CN103320663A - Quasicrystal-containing magnesium alloy with high corrosion resistance and preparation method and application thereof - Google Patents
Quasicrystal-containing magnesium alloy with high corrosion resistance and preparation method and application thereof Download PDFInfo
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- CN103320663A CN103320663A CN201310214206XA CN201310214206A CN103320663A CN 103320663 A CN103320663 A CN 103320663A CN 201310214206X A CN201310214206X A CN 201310214206XA CN 201310214206 A CN201310214206 A CN 201310214206A CN 103320663 A CN103320663 A CN 103320663A
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Abstract
The invention relates to the field of magnesium alloy, specifically to a quasicrystal-containing magnesium alloy with high corrosion resistance and a preparation method and an application thereof, especially to a quasicrystal-containing magnesium alloy material which has good uniform corrosion and high pitting resistance in a NaCl aqueous solution at room temperature and a method for preparing the alloy material. According to the invention, the poor corrosion resistance problem of magnesium alloy is solved. Through reasonable selection of alloying elements, a quasicrystal phase is introduced into a magnesium alloy matrix so as to prepare the quasicrystal-containing Mg-Li alloy with high corrosion resistance. The quasicrystal-containing magnesium alloy can be a quasicrystal phase reinforced magnesium alloy of the alpha-Mg monophase field and alpha-Mg+beta-Li diphasic filed, and contains the following components: by weight, 0-11.5% of Li, 5-10% of Zn, 0.5-2% of Y and the balance Mg. A product is obtained after alloy smelting and subsequent homogenization treatment. The treatment technology is simple and convenient to operate.
Description
Technical field
The present invention relates to the magnesium alloy field, what be specially a kind of high resistance to corrosion contains accurate grained magnesium alloy and its preparation method and application, particularly has at ambient temperature containing accurate brilliant ultralight magnesium alloy materials and preparing the method for this alloy material of better uniform corrosion and higher pitting corrosion resistant performance in the NaCl aqueous solution.
Background technology
Magnesium lithium alloy is the lightest structural metallic materials during present engineering is used, and its density is at 1.35-1.65g/cm
3Between, and have specific tenacity and the characteristic such as high, the cold and hot deformability of specific rigidity is strong, anisotropy is not obvious and low-temperature performance is good.Magnesium lithium alloy also has the plurality of advantages of magnesium alloy, strong such as anti-high energy particle penetrativity, capability of electromagnetic shielding good, damping capacity good, machinability is good etc., the desirable lightweight structural materials in field such as space flight, aviation, electronics and military affairs, so that the Mg-Li alloy has potential wide application prospect at high-technology fields such as aerospace and automobiles.Yet the erosion resistance extreme difference of magnesium lithium alloy has seriously restricted the application of alloy and further development.Document (Corrosion Science (corrosion science) 51 (2009) 1087) has reported that the chemically reactive of element Li is very strong, the corrosion resistance of the magnesium lithium alloy after the alloying will be very poor with it, and corrosion can preferentially occur at α-Mg and β-Li phase interface place.
In recent years, become the hot issue of magnesium alloy research about accurate brilliant formation in magnesium alloy strengthening mechanism machine-processed and alloy.Accurate brilliant (being crystal quasi-periodicity) is a kind of solid-state ordered phase that has simultaneously the orderly and noncrystal rotational symmetry of long-range translation quasi-periodicity, has typical five times and ten inferior special symmetry, is a kind of novel solid-state structure.Document (Science (science) 261 (1993) 737) has reported that accurate crystalline substance has some superior especially performances such as high hardness, high resistance to corrosion, low interfacial energy, high thermostability and low frictional coefficient etc.In addition, document (Trans.Nonferrou Met.Soc.China. (China YouSe Acta Metallurgica Sinica) 19 (2009) 1093) and (Mater.Sci.Eng.A. (Materials Science and Engineering) 488 (2008) 102) have reported that accurate crystalline phase can effectively reduce the erosion rate of Mg-Zn-Y magnesium alloy as second-phase.Can predict, should help the raising of Alloy Anti corrosive nature by the accurate crystalline phase of self-generating in the Mg-Li alloy, can and enlarge its range of application for performance under the actual Service Environment that improves magnesium lithium alloy provides a kind of novel solution.
