneously
Standby the highest than yield strength and the excellent properties combination of hypopolarization electric current in 0.1 mole of saline.
Noting, industrial alloy current of polarization comes from document, magnesium therein and alloy thereof, its electricity that polarizes
Stream is varied from because test condition is different.
Fig. 5 illustrates the superior corrosion resistance of this alloy and anticorrosive principle thereof.A () demonstrates
The standard dynamic potential polarization curve that this alloy and pure magnesium are tested in 0.1 mole of saline, this song
In line, this alloy is respectively 6 and 10 μ A/cm with the standard potentiodynamic polarization electric current of pure magnesium2, (b)
Be this alloy and pure magnesium soak 3 days in 0.1 mole of saline after carried out electrochemical AC impedance
General, disclose this nanometer Mg alloy dissolution kinetics and be significantly less than there is best corrosion resistance
The pure magnesium of energy, it is, (a) and (b) jointly discloses the pure magnesium of this alloy ratio and has more excellent
Corrosion resistance more, figure (c) and (d) are by XPS Deep Analysis technology, test point
This alloy surface chemistry tissue has been arrived in analysis, discloses and defines one layer of cause at nanometer Mg alloy surface
Close is insoluble in water Li2CO3Protecting film, protects this alloy from corrosion further.
Detailed description of the invention
The described present invention for containing 7-16Wt.% lithium and quenching after Vickers hardness increase to 100HV with
On, as Mg-13%Li-5%Al, Mg 10%Li 3.9%Zn 2.5%Al 1.8%Cu,
Mg-11%Li-3.3%Al-0.6%Y-0.2%Zr, Mg-13%Li-3%Al and
Ternary and the polynary magnesium lithiums such as Mg-13%Li-3%Al-1%Zn (composition be weight percentage Wt.%)
The green shape of alloy, according to the method described in the present invention and step, prepares in its tissue
Go out to have following described nano-structure, and when this nano-structure imparts this magnesium alloy room temperature simultaneously
Possess improved corrosion, high intensity, deformation performance excellent, thus make anticorrosive high-strength deformation
Nanometer Mg alloy.
The anticorrosive high-strength deformation nanometer Mg alloy structure of the inventive method is: at rich magnesio
Nano level rich lithium accumulation regions and nanoscale richness aluminum accumulation regions are distributed in body, and other element is received
Rice accumulation regions.A the nanoscale richness lithium accumulation regions described in () is defined as lithium atom in this alloy structure
The region of percentage composition >=50At.%, the lithium atom percentage composition in this region is by its surface
50At.% steps up the 50-99.99At.% at center, this accumulation regions bulk averaged value model
Enclose for 100-8000 cubic nanometer, account for material volume content range, according to composition, place's science and engineering
Skill and parameter are different, for 5%-35%；B the nanoscale richness aluminum accumulation regions described in () is defined as this
The region of aluminum atomic percentage conc >=20At.% in alloy structure, the aluminum atom hundred in this region
Content is divided to be brought up to the 20-99At.% at center, rich aluminum accumulation regions body by the 20At.% on surface
Long-pending average value ranges is 100-30000 cubic nanometer, accounts for material volume content, according to composition,
Processing technique and parameter is different, scope is 0-25%；C () is different with processing technique according to composition,
This alloy also can be containing element aggregation districts such as nanoscale zinc-rich, Fu Yin, copper-rich, every kind of enrichment unit
Element atom content >=20At.% in its each nanoscale accumulation regions, and by surface to center
Bringing up to 20-90At.% successively, every kind of accumulation regions bulk averaged value scope is 100-125000
Cubic nanometer, accounting for material volume content range is 0-10%；Rich magnesium matrix definition described in (d)
Beyond above-mentioned various element nanoscale accumulation regions and other phase composition, magnesium atom content is big
Region in 50At.%.
The room-temperature property of described anticorrosive high-strength deformation nanometer Mg alloy is: at 0.1 mole
Potentiodynamic polarization electric current in saline is 3-12 μ A/cm2, when being exposed to surrounding, close
The components such as the water in its surface and air of the metallic element in gold, oxygen, carbon dioxide occur
Chemical reaction, Li that form a kind of densification, that be insoluble in water2CO3Protecting film, protects this conjunction
Gold body is from corrosion further, thus gives this alloy improved corrosion performance.Nano-structure is also
Impart simultaneously this alloy 100-250 kilonewton meter/kilogram high than yield strength, the highest can
Reach the high-elongation of 60% and good deformation at room temperature ability.
