CN106148783B - Anticorrosive high-strength deformation nanometer magnesium alloy and its preparation method and application - Google Patents
Anticorrosive high-strength deformation nanometer magnesium alloy and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to anticorrosive high-intensitive deformation at room temperature nanometer magnesium alloys and its preparation method and application.By carrying out short route processing to particular category magnesium lithium alloy, it produces with the nanometer magnesium alloy that nanoscale richness lithium accumulation regions and nanoscale richness aluminium accumulation regions are distributed in rich magnesium matrix, wherein lithium atom percentage composition >=50-99% of nanoscale richness lithium accumulation regions, bulk averaged value range are 100-8000 cubic nanometer and volumn concentration range is 5-35%；Aluminium atom percentage composition >=20-99% of nanoscale richness aluminium accumulation regions, bulk averaged value range are 100-30000 cubic nanometer and volumn concentration range is 0-25%.At room temperature, being provided simultaneously with ultralight specific gravity, the polarization current in 0.1 mole of salt water can be down to 3 μ A/cm for this nanometer of magnesium alloy2Corrosion resistance, 100-250 kilonewton meter/kilogram ratio surrender the excellent properties combination of elongation percentage that is strong, reaching as high as 60% and good deformation performance, thus can be widely applied in mobile communication equipment, computer, camera, the vehicles, aerospace and defence product.
Description
Technical field
The present invention relates to a kind of new metallic materials and the preparation method and application thereof, more particularly, to a kind of anticorrosive, high
Intensity, deformation at room temperature performance be good, ultralight nano-structure wrought magnesium alloy and its preparation method and application.
Background technique
The development of modern science and technology has important dependence and requirement to new metallic material, it is desirable that its is light-weight, intensity
Height, anticorrosive, processability is good, easy to process.Mainly there is aluminium in the world, magnesium, three kinds of light metals of titanium, specific gravity is respectively 2.7,
1.74 and 4.5 grams/cc, wherein magnesium is most light.Magnesium alloy has relatively good ratio in these three alloy structure materials
Intensity and Castability, still, (1) because its hexagonal lattice structure slip system is less, deformation at room temperature performance is low；(2) corrosion resistance
Can be up to the present poor because one layer of fine and close protective film cannot be formed, and without a kind of sacrificial anode material can to it
It is protected as zinc coat is to steel surface on surface.Therefore this two problems of magnesium alloy are to restrict it extensively all the time
The bottleneck of application.
By the way that lithium is added to magnesium, magnesium lithium alloy is formed, can effectively solve the problem that the low problem of magnesium alloy deformation at room temperature performance.When
When lithium content is less than 5Wt.% (weight percent), magnesium lithium alloy still keeps the hexagonal lattice structure (referred to as α phase) of magnesium；When being more than
After 5Wt.%, magnesium hexagoinal lattice crystal structure starts body-centered cubic structure (β phase) more to slip system, that deformation at room temperature performance is good and turns
Become；After more than 10.5Wt.%, it is completely converted into body-centered cubic structure.So working as lithium content for Binary Mg Li Alloy
Less than 5Wt.%, for 5Wt.%-10.5Wt.% and be greater than 10.5Wt.% when, be respectively provided with single α phase, alpha+beta phase and single β
Phase constitution.It is less that α phase contains lithium amount, has high rigidity and intensity (intensity is generally about equal to 3 times of Vickers hardnesses), but deformation performance
Difference, and β phase is just the opposite, has soft, low-intensity but high deformation performance.So usual magnesium lithium alloy lithium content is higher,
β phase content is higher in tissue, and intensity and hardness are lower, and plastically deformed performance is better.One or more other alloying elements are added
To after Mg-Li alloy, ternary or polynary magnesium lithium alloy are formed, will cause the above-mentioned 5Wt.% and 10.5Wt.% lithium content of Li alloy
Tissue critical line movement and other phases formation in the tissue.These magnesium lithiums based on alpha+beta phase or β phase constitution close
For gold due to the presence of body-centered cubic crystal structure β phase, the magnesium alloy of deformation at room temperature performance opposite only hexagoinal lattice (α phase) is big
Width improves, and room temperature elongation percentage may be up to 80% or more.So the appearance of this kind of magnesium lithium alloy efficiently solves magnesium alloy room temperature
The low problem of deformation performance also further reduced magnesium alloy simultaneously as the specific gravity of lithium is very low (0.534 gram/cc)
Specific gravity is to 1.30-1.65g/cm3.Thus, magnesium lithium alloy based on alpha+beta phase or β phase constitution has ultralight, high ratio modulus, excellent
Ratio rigid, thermally conductive, conductive, outstanding absorption impact and damping performance, excellent electromagnetic shielding performance, weldability energy, good
Good machining property and cold deformation and processability.