Summary of the invention
What the object of the present invention is to provide a kind of high resistance to corrosion contains accurate grained magnesium alloy and its preparation method and application, solve the problem of Magnesium Anti-Corrosion extreme difference, by the choose reasonable alloying element, accurate crystalline phase is incorporated in the magnesium alloy substrate, has prepared the accurate brilliant single-phase and two-phase ultralight magnesium alloy that contains that has better uniform corrosion and higher pitting corrosion resistant performance in the NaCl aqueous solution at ambient temperature.
Technical scheme of the present invention is:
A kind of contain accurate brilliant high corrosion resistance can magnesium alloy, magnesium alloy is in α-Μ g single phase region or the quasi crystal phase fortified magnesium alloy of α-Μ g+ β-Li two-phase region, percentage ratio meter by weight, its component and content thereof are: lithium content is 0-11.5%; Zinc content is 5-10%; Yttrium content is 0.5-2%; Mg content is the balance surplus.
Described contain accurate brilliant high corrosion resistance can magnesium alloy, the weight ratio Zn/Y of zinc and yttrium is 5-10.
Described contain accurate brilliant high corrosion resistance can magnesium alloy, zinc content preferable range is 6-8%, yttrium content preferable range is 1.0-1.5%, the weight ratio Zn/Y preferable range of zinc and yttrium is 6-7; The lithium content preferable range is 6-8%.
The described preparation method who contains accurate brilliant high corrosion resistance energy magnesium alloy, alloy melting and subsequent thermal extrusion processing deformation process are as follows:
1) takes by weighing out alloying element zinc and yttrium by zinc yttrium weight ratio Zn/Y=5-10 ratio;
2) when temperature is 720-740 ℃, add the pure magnesium of alloy raw material;
2) when temperature is 750-760 ℃, add alloying element zinc and magnesium yttrium master alloy Mg-24wt%Y;
3) when temperature is down to 730-740 ℃, add the alloying element lithium; When lithium content is zero, omit this step;
4) when temperature is 720-730 ℃, alloy carries out refining;
5) be 750-760 ℃ in temperature, cast;
6) with the ingot casting of casting, the homogenizing of carrying out under 350-400 ℃ 4-16 hour is processed into goods.
The described preparation method who contains accurate brilliant high corrosion resistance energy magnesium alloy when the addition element lithium, adopts LiCl and LiF insulating covering agent, and logical CO
2Or air and SF
6Mixed gas is protected, and the weight ratio of LiCl and LiF is (3:1)-(4:1), and the weight of LiCl and LiF accounts for the 2-4% of alloy gross weight; Per-cent by volume, mixed gas is the CO of 99-99.5%
2Or air, 0.5-1%SF6 mix.
The described preparation method who contains accurate brilliant high corrosion resistance can magnesium alloy in the refining process, spreads refining agent LiBr alloy at the crest of melt and carries out refining, and consumption is the 0.5-2.5% of furnace charge gross weight.
The described preparation method who contains accurate brilliant high corrosion resistance energy magnesium alloy, when casting, protect with the sulphur of weight ratio (0.6:1)-(1.4:1) and boric acid mixed powder and/or mixed gas, the add-on of sulphur and boric acid accounts for the 0.5-1% of alloy gross weight; Per-cent by volume, mixed gas is 99-99.5%CO
2Or air and 0.5-1%SF
6Mix.
The described preparation method who contains accurate brilliant high corrosion resistance energy magnesium alloy, after refining finished, bath surface spread with LiCl and LiF insulating covering agent, and the weight ratio of LiCl and LiF is (3:1)-(4:1), and the weight of LiCl and LiF accounts for the 2-4% of furnace charge gross weight; After crucible temperature was stabilized in 760-780 ℃, melt left standstill 20-30 minute; Then, per-cent by volume is at 99-99.5% air or CO
2, 0.5-1%SF6 draws slag under mixed gas protected.