A kind of 1 millimeters thick Mg-11%Li-3.3%Al-0.6%Y-0.2%Zr anticorrosive height is presented herein below
The concrete preparation method of strength and deformation nanometer Mg latten, this preparation method step is as follows:
(1) choose 3 millimeters thick, 100-500 mm wide, the above length of 500-1000 millimeter,
Composition be the hot extrusion sheet material of Mg-11%Li-3.3%Al-0.6%Y-0.2%Zr as original material,
This material proportion is 1.4 grams every cubic centimetre, hardness is 63 ± 5HV and in 0.1 molar salt
Standard potentiodynamic polarization electric current in water is 12-15 μ A/cm2Above；
(2) above-mentioned hot extrusion pressing plate is put into 250-450 DEG C of electric furnace, be incubated more than 5-100 minute
After time, carry out Quenching Treatment, obtain Vickers hardness 135 ± 15HV and in 0.1 molar salt
Standard potentiodynamic polarization electric current 8 ± 2 μ A/cm in water2Quenching structure plate；
(3) to above-mentioned quenching structure plate time more than 10-100 DEG C of timeliness 0.5-1000 hour,
Obtain hardness be 90-135HV, in 0.1 mole of saline, potentiodynamic polarization electric current is 6-12
μA/cm2Aging Microstructure plate；
(4) milling train is utilized to roll above-mentioned Aging Microstructure plate, rolling direction, laterally and hang down
Nogata is to being the length of material, width and thickness direction respectively；
(5) every time under the amount of rolling 5-20%, mill speed is 3-20 rice per minute, until plate thickness
It is reduced to 1 millimeter by 3 millimeters, obtains described anticorrosive high-strength deformation nanometer Mg alloy；
(6) this anticorrosive high-strength deformation nanometer Mg alloy has and body is distributed in rich magnesium matrix
Long-pending average value ranges is 200-1800 cubic nanometer, and volumn concentration scope is 5-35%'s
Three-dimensional polyhedron richness lithium accumulation regions and bulk averaged value scope are 150-3000 cubic nanometer,
Volumn concentration scope is the nano-structure of the three-dimensional polyhedron richness aluminum accumulation regions of 3-8%；
(7) this anticorrosive high-strength deformation nanometer Mg alloy sheets, is provided simultaneously with at ambient temperature:
(a) high corrosion resistance, the standard potentiodynamic polarization electric current carried out in 0.1 mole of saline
The current of polarization recorded in test is 5-10 μ A/cm2, when its surface is exposed to surrounding,
There is chemistry in the components such as the metallic element in alloy can be with the water in air, oxygen, carbon dioxide
Reaction, Li that form a kind of densification, that be insoluble in water2CO3Protecting film, protection sheet material is subject to
Corrosion further；B () yield strength 230 ± 20MPa, than yield strength 165 ± 15,000
Newton meter/kilogram, and (c) elongation percentage 10-35%；
(8) due to described anticorrosive high-strength nano wrought magnesium alloy have ultralight, improved corrosion,
The excellent properties combination of high intensity and high deformation performance, thus can be applicable to manufacture ultralight magnesium alloy
Parts, are applied in following product:
Electronic apparatus class, such as mobile communication equipment, computer, photographing unit,
The vehicles, such as automobile, train, bicycle and civil aircraft,
Aero-Space, such as satellite, airship, space shuttle, moonfall device and rocket,
And defence product, if any people and unmanned military aircraft, guided missile, aerial bomb,
Big gun is penetrated or scatterable mine and submarine mine, radar, tank composite armour, automatic rifle
The artillery equipments such as sighting device, magazine and gun stock.
Can effectively alleviate these products weight, improve its payload, increase its intensity and rigidity,
Reduce vibration, absorb impact and effectively reduce the external environment condition electromagnetic interference to product.
Claims (7)
- The most anticorrosive high-strength deformation nanometer Mg alloy, (a) its tissue signature is, at it Nanoscale richness lithium accumulation regions and nanoscale richness aluminum accumulation regions, wherein nanometer are distributed in rich magnesium matrix The bulk averaged value scope of the rich lithium accumulation regions of level is 100-8000 cubic nanometer, and content accounts for material Cumulative volume scope is 5-35%；The bulk averaged value scope of nanoscale richness aluminum accumulation regions is 100-30000 cubic nanometer, content accounts for all materials and amasss scope is 0-25%；Receive described in (b) Rice Properties of Magnesium Alloy is characterised by, is provided simultaneously with following excellent properties at ambient temperature and combines: Potentiodynamic polarization electric current ultralight, in 0.1 mole of saline is 3-12 μ A/cm2Anticorrosive Property, 100-250 kilonewton meter/kilogram ratio yield strength, reach as high as 60% elongation percentage With good deformation performance.