In general, magnesium lithium alloy in the world is mainly ternary and multicomponent alloy, preparation method and process route are as follows: (1)
The raw material such as Mg, Li and other alloying elements and melting fusing are chosen, are melted in the electric furnace of protective atmosphere or clinker
After refining or fusing, (2) are cast into the ingot of various shape size, and (3) ingot after high temperature homogenizing annealing is handled, directly passes through
Bar, wire rod, plate, band, tubing and various profiles is made in the various thermal processing methods such as extruding, hot rolling, forging.
It is prepared through above-mentioned technical process, the ternary containing 7-16Wt.% lithium and multicomponent alloy profile are organized as alpha+beta phase
Or the tissue based on β phase, its usual mean grain size size is in for 50-300 micron range, and Vickers hardness range is in 50-
In 75HV, after being quenched, wherein some particular category alloy, hardness can reach 100HV or more, but through it is natural or artificial when
After effect, hardness can gradually fall back to state before quenching.
Currently, it is common these two types alpha+beta phase or β phase constitution based on ternary and polynary magnesium lithium alloy, although solving magnesium
The low problem of Alloy At Room Temperature deformation performance still since the chemical activity of lithium is high, causes original corrosion resistance to close with regard to poor magnesium
Golden corrosion resistance further deteriorates, that is to say, that not only current magnesium lithium alloy does not have asking for solution magnesium alloy corrosion resistance difference
Topic, renvoi deteriorates it more, becomes the alloy that corrosion resistance classification is worst in current all magnesium alloys, at the same intensity also into
One step reduces.For example, typical LA141 magnesium lithium alloy tensile strength in room temperature is 132-166MPa, surrenders in magnesium lithium alloy
Intensity is 106-158MPa and elongation percentage is 11%-24%.
So up to the present, not being documented in the world while there is anticorrosive, high-intensitive, deformation at room temperature
The appearance of wrought magnesium alloy that can be good.This kind of magnesium alloy thus is developed, one of international most important target of Mei Ye association is classified as, is
World today's magnesium alloy manufacturing industry and researcher worldwide technological puzzle in the urgent need to address.
Summary of the invention
The present invention by contain 7-16Wt.% lithium, and quench after Vickers hardness can increase 100HV or more ternary and
Polynary magnesium lithium alloy material, carries out further processing processing, and nanoscale extremely rare in metal material has been obtained in its tissue
The tissue in element aggregation area, the tissue impart the unusual performance of this magnesium alloy: while there is improved corrosion performance, high-strength
The good excellent properties combination of degree, deformation at room temperature performance.Therefore this anticorrosive high-strength deformation nanometer magnesium alloy has been invented, and its
Preparation method and application.The present invention has successfully hewed out a completely new approach, and solve not while having in the world at present
This worldwide technological puzzle of corrosion resistance is good, intensity is high and deformation at room temperature performance is good magnesium alloy.
The technical scheme of the invention to solve the technical problem is:
By to contain 7-16Wt.% lithium, and quench after Vickers hardness can increase 100HV or more ternary and polynary magnesium
Lithium alloy bar, plate, band, wire rod, tubing or profile semi-finished product, according to preparation method of the invention below, in its group
Nano scaled elemental accumulation regions are prepared in knitting, and form nano-structure, it is unique excellent which assigns this alloy
Combining properties, to prepare the anticorrosive high-strength nano wrought magnesium alloy.