The described preparation method who contains accurate brilliant high corrosion resistance energy magnesium alloy preferably, after casting is finished, processes the homogenizing that the ingot casting of casting carried out 4-8 hour under 360-380 ℃, with the segregation of elimination alloying element, and MgZn low melting point phase is fallen in abundant solid solution.
The described application that contains accurate brilliant high corrosion resistance can magnesium alloy, described used for magnesium alloy be in the lightweight magnesium alloy material with anticorrosive destructiveness, at ambient temperature the corrosion potential E in the 0.1M NaCl solution
Corr=-1.65～-1.50V
SCE, corrosion electric current density is i
Corr=5-60 μ A/cm
2, weight loss rate is 0.24-6.52mg/cm
2/ day, density is 1.30-1.85g/cm
3
Advantage of the present invention and beneficial effect are:
1, the present invention is incorporated into accurate crystalline phase in the magnesium alloy substrate of Different L i content than (Zn/Y) by zinc yttrium in the control alloying element.
2, the present invention adopts that the method has obtained to have low density, the magnesium alloy of high corrosion resistance, is particularly suitable for lightweight engineered material demand, and can has higher anticorrosive destructiveness under certain service condition.
3, the goods of the present invention after alloy melting and the processing of follow-up homogenizing, its processing technological operation is simple, convenient.
Description of drawings
Fig. 1 contains and does not contain the at ambient temperature macro etch pattern photo after 0.1M NaCl solution soaking of accurate grained magnesium alloy (embodiment 1, embodiment 2 and embodiment 3).
Wherein, a) Mg-1%Li; B) Mg-5%Li; C) Mg-6%Li; D) Mg-5%Li-6%Zn-1.2Y%(embodiment 3); E) Mg-6%Li-6%Zn-1.2Y%(embodiment 1); F) Mg-8%Li-6%Zn-1.2Y%(embodiment 2).
Fig. 2 does not contain accurate brilliant Mg-6%Li magnesium alloy and contains the at ambient temperature cross section erosion profile photo after 0.1M NaCl solution soaking of accurate brilliant Mg-6%Li-6%Zn-1.2%Y magnesium alloy (embodiment 1).
Wherein, a) Mg-6%Li; B) Mg-6%Li-6%Zn-1.2Y%(low power); C) Mg-6%Li-6%Zn-1.2Y%(high power).
Embodiment
The high resistance to corrosion of the present invention contain accurate grained magnesium alloy, the aluminum magnesium containing alloy materials brilliant reinforced magnesium alloy that is as the criterion, that magnesium alloy is at the accurate brilliant reinforced magnesium alloy of α-Μ g single phase region and α-Μ g+ β-Li two-phase region, its component and content thereof are: lithium (Li) content is that 0-11.5%(is preferably 6-8%, perhaps 0-5%); Zinc (Zn) content is that 5-10%(is preferably 6-8%); Yttrium (Y) content is that 0.5-2%(is preferably 1.1-1.5%) and the magnesium (Mg) of surplus form, all percentage ratios are weight percentage.The introducing of accurate crystalline phase and zinc, yttrium content are closely relevant, and the weight ratio of zinc and yttrium (Zn/Y) is preferably 6-7% for 5-10().
The technical indicator of magnesium alloy materials of the present invention is as follows:
The corrosion potential E in the 0.1M NaCl solution at ambient temperature
Corr=-1.65～-1.50V
SCE, corrosion electric current density is i
Corr=5-60 μ A/cm
2, weight loss rate is 0.24-6.52mg/cm
2/ day, density only is 1.30-1.85g/cm
3
The most important discovery of the present invention is: by choosing certain zinc yttrium than (Zn/Y=5-10), accurate crystalline phase is incorporated in the matrix of different lithium content magnesium alloy material, makes alloy obtain higher corrosion resistance.
Mechanism of the present invention is mainly: the high resistance to corrosion that accurate crystalline phase has, low interfacial energy, have the coherence relation and to characteristics such as the raising effect of Corrosion Behaviors of Magnesium Alloys performance are remarkable, can effectively improve the corrosion resistance of the single-phase of different lithium content and two-phase magnesium alloy materials with matrix.