- Anticorrosive high-strength deformation nanometer Mg alloy the most according to claim 1, it is special Levying and be, described magnesium alloy is containing 7-16Wt.% (weight percentage) lithium (Li), And Vickers hardness can increase to the ternary of more than 100HV and polynary magnesium lithium alloy after quenching.
- Anticorrosive high-strength deformation nanometer Mg alloy the most according to claim 1, it becomes Point distribution characteristics is: the nanoscale richness lithium accumulation regions described in (a) is defined as in this alloy structure The region of lithium atom percentage composition >=50At.%, the lithium atom percentage composition in this region is by it The 50At.% on surface steps up the 50-99.99At.% at center；Nanometer described in (b) The rich aluminum accumulation regions of level is defined as the region of aluminum atomic percentage conc >=20At.% in this alloy structure, Aluminum atomic percentage conc in this region is brought up to the 20-99 at center by the 20At.% on surface At.%；(c) according to composition with process technique different, this alloy also can contain nanoscale zinc-rich, The element aggregation such as Fu Yin, copper-rich district, every kind of enriched element is in its each nanoscale accumulation regions Atom content >=20At.%, and brought up to 20-90At.% successively to center by surface, every kind Nanoscale accumulation regions, bulk averaged value scope is 100-125000 cubic nanometer, accounts for material total Volume content scope is 0-10%；D the rich magnesium matrix described in () is defined as above-mentioned various element and receives Beyond meter level accumulation regions and other phase composition, the magnesium atom content region more than 50At.%.
- Anticorrosive high-strength deformation nanometer Mg alloy the most according to claim 1, it resists Corrosive characteristics is, when this alloy is exposed to surrounding, can form one on its surface Stable, fine and close, be insoluble in the Li of water2CO3Protecting film, gives this alloy improved corrosion performance, Protect this magnesium alloy from corrosion further.
- The preparation of anticorrosive high-strength deformation nanometer Mg alloy the most according to claim 1 Method, it is characterised in that this preparation method step is as follows:(1) choose above-mentioned containing 7-16Wt.% lithium and quenching after Vickers hardness can increase to 100 The ternary of more than HV and polynary magnesium lithium alloy bar, sheet material, band, wire rod, tubing or type The semi-finished product of material；(2) above-mentioned semi-finished product are heated to 200 DEG C of temperatures above, be incubated 1-100 minute with The upper time, carried out Quenching Treatment, and obtained more than Vickers hardness 100HV, in 0.1 molar salt Standard potentiodynamic polarization electric current in water is 3-12 μ A/cm2Quenching structure material；(3) above-mentioned quenching structure material being carried out nature or artificial aging, aging temp is permissible More than room temperature to 200 DEG C, aging time was from more than 1 minute to 10000 hour, after timeliness Material Vickers hardness reduce more than 1-50HV, in 0.1 mole of saline potentiodynamic polarization electricity Stream raises 0.1-10 μ A/cm2Above；(4) material after above-mentioned timeliness is carried out deformation process, when deflection reaches 2-20% After above, i.e. make described anticorrosive high-strength deformation nanometer Mg alloy.
- The preparation of anticorrosive high-strength deformation nanometer Mg alloy the most according to claim 5 Method, it is characterised in that the deformation process in described step (4) is: rolling, roll-in, forging Make, swage, extrude, one or more in drawing and stamping, deep draw and reaming.
- Anticorrosive high-strength deformation nanometer Mg alloy the most according to claim 1 can be applied In manufacture, there is anticorrosive, high specific strength, high specific stiffness, high damping and capability of electromagnetic shielding Excellent ultralight Magnesium Alloys Components, is applied in following product:Electronic apparatus class, such as mobile communication equipment, computer, photographing unit,The vehicles, such as automobile, train, bicycle and civil aircraft,Aero-Space, such as satellite, airship, space shuttle, moonfall device and rocket,And defence product, if any people and unmanned military aircraft, guided missile, aerial bomb, Big gun is penetrated or scatterable mine and submarine mine, radar, tank composite armour, automatic rifle The artillery equipments such as sighting device, magazine and gun stock.Can effectively alleviate these products weight, improve its payload, increase its intensity and rigidity, Reduce vibration, absorb impact and effectively reduce the external environment condition electromagnetic interference to product.
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