The preparation method of the anticorrosive high-strength nano wrought magnesium alloy, which is characterized in that the preparation method step
It is as follows:
(1) choosing above-mentioned Vickers hardness containing 7-16Wt.% lithium and after quenching can increase the ternary of 100HV or more and more
First magnesium lithium alloy bar, plate, band, wire rod, tubing or profile semi-finished product；
(2) 200-450 DEG C or more is heated to above-mentioned semi-finished product, heat preservation 1-100 minutes or more time, carried out at quenching
Reason, obtaining Vickers hardness 100HV or more and the standard potentiodynamic polarization electric current in 0.1 mole of salt water is 3-12 μ A/cm2's
Quenching structure material；
(3) nature or artificial aging carried out to above-mentioned quenching structure material, aging temp can be from room temperature to 200 DEG C with
On, aging time is from 1 minute to 10000 hour or more；Tissue after timeliness, relative to quenching structure, according to aging temp, time
And the ingredient of alloy is different, Vickers hardness reduces 1-50HV or more and potentiodynamic polarization electric current increases in 0.1 mole of salt water
0.1-10μA/cm2More than；
(4) to after above-mentioned timeliness material carry out deformation process, processing mode be roll, forge, swaging, squeezing, drawing,
It is one of or several in roll-in, punching press, deep draw and reaming, when deflection is greater than 2-20% or more, obtain described anti-
Corrode high-strength nano wrought magnesium alloy, has nano-structure below；
(5) the nano-structure feature is that nanoscale richness lithium accumulation regions, the aggregation of nanoscale richness aluminium are distributed in rich magnesium matrix
Area and other element nanometers accumulation regions, tissue signature are: the nanoscale richness lithium accumulation regions described in (a) are defined as this alloy
The region lithium atom percentage composition >=50At.% in tissue, lithium atom percentage composition in the region by its surface 50At.%
Step up the 50-99.99At.% to center；(b) it is former that the nanoscale richness aluminium accumulation regions described in are defined as aluminium in this alloy structure
The region of sub- percentage composition >=20At.%, the aluminium atom percentage composition in the region are increased to center by the 20At.% on surface
20-99At.%；(c) according to ingredient and treatment process difference, this alloy can also contain the elements such as nanoscale zinc-rich, Fu Yin, copper-rich
Accumulation regions, atom content >=20At.% of the every kind of enriched element in its respectively nanoscale accumulation regions, and from surface to center according to
Secondary to be increased to 20-90At.%, every kind of nanoscale accumulation regions, bulk averaged value range is 100-125000 cubic nanometer, accounts for material
Total volume content range is 0-10%；(d) the rich magnesium matrix described in be defined as above-mentioned various elements nanoscale accumulation regions and its
Other than its phase composition, magnesium atom content is greater than the region of 50At.%.The nanostructure imparts the anticorrosive high intensity and receives
Following performances of rice wrought magnesium alloy.
(6) there is the anticorrosive high-strength nano wrought magnesium alloy of above-mentioned nano-structure feature, performance characteristic exists
In being provided simultaneously with improved corrosion, high intensity and high deformation performance at room temperature: the dynamic electricity of standard in 0.1 mole of salt water
Bit polarization electric current 3-12 μ A/cm2, when it is exposed to ambient enviroment, surface and the oxygen in ambient enviroment, carbon dioxide,
Moisture etc. is reacted, and a kind of Li that is fine and close, being insoluble in water is formed2CO3Protective film, such as the Al formed in aluminium surface2O3Film
Protect the Cr of aluminium and stainless steel surface2O3Film protect stainless steel it is the same, assign this alloy improved corrosion performance, protect alloy from
It further corrodes；Meanwhile nanostructure assign the magnesium alloy height than yield strength up to 100-250 kilonewton meter/kilogram, and body
The rich lithium accumulation regions of heart cubic structure, impart the high deformation performance of the magnesium alloy, and elongation percentage reaches as high as 60%.
Here it is the preparation methods of the anticorrosive high-strength nano wrought magnesium alloy and its gained nano-structure to receive with this
Rice tissue assigns the excellent properties combination of this alloy.
(7) since the anticorrosive high-strength nano wrought magnesium alloy has ultralight, improved corrosion, high intensity and high deformation
The excellent properties of performance combine, thus can be applied to manufacture ultralight Magnesium Alloys Components, are applied in following products:
Electronic apparatus class, such as mobile communication equipment, computer, camera,
The vehicles, such as automobile, train, bicycle and civil aircraft,
Aerospace, such as satellite, airship, space shuttle, moonfall device and rocket,
And defence product, as someone and unmanned military aircraft, guided missile, aerial bomb, big gun penetrate or scatterable mine and submarine mine,
The artillery such as radar, tank composite armour, automatic rifle sighting device, magazine and gun stock equipment.
Can effectively mitigate the weight of these products, improve its payload, increase its intensity and rigidity, reduce vibration,
It absorbs impact and external environment is effectively reduced to the electromagnetic interference of product.
The technological progress achieved by the present invention is by adopting the above technical scheme:
The present invention by containing 7-16Wt.% lithium and quench after Vickers hardness can increase 100HV or more ternary and
Polynary magnesium lithium alloy semi-finished product carry out further processing processing, have obtained having excellent corrosion protection energy, be provided simultaneously with it is high-intensitive,
The good nanometer magnesium alloy of deformation at room temperature performance, preparation method and application, successfully solving in the world not while having highly resistance
Corrosive nature, high intensity and good magnesium alloy this worldwide technological puzzle of deformation at room temperature performance.