Alloying constituent of the present invention is to determine like this:
Lithium of the present invention (Li) content is 0-11.5%, because the interpolation of Li, magnesium alloy has lower density and plasticity, so the design of lithium content of the present invention is to obtain the erosion resistance magnesium alloy that different lightweights require.
Zinc of the present invention (Zn) and yttrium (Y) content are respectively 5-10% and 0.5-2%, because introducing and the zinc of accurate crystalline phase, yttrium content is closely relevant.When the weight ratio (Zn/Y) of zinc and yttrium is 5-10, zinc and yttrium will be present in the alloy substrate with accurate crystalline phase form.Therefore, the design of zinc and yttrium content is fully to guarantee accurate crystalline phase is incorporated in the alloy substrate among the present invention, reaches the purpose that improves the Alloy Anti corrosive nature.
The preparation method of high corrosion resistance energy magnesium alloy of the present invention comprises in alloy substrate and introduces accurate crystalline phase and follow-up homogenizing processing.The concrete steps that its concrete metallurgy and foundry and follow-up homogenizing are processed are as follows:
1) oven dry and preheating: the bake out temperature of conventional auxiliary material (insulating covering agent/refining agent) is 120-180 ℃; The preheating temperature of various batchings and casting die is 150-300 ℃; Common tool (agitator, sludge ladle, bell cover, casting with scoop etc.) cleans and preheating in 700-740 ℃ molten state washing flux.
Among the present invention, insulating covering agent can be the mixture of LiCl and LiF, and wherein the weight ratio of LiCl and LiF is (3:1)-(4:1), their weight and the 2-4% that accounts for the furnace charge gross weight.In addition, refining agent can be LiBr.
2) fusing of magnesium ingot: design temperature 720-740 ℃, heat up; When crucible was preheated to garnet (400-500 ℃), residue in the cleaning crucible passed into CO
2The air of gas displacement crucible inside, then crucible inwall and bottom even sprinkle one deck insulating covering agent; The magnesium ingot that adds preheating, and sprinkle one deck insulating covering agent at furnace charge; The insulating covering agent consumption accounts for the 0.1-1.0% of charging weight in this process; Continue to heat up.
3) adding of batching: when the magnesium melt temperature reaches 750-760 ℃, under the insulating covering agent protection, add various preheated magnesium yttrium master alloy (Mg-24wt%Y) and spelters according to batching fusing point order from high to low; Batching was stirred 4-6 minute, so that homogeneous chemical composition after all melting; Then, remove surperficial slag, bath surface spreads with insulating covering agent.Powered-down treats that temperature is down to 730-740 ℃, opening power, add Li, fully (add LiCl and LiF insulating covering agent in this process, the weight ratio of LiCl and LiF is (3:1)-(4:1), and the weight of LiCl and LiF accounts for the 2-4% of furnace charge gross weight with its fusing in stirring; And logical CO
2Or air and SF6 shielding gas, per-cent by volume is at 99-99.5%CO
2Or air+0.5-1%SF
6); The add-on of insulating covering agent is not burnt with bath surface and is as the criterion in this operation.
4) refining of melt: when treating that temperature is 720-730 ℃, stirred melt 7-10 minute, melt is rolled from bottom to top, must not splash, and constantly spread with refining agent (LiBr) at the crest of melt, its consumption is the 0.5-2.5% of furnace charge gross weight.
5) insulation of melt is left standstill: after refining finishes, remove the slag that aluminium alloy surface, sidewall of crucible etc. are located, per-cent by volume is at 99-99.5% air (or CO
2)+0.5-1%SF
6Draw slag under mixed gas protected, then bath surface spreads with insulating covering agent, and consumption does not burn with bath surface and is as the criterion; Melt is warming up to 760-780 ℃, and insulation was left standstill 20-30 minute.
6) cast molding operation: melt is cooled to 750-760 ℃, in the 0.6:1-1.4:1(weight ratio) sulphur and boric acid mixed powder (add-on of sulphur and boric acid accounts for the 0.5-1% of alloy gross weight), and/or mixed gas (per-cent by volume is at 99-99.5%CO
2Or air+0.5-1%SF
6) protection under cast.