Why the magnesium-alloy material of the method for the present invention production, be able to solve this global problem, is attributed to the fact that (a) is selected
Present invention particular category magnesium alloy semifinished material as defined in above-mentioned paragraph, (b) with preparation side described in the invention
Method (c) is produced, and nanometer the special nano-structure being described in detail in the preceding paragraph: is distributed in rich magnesium matrix
Rich lithium accumulation regions, nanoscale richness aluminium accumulation regions and the other element nanometers accumulation regions of grade.
In general, the material containing tissue size less than 100 nanometers is known as nano-structure material, the material is because of its tissue size
Significantly it is lower than common micro grade organization material, thus is very different from micron organization material in performance.To micron tissue material
For material, corrosion resistance, strength character and deformation at room temperature performance be it is conflicting, this grows that relationship to disappear, is extremely difficult to
All these performance indicators are in optimum state simultaneously.So the special nano-structure of this alloy, has broken micron organization material
This limitation, impart this magnesium alloy be so different from the unique improved corrosion of usual micron order magnesium alloy, high intensity and
The excellent properties of deformation at room temperature performance combine.
Dynamic voltage polarizing electric current of this Magnesium Anti-Corrosion in 0.1 mole of salt water is 3-12 μ A/cm2, the electric current
Smaller corrosion resistance is better, so, 1 μ A/cm of this alloy corrosion electric current between fine aluminium in most cases2With the 10 of pure magnesium
μA/cm2Centre, and fine aluminium and pure magnesium have best corrosion resistance in aluminium alloy and magnesium alloy respectively.That is, this
Carry out the worst specific magnesium lithium alloy of the corrosion resistance in all magnesium alloys, is required according to condition, at the art of this patent processing
Reason, after forming nano-structure, corrosion resistance substantially surmounts pure magnesium and other classification magnesium alloys, and it is best to become corrosion resistance
Magnesium alloy.In ambient atmosphere environment, the generations such as this alloy surface and oxygen, moisture and carbon dioxide in atmosphere and environment are anti-
It answers, forms one layer of fine and close Li for being insoluble in water2CO3Protective film.This layer of protective film, just as aluminium alloy and stainless steel surface
The Al of formation2O3And Cr2O3Protective film is the same, protects its alloy bulk from further corroding, assigns this alloy high corrosion resistance
Energy.Meanwhile nano-structure also assign 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 so excellent combining properties, obtain important breakthrough in field of magnesium alloy, be attributed to the fact that for
Meet this patent particular requirement containing 7-16Wt.% lithium and quench after Vickers hardness can increase 100HV or more ternary and
Complex magnesium alloy bar, plate, wire rod, tubing or profile semi-finished product, according to the processing method of this patent, carry out further plus
The obtained unique nano-structure of work forms the anticorrosive high-strength deformation nanometer magnesium alloy.
Since the anticorrosive high-strength nano wrought magnesium alloy has ultralight, improved corrosion, high intensity and high morphotropism
The excellent properties combination of energy, thus can be applied to manufacture ultralight Magnesium Alloys Components, it is applied in following products:
Electronic apparatus class, such as mobile communication equipment, computer, camera,
The vehicles, such as automobile, train, bicycle and civil aircraft,
Aerospace, such as satellite, airship, space shuttle, moonfall device and rocket,
And defence product, as someone and unmanned military aircraft, guided missile, aerial bomb, big gun penetrate or scatterable mine and submarine mine,
The artillery such as radar, tank composite armour, automatic rifle sighting device, magazine and gun stock equipment.
Can effectively mitigate the weight of these products, improve its payload, increase its intensity and rigidity, reduce vibration,
It absorbs impact and external environment is effectively reduced to the electromagnetic interference of product.
Detailed description of the invention
Fig. 1 is atom distribution of this anticorrosive high-strength deformation nanometer magnesium alloy in 40x40x70 nanometers of three-dimensional space
And its organization chart；
Fig. 2 is atom distribution and its tissue of this anticorrosive high-strength deformation nanometer magnesium alloy in bigger three-dimensional space
Figure；
Fig. 3 presents this anticorrosive high-strength deformation nanometer magnesium alloy and existing industrial titanium alloy, aluminium alloy and existing magnesium
Performance comparison of the alloy in specific strength and elongation percentage performance space；
Fig. 4 presents this anticorrosive high-strength deformation nanometer magnesium alloy and existing industrial magnesium alloys, than yield strength and
Elongation percentage performance space, and its performance pair in the performance space than yield strength and the polarization current for representing corrosion resistance
Than；
Fig. 5 is that this anticorrosive high-strength deformation nanometer magnesium alloy and the pure magnesium alloy of existing best corrosion resistance behavior exist
Experimental result comparison in corrosion resistance test, and its better than the Corrosion resistance mechanism of pure magnesium corrosion resistance.
In figure 1 above, 1- rich magnesium matrix, 2- richness lithium accumulation regions, 3- richness aluminium accumulation regions.
Wherein, Fig. 1, three-dimensional atom probe reconstruct image disclose this magnesium alloy in a 40x40x70 nanometers of three-dimensional space areas
Tissue and atom distribution map in domain.It is (dark that (1-a) illustrates the rich lithium accumulation regions in rich magnesium matrix (loose sand shape region)
Particulate matter) and rich aluminium accumulation regions (lighter colored particles object) appearance and size and spatial distribution.Rich lithium accumulation regions and rich aluminium accumulation regions,
Be respectively defined as by atomic percentage content be 50At.% lithium, 20At.% aluminium equal size interface, area encompassed.(1-b)
It can be seen that lithium atom percentage composition from left to right from rich magnesium matrix into rich lithium accumulation regions the equal size interface of 50At.% and in
The heart, the distribution situation successively increased.(1-c) illustrates aluminium atom percentage composition from left to right from rich magnesium matrix to rich aluminium accumulation regions
The distribution situation that the equal size interface of middle 20At.% and aggregation district center successively increase.
Fig. 2, three-dimensional atom probe reconstruct image disclose: the ruler of the rich lithium accumulation regions (dark particulate matter) in (A) this alloy
Very little, pattern and spatial distribution state.Rich lithium accumulation regions are defined as the equal size interface institute by atomic percentage content for 50At.% lithium
The region of encirclement；(B) rich magnesium matrix (the loose sand shape of the rich lithium accumulation regions (dark particulate matter) and its place in figure (A) is illustrated
Region is defined as other than all elements accumulation regions and other phase constitutions, magnesium atom content be greater than 50At.% region) group
It knits；Figure (C) illustrates in figure (B), and the diameter that the rectangular item of central part is indicated is in 10 nm cylinder shape regions, and magnesium and lithium are former
Son discloses magnesium and lithium atom distribution situation in rich magnesium matrix and rich lithium accumulation regions along the distribution map in body length direction.
Fig. 3 is this nanometer of magnesium alloy and existing industrial titanium alloy, aluminium alloy and magnesium alloy in specific strength and elongation percentage performance
Performance comparison in space；The specific strength and elongation percentage of usual material are that this rises that drop as shown in alloys other in this figure
Relationship.This comparison has disclosed this nanometer of magnesium alloy, compared with industrial aluminum, magnesium, titanium alloy, possesses high specific strength, with Gao Yan
Stretch the excellent properties combination of rate and high deformation performance.
Fig. 4-a shows this alloy and existing industrial magnesium alloys, than the performance in yield strength-elongation percentage performance space
Comparison.Two performance indicators of ratio yield strength and elongation percentage of usual material are this liters as shown in magnesium alloys other in this figure
The relationship of that drop.The comparison discloses this alloy compared with current existing industrial magnesium alloys, while having very high stronger than surrendering
The excellent properties of degree and elongation percentage combine.
Fig. 4-b shows this alloy and other existing industrial magnesium alloys in than yield strength-polarization current performance space
Performance comparison shows this alloy compared with industrial magnesium alloys, is provided simultaneously with very high than yield strength and in 0.1 mole of salt water
The excellent properties of hypopolarization electric current combine.Note that industrial alloy polarization current is from document, magnesium and its alloy therein,
Polarization current is varied because test condition is different.
Fig. 5 illustrates the superior corrosion resistance of this alloy and its anticorrosive principle.(a) show that this alloy and pure magnesium exist
The standard dynamic potential polarization curve tested in 0.1 mole of salt water, the standard potentiodynamic polarization of this alloy and pure magnesium in the curve
Electric current is respectively 6 and 10 μ A/cm2, it is (b) to have carried out electrochemistry friendship after this alloy and pure magnesium impregnate 3 days in 0.1 mole of salt water
Flow impedance is general, has disclosed this nanometer of magnesium alloy dissolution kinetics and has been significantly less than the pure magnesium with best corrosion resistance, also
It is that (a) and (b) discloses the pure magnesium of this alloy ratio jointly and possess more superior corrosion resistance, and figure (c) and (d) pass through XPS deep layer
Anatomy technology, test analysis have arrived this alloy surface chemistry tissue, disclose and form one layer of densification in nanometer Mg alloy surface
Be insoluble in water Li2CO3Protective film protects this alloy from further corroding.