7) homogenizing operation: the homogenizing that ingot casting carried out under 350-400 ℃ 4-16 hour is processed, and with the segregation of elimination alloying element, and fully the low melting point phases such as MgZn are fallen in solid solution.
Among the present invention, the difference of purpose alloy gross weight, alloy gross weight and furnace charge gross weight is: purpose alloy gross weight is refered in particular to the gross weight of the alloying element of joining when certain is smelted, the gross weight of the alloying element of joining when the alloy gross weight refers to smelt, the furnace charge gross weight refers to alloy smelting time institute's addition element, insulating covering agent and the weight sum of refining agent.
Below by embodiment in detail the present invention is described in detail.
I), alloy composition
Each element by the alleged taking-up of following proportioning 15 kilograms of Mg-Li-Zn-Y magnesium lithium alloy materials of configuration is: the magnesium (Mg) of lithium (Li) 900 grams, zinc (Zn) 900 grams, magnesium yttrium master alloy (Mg-24wt%Y) 750 grams and surplus.
II), alloy smelting and casting
The smelting of alloy is carried out in the crucible of 15 kg capacity and resistance furnace.Crucible and casting molds adopt low-carbon steel material.The below elaborates smelting and the casting technique of alloy take embodiment 1 as example.
1) setting the crucible target temperature is 720 ℃, begins heating; Then the various batchings such as pure magnesium, pure zinc, magnesium yttrium master alloy, pure lithium are placed on and are preheated to 150 ℃ in the baking oven, the insulating covering agent (insulating covering agent adopts LiCl and LiF, and the weight ratio of LiCl and LiF is 3:1) that will account for simultaneously furnace charge gross weight 2% is put into baking oven and is toasted; Casting is preheated to 300 ℃ with mould in other box-type furnace.
2) when crucible is warming up to 300 ℃, pass into CO
2Gas carries out gas displacement to crucible, then add about 1/2 the insulating covering agent that has toasted in crucible bottom, afterwards preheated pure magnesium batching is put into crucible again.
3) fusing of pure magnesium batching and etc. after crucible temperature is stabilized in 750 ℃, add successively from high to low magnesium yttrium master alloy and the pure zinc of preheating according to fusing point, then melt carried out stir about 8 minutes; In this process, take the circumstances into consideration to add the remaining insulating covering agent that has toasted, do not fire with the surface and be as the criterion.
4) after crucible temperature is down to 730 ℃, add Li and stir its fusing, in this process, add LiCl and LiF insulating covering agent, the weight ratio of LiCl and LiF is 3:1, the weight of LiCl and LiF accounts for 2% of alloy gross weight; And by volume per-cent passes through 99.5%CO
2+ 0.5%SF
6Mixed gas is protected;
When 5) treating that crucible temperature is 720 ℃, melt is carried out refining, stirred melt approximately 10 minutes, melt is rolled from bottom to top, must not splash, and constantly spread with refining agent (LiBr) at the crest of melt, the refining agent consumption is 1.5% of furnace charge gross weight.
6) after crucible temperature was stabilized in 750 ℃, melt left standstill 20 minutes, and per-cent by volume is at 99.5%CO
2+ 0.5%SF
6Draw slag under mixed gas protected;
7) draw slag complete after, keep crucible temperature and be stabilized in 750 ℃, per-cent by volume is at 99.5%CO
2+ 0.5%SF
6Mixed gas protected lower cast molding.
In the present embodiment, the final Mg-Li-Zn-Y magnesium lithium alloy that obtains is at containing of α-Μ g and β-Li two-phase region of accurate brilliant two-phase magnesium lithium alloy, percentage ratio meter by weight, and its component and content thereof are: lithium content is 6%; Zinc content is 6%; Yttrium content is 1.2%; Mg content is the balance surplus.
III), homogenizing is processed
The homogenizing that ingot casting carried out under 380 ℃ 4 hours is processed, and with the segregation of elimination alloying element, and fully the low melting point phases such as MgZn are fallen in solid solution.