Specific embodiment
The present invention is increases to 100HV or more to containing Vickers hardness after 7-16Wt.% lithium and quenching, such 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%
Ternarys such as Zr, Mg-13%Li-3%Al and Mg-13%Li-3%Al-1%Zn (ingredient be weight percentage Wt.%) and polynary
The green shape of magnesium lithium alloy is prepared in its tissue with following described according to the method described in the present invention and step
Nano-structure, and when nano-structure imparts the magnesium alloy room temperature, to be provided simultaneously with improved corrosion, high intensity, deformation performance excellent
It is good, so that anticorrosive high-strength deformation nanometer magnesium alloy be made.
The anticorrosive high-strength deformation nanometer Magnesium Alloy of the method for the present invention are as follows: nanoscale is distributed in rich magnesium matrix
Rich lithium accumulation regions and nanoscale richness aluminium accumulation regions and other element nanometers accumulation regions.(a) the nanoscale richness lithium accumulation regions described in
It is defined as the region lithium atom percentage composition >=50At.% in this alloy structure, the lithium atom percentage composition in the region is by it
The 50At.% on surface steps up the 50-99.99At.% to center, and the accumulation regions bulk averaged value range is vertical for 100-8000
Square nanometer accounts for material volume content range, different according to ingredient, treatment process and parameter, is 5%-35%；(b) receiving described in
Meter level richness aluminium accumulation regions are defined as the region aluminium atom percentage composition >=20At.% in this alloy structure, and the aluminium in the region is former
Sub- percentage composition is increased to the 20-99At.% at center by the 20At.% on surface, and rich aluminium accumulation regions bulk averaged value range is
100-30000 cubic nanometer accounts for material volume content, different according to ingredient, treatment process and parameter, range 0-25%；(c)
According to ingredient and treatment process difference, this alloy can also contain the element aggregations areas such as nanoscale zinc-rich, Fu Yin, copper-rich, every kind of richness
Collect atom content >=20At.% of the element in its respectively nanoscale accumulation regions, and is successively increased to 20- from surface to center
90At.%, every kind of accumulation regions bulk averaged value range are 100-125000 cubic nanometer, and accounting for material volume content range is 0-
10%；(d) the rich magnesium matrix described in is defined as other than above-mentioned various elements nanoscale accumulation regions and other phase compositions, and magnesium is former
Sub- content is greater than the region of 50At.%.
The room-temperature property of the anticorrosive high-strength deformation nanometer magnesium alloy are as follows: the electrokinetic potential pole in 0.1 mole of salt water
Galvanic current is 3-12 μ A/cm2, when being exposed to ambient enviroment, the metallic element in alloy is on its surface and water, the oxygen in air
The components such as gas, carbon dioxide chemically react, and form a kind of Li that is fine and close, being insoluble in water2CO3Protective film protects this alloy
Ontology assigns this alloy improved corrosion performance from further corroding.Nano-structure also imparts this alloy 100- simultaneously
250 kilonewton meters/kilogram height than yield strength, reach as high as 60% high-elongation and good deformation at room temperature ability.
Here is the anticorrosive high-strength deformation nanometer of 1 millimeters thick Mg-11%Li-3.3%Al-0.6%Y-0.2%Zr of one kind
The specific preparation method of magnesium alloy sheet, steps are as follows for the preparation method:
(1) 3 millimeters thicks, 100-500 mm wide, 500-1000 millimeters or more length, ingredient Mg-11%Li- are chosen
For the hot extrusion plate of 3.3%Al-0.6%Y-0.2%Zr as original material, which is 1.4 grams per cubic centimeter, firmly
Degree is 63 ± 5HV and the standard potentiodynamic polarization electric current in 0.1 mole of salt water is 12-15 μ A/cm2More than；
(2) above-mentioned hot extrusion pressing plate 250-450 DEG C of electric furnace is put into after heat preservation 5-100 minutes or more time to carry out at quenching
Reason, obtains 135 ± 15HV of Vickers hardness and 8 ± 2 μ A/cm of standard potentiodynamic polarization electric current in 0.1 mole of salt water2Quenching
Group textile board；
(3) to above-mentioned quenching structure plate in 10-100 DEG C of timeliness 0.5-1000 hours or more time, obtaining hardness is 90-
135HV, potentiodynamic polarization electric current is 6-12 μ A/cm in 0.1 mole of salt water2Aging Microstructure plate；
(4) above-mentioned Aging Microstructure plate is rolled using milling train, rolling direction is laterally and vertically material respectively
Length, width and thickness direction；
(5) every time under the amount of rolling 5-20%, mill speed be 3-20 meter per minute, until plate thickness by 3 millimeters be reduced to 1 in the least
Rice, obtains the anticorrosive high-strength deformation nanometer magnesium alloy；
(6) this anticorrosive high-strength deformation nanometer magnesium alloy, which possesses, bulk averaged value range is distributed in rich magnesium matrix is
200-1800 cubic nanometer, three-dimensional polyhedron richness lithium accumulation regions and the bulk averaged value that volumn concentration range is 5-35%
Range is 150-3000 cubic nanometer, and volumn concentration range is the nanometer group of the three-dimensional polyhedron richness aluminium accumulation regions of 3-8%
It knits；
(7) this anticorrosive high-strength deformation nanometer magnesium alloy plate, is provided simultaneously at room temperature: (a) high corrosion resistance,
The polarization current measured in the standard potentiodynamic polarization current testing carried out in 0.1 mole of salt water is 5-10 μ A/cm2, when it
When surface is exposed to ambient enviroment, the metallic element in alloy can be with the water in air, oxygen, the components such as carbon dioxide
Reaction is learned, a kind of Li that is fine and close, being insoluble in water is formed2CO3Protective film, protection plate are further corroded；(b) surrender is strong
Spend 230 ± 20MPa, than 165 ± 15 kilonewton meter of yield strength/kilogram, and (c) elongation percentage 10-35%；
(8) since the anticorrosive high-strength nano wrought magnesium alloy has ultralight, improved corrosion, high intensity and high deformation
The excellent properties of performance combine, thus can be applied to manufacture ultralight Magnesium Alloys Components, are applied in following products:
Electronic apparatus class, such as mobile communication equipment, computer, camera,
The vehicles, such as automobile, train, bicycle and civil aircraft,
Aerospace, such as satellite, airship, space shuttle, moonfall device and rocket,
And defence product, as someone and unmanned military aircraft, guided missile, aerial bomb, big gun penetrate or scatterable mine and submarine mine,
The artillery such as radar, tank composite armour, automatic rifle sighting device, magazine and gun stock equipment.
Can effectively mitigate the weight of these products, improve its payload, increase its intensity and rigidity, reduce vibration,
It absorbs impact and external environment is effectively reduced to the electromagnetic interference of product.
Claims (6)
1. anticorrosive high-strength deformation nanometer magnesium alloy, which is characterized in that it is 7- that the magnesium alloy, which is containing weight percentage,
The lithium of 16Wt.%, and quench after Vickers hardness can increase 100HV or more ternary and polynary magnesium lithium alloy；
(a) its tissue signature is, nanoscale richness lithium accumulation regions and nanoscale richness aluminium accumulation regions are distributed in its rich magnesium matrix,
Wherein the bulk averaged value range of nanoscale richness lithium accumulation regions is 100-8000 cubic nanometer, and content accounts for material total volume range and is
5-35%；The bulk averaged value range of nanoscale richness aluminium accumulation regions is 100-30000 cubic nanometer, and content accounts for material total volume model
It encloses for 0-25%, does not include at 0 point；(b) the nanometer Properties of Magnesium Alloy is characterized in that, is provided simultaneously at room temperature following excellent
Different combining properties: potentiodynamic polarization electric current ultralight, in 0.1 mole of salt water is 3-12 μ A/cm2Corrosion resistance, 100-250
Kilonewton meter/kilogram ratio yield strength, reach as high as 60% elongation percentage and good deformation performance；
The preparation of the nanometer magnesium alloy includes at least following steps:
(1) choose it is above-mentioned containing 7-16Wt.% lithium and quench after Vickers hardness can increase 100HV or more ternary and polynary magnesium
Lithium alloy；
(2) 200 DEG C or more are heated to above-mentioned alloy, heat preservation 1 minute or more time, are quenched, obtain Vickers hardness
100HV or more, the standard potentiodynamic polarization electric current in 0.1 mole of salt water are 3-12 μ A/cm2Quenching structure material；
(3) timeliness is carried out to above-mentioned quenching structure material, aging temp is more than room temperature, and aging time was at 1 minute or more, timeliness
Material Vickers hardness afterwards reduces by 1 or more, potentiodynamic polarization electric current increases 0.1 μ A/cm in 0.1 mole of salt water2More than；
(4) deformation process is carried out to the material after above-mentioned timeliness, after deflection reaches 2-20%, that is, be made described anticorrosive
High-strength deformation nanometer magnesium alloy.