IV), corrosive nature test
Adopt No. 1000 silicon carbide silicon carbide papers to polish 20(long) * 20(is wide) * 5mm(is thick) each surface of sample; Then at ambient temperature sample is put into 0.1M NaCl solution and carried out immersion test.After experiment finishes, with banister brush the corrosion product of specimen surface is removed, claimed the weight of its loss, calculate rate of weight loss.Utilize resin that sample is sealed, only the sample in cross section of exposing 10 * 10mm is carried out the measurement of electrokinetic potential polarization curve, determine the corresponding parameters of electrochemical corrosion of alloy, its rate of weight loss is 1.32mg/cm
2/ day, corrosion potential E
Corr=-1.54V
SCE, corrosion current i
Corr=16 μ A/cm
2, see Fig. 1 e.
V), the grand microcosmic of erosion profile characterizes
Macro morphology to the corrosion sample after cleaning carries out macroscopical photo-optics; Taking a sample in cross section to the corrosion sample, adopts No. 1000 silicon carbide silicon carbide papers to polish its surface, adopts the mechanical polishing of oil base diamond paste; Observation is observed in the distribution situation of the accurate crystalline phase of spot corrosion and/or position, the end, hole.As seen, the accurate brilliant main mechanism that improves Mg-Li Alloy Anti corrosive nature is that it can effectively hinder further developing of spot corrosion and pitting corrosion, sees accompanying drawing 2.As shown in Figure 2, a) Mg-6%Li; B) Mg-6%Li-6%Zn-1.2Y%(low power); And c) Mg-6%Li-6%Zn-1.2Y%(high power), by not containing accurate brilliant Mg-6%Li magnesium alloy and containing the at ambient temperature cross section erosion profile photo contrast after 0.1M NaCl solution soaking of accurate brilliant Mg-6%Li-6%Zn-1.2%Y magnesium alloy (embodiment 1), can find out: be distributed in matrix and the β accurate brilliant eutectic born of the same parents around mutually and can be used as barrier and well hinder further carrying out of corrosion, thereby effectively improved the resistance to corrosion that contains accurate brilliant magnesium lithium alloy.
Embodiment 2
Difference from Example 1 is,
I), alloy composition
Each element by the alleged taking-up of following proportioning 15 kilograms of Mg-Li-Zn-Y magnesium lithium alloy materials of configuration is: the magnesium (Mg) of lithium (Li) 1200 grams, zinc (Zn) 900 grams, magnesium yttrium master alloy (Mg-24wt%Y) 750 grams and surplus.
II), alloy smelting and casting
The smelting of reference example 1 and casting, the final Mg-Li-Zn-Y magnesium lithium alloy that obtains is at containing of α-Μ g and β-Li two-phase region of accurate brilliant two-phase magnesium lithium alloy, percentage ratio meter by weight, its component and content thereof are: lithium content is 8%; Zinc content is 6%; Yttrium content is 1.2%; Mg content is the balance surplus.
III), homogenizing is processed
The homogenizing that ingot casting carried out under 360 ℃ 6 hours is processed, and with the segregation of elimination alloying element, and fully the low melting point phases such as MgZn are fallen in solid solution.
IV), corrosive nature test
The corrosive nature test of reference example 1, its rate of weight loss is 2.32mg/cm
2/ day, corrosion potential E
Corr=-1.56V
SCE, corrosion current i
Corr=26 μ A/cm
2
V), the grand microcosmic of erosion profile characterizes
The grand microcosmic of the erosion profile of reference example 1 characterizes, and sees accompanying drawing 2 and Fig. 1 f.
Embodiment 3
Difference from Example 1 is,
I), alloy composition
Each element by the alleged taking-up of following proportioning 15 kilograms of Mg-Li-Zn-Y magnesium lithium alloy materials of configuration is: the magnesium (Mg) of lithium (Li) 750 grams, zinc (Zn) 900 grams, magnesium yttrium master alloy (Mg-24wt%Y) 750 grams and surplus.
II), alloy smelting and casting
The smelting of reference example 1 and casting, the final Mg-Li-Zn-Y magnesium lithium alloy that obtains is at containing of α-Μ g and β-Li two-phase region of accurate brilliant two-phase magnesium lithium alloy, percentage ratio meter by weight, its component and content thereof are: lithium content is 5%; Zinc content is 6%; Yttrium content is 1.2%; Mg content is the balance surplus.
III), homogenizing is processed
The homogenizing that ingot casting carried out under 380 ℃ 8 hours is processed, and with the segregation of elimination alloying element, and fully the low melting point phases such as MgZn are fallen in solid solution.
IV), corrosive nature test
The corrosive nature test of reference example 1, its rate of weight loss is 2.13mg/cm
2/ day, corrosion potential E
Corr=-1.55V
SCE, corrosion current i
Corr=22 μ A/cm
2
V), the grand microcosmic of erosion profile characterizes
The grand microcosmic of the erosion profile of reference example 1 characterizes, and sees accompanying drawing 1d.
Embodiment 4
Difference from Example 1 is,
I), alloy composition
Each element by the alleged taking-up of following proportioning 15 kilograms of Mg-Zn-Y magnesium alloy materials of configuration is: the magnesium (Mg) of zinc (Zn) 1155 grams, magnesium yttrium master alloy (Mg-24wt%Y) 687.5 grams and surplus.
II), alloy smelting and casting
The smelting of reference example 1 and casting omit to add alloying element lithium step, and the final Mg-Zn-Y alloy that obtains is the accurate grained magnesium alloy that contains in α-Μ g single phase region, percentage ratio meter by weight, and its component and content thereof are: zinc content is 7.7%; Yttrium content is 1.1%; Mg content is the balance surplus.
III), homogenizing is processed
The homogenizing that ingot casting carried out under 370 ℃ 6 hours is processed, and with the segregation of elimination alloying element, and fully the low melting point phases such as MgZn are fallen in solid solution.
IV), corrosive nature test
The corrosive nature test of reference example 1, its rate of weight loss is 1.86mg/cm
2/ day, corrosion potential E
Corr=-1.58V
SCE,Corrosion current i
Corr=20 μ A/cm
2
V), the grand microcosmic of erosion profile characterizes
The grand microcosmic of the erosion profile of reference example 1 characterizes.
Comparative example 1, comparative example 2 and comparative example 3
As shown in Figure 1, a) Mg-1%Li; B) Mg-5%Li; C) Mg-6%Li; D) Mg-5%Li-6%Zn-1.2Y%(embodiment 3); E) Mg-6%Li-6%Zn-1.2Y%(embodiment 1); F) Mg-8%Li-6%Zn-1.2Y%(embodiment 2).By containing and not containing the at ambient temperature contrast of the macro etch pattern photo after 0.1M NaCl solution soaking of accurate grained magnesium alloy, can find out: be distributed in matrix and the β accurate brilliant eutectic born of the same parents around mutually and can be used as barrier and well hinder further carrying out of corrosion, thereby effectively improved the resistance to corrosion that contains accurate brilliant magnesium lithium alloy.
Embodiment result shows, the high resistance to corrosion of the present invention contain accurate brilliant single-phase and two-phase magnesium alloy and preparation method thereof, have at ambient temperature better uniform corrosion and higher pitting corrosion resistant performance in the NaCl aqueous solution, solve the problem of magnesium alloy resistance to corrosion extreme difference, by the choose reasonable alloying element, accurate crystalline phase is incorporated in the magnesium alloy substrate, has prepared the accurate grained magnesium alloy that contains that has than the high corrosion resistance energy.
Claims (10)
- One kind contain accurate brilliant high corrosion resistance can magnesium alloy, it is characterized in that: magnesium alloy is in α-Μ g single phase region or the quasi crystal phase fortified magnesium alloy of α-Μ g+ β-Li two-phase region, percentage ratio meter by weight, its component and content thereof are: lithium content is 0-11.5%; Zinc content is 5-10%; Yttrium content is 0.5-2%; Mg content is the balance surplus.
- According to claimed in claim 1 contain accurate brilliant high corrosion resistance can magnesium alloy, it is characterized in that: the weight ratio Zn/Y of described zinc and yttrium is 5-10.