2. anticorrosive high-strength deformation nanometer magnesium alloy according to claim 1, component distributing are characterized in that: (a) institute
The nanoscale richness lithium accumulation regions stated are defined as the region lithium atom percentage composition >=50At.% in the alloy structure, in the region
Lithium atom percentage composition the 50-99.99At.% to center is stepped up by the 50At.% on its surface；(b) nanometer described in
Grade rich aluminium accumulation regions are defined as the region aluminium atom percentage composition >=20At.% in the alloy structure, the aluminium atom in the region
Percentage composition is increased to the 20-99At.% at center by the 20At.% on surface；(c) described according to ingredient and treatment process difference
Nanometer magnesium alloy can also contain nanoscale zinc-rich, Fu Yin, copper-rich element aggregation area, and respectively nanoscale is poly- at its for every kind of enriched element
Collect atom content >=20At.% in area, and is successively increased to 20-90At.%, every kind of nanoscale aggregation from surface to center
Area, bulk averaged value range are 100-125000 cubic nanometer, and accounting for material total volume content range is 0-10%, do not include at 0 point；
(d) the rich magnesium matrix described in is defined as other than above-mentioned various elements nanoscale accumulation regions and other phase compositions, and magnesium atom contains
Amount is greater than the region of 50At.%.
3. anticorrosive high-strength deformation nanometer magnesium alloy according to claim 1, which is characterized in that the nanometer magnesium alloy
When being exposed to ambient enviroment, Li can be formed on its surface2CO3Protective film.
4. anticorrosive high-strength deformation nanometer magnesium alloy according to claim 1, which is characterized in that the nanometer magnesium alloy
It can be applied to manufacture Magnesium Alloys Components, to be applied to electric equipment products, vehicles product, Aerospace Products, national defence
Product.
5. a kind of preparation method of anticorrosive high-strength deformation nanometer magnesium alloy as described in claim 1, which is characterized in that should
Steps are as follows for preparation method:
(1) choose it is above-mentioned containing 7-16Wt.% lithium and quench after Vickers hardness can increase 100HV or more ternary and polynary magnesium
Lithium alloy；
(2) 200 DEG C of temperatures above are heated to above-mentioned alloy, heat preservation 1 minute or more time, are quenched, obtain Vickers
Hardness 100HV or more, the standard potentiodynamic polarization electric current in 0.1 mole of salt water are 3-12 μ A/cm2Quenching structure material；
(3) timeliness is carried out to above-mentioned quenching structure material, aging temp is more than room temperature, and aging time was at 1 minute or more, timeliness
Material Vickers hardness afterwards reduces by 1 or more, potentiodynamic polarization electric current increases 0.1 μ A/cm in 0.1 mole of salt water2More than；
(4) deformation process is carried out to the material after above-mentioned timeliness, after deflection reaches 2-20%, that is, be made described anticorrosive
High-strength deformation nanometer magnesium alloy.
6. the preparation method of anticorrosive high-strength deformation nanometer magnesium alloy according to claim 5, which is characterized in that described
Deformation process in step (4) are as follows: rolling roll-in, is forged, swaged, squeezing, one of drawing and stamping, deep draw and reaming
Or it is several.
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| CN103882354A (en) * | 2014-02-18 | 2014-06-25 | 中南大学 | Hot treatment process for remarkably improving comprehensive performance of aluminum alloy |
| CN104131247A (en) * | 2014-08-12 | 2014-11-05 | 中国科学院金属研究所 | Heat treatment process for inhibiting plastic instability of quasi-crystal reinforced magnesium lithium alloys |
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| CN103882354A (en) * | 2014-02-18 | 2014-06-25 | 中南大学 | Hot treatment process for remarkably improving comprehensive performance of aluminum alloy |
| CN104131247A (en) * | 2014-08-12 | 2014-11-05 | 中国科学院金属研究所 | Heat treatment process for inhibiting plastic instability of quasi-crystal reinforced magnesium lithium alloys |
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