- According to claimed in claim 1 contain accurate brilliant high corrosion resistance can magnesium alloy, it is characterized in that: in the described magnesium alloy, zinc content preferable range is 6-8%, and yttrium content preferable range is 1.0-1.5%, and the weight ratio Zn/Y preferable range of zinc and yttrium is 6-7; The lithium content preferable range is 6-8%.
- 4. a preparation method who contains accurate brilliant high corrosion resistance energy magnesium alloy claimed in claim 1 is characterized in that, alloy melting and subsequent thermal extrusion processing deformation process are as follows:1) takes by weighing out alloying element zinc and yttrium by zinc yttrium weight ratio Zn/Y=5-10 ratio;2) when temperature is 720-740 ℃, add the pure magnesium of alloy raw material;2) when temperature is 750-760 ℃, add alloying element zinc and magnesium yttrium master alloy Mg-24wt%Y;3) when temperature is down to 730-740 ℃, add the alloying element lithium; When lithium content is zero, omit this step;4) when temperature is 720-730 ℃, alloy carries out refining;5) be 750-760 ℃ in temperature, cast;6) with the ingot casting of casting, the homogenizing of carrying out under 350-400 ℃ 4-16 hour is processed into goods.
- 5. according to the preparation method who contains accurate brilliant high corrosion resistance energy magnesium alloy claimed in claim 4, it is characterized in that: when the addition element lithium, adopt LiCl and LiF insulating covering agent, and logical CO 2Or air and SF 6Mixed gas is protected, and the weight ratio of LiCl and LiF is (3:1)-(4:1), and the weight of LiCl and LiF accounts for the 2-4% of alloy gross weight; Per-cent by volume, mixed gas is the CO of 99-99.5% 2Or air, 0.5-1%SF 6Mix.
- 6. according to the preparation method who contains accurate brilliant high corrosion resistance can magnesium alloy claimed in claim 4, it is characterized in that: in the refining process, spread refining agent LiBr alloy at the crest of melt and carry out refining, consumption is the 0.5-2.5% of furnace charge gross weight.
- 7. according to the preparation method who contains accurate brilliant high corrosion resistance energy magnesium alloy claimed in claim 4, it is characterized in that: when casting, protect with the sulphur of weight ratio (0.6:1)-(1.4:1) and boric acid mixed powder and/or mixed gas, the add-on of sulphur and boric acid accounts for the 0.5-1% of alloy gross weight; Per-cent by volume, mixed gas is 99-99.5%CO 2Or air and 0.5-1%SF 6Mix.
- 8. according to the preparation method who contains accurate brilliant high corrosion resistance energy magnesium alloy claimed in claim 4, it is characterized in that: after refining finishes, bath surface spreads with LiCl and LiF insulating covering agent, and the weight ratio of LiCl and LiF is (3:1)-(4:1), and the weight of LiCl and LiF accounts for the 2-4% of furnace charge gross weight; After crucible temperature was stabilized in 760-780 ℃, melt left standstill 20-30 minute; Then, per-cent by volume is at 99-99.5% air or CO 2, 0.5-1%SF 6Draw slag under mixed gas protected.
- 9. according to the preparation method who contains accurate brilliant high corrosion resistance energy magnesium alloy claimed in claim 4, it is characterized in that: preferably, after casting is finished, the homogenizing that the ingot casting of casting carried out under 360-380 ℃ 4-8 hour is processed, with the segregation of elimination alloying element, and fully MgZn low melting point phase is fallen in solid solution.
- 10. application that contains accurate brilliant high corrosion resistance can magnesium alloy claimed in claim 1 is characterized in that: described used for magnesium alloy is in the lightweight magnesium alloy material with anticorrosive destructiveness, at ambient temperature the corrosion potential E in the 0.1MNaCl solution Corr=-1.65～-1.50V SCE, corrosion electric current density is i Corr=5-60 μ A/cm 2, weight loss rate is 0.24-6.52mg/cm 2/ day, density is 1.30-1.85g/cm 3
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| CN106856651A (en) * | 2016-12-20 | 2017-06-16 | 太仓市天丝利塑化有限公司 | A kind of environment-friendly type upper mealiness liquid crystal display metal shell high and electrostatic painting process |
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| CN108456814A (en) * | 2018-01-24 | 2018-08-28 | 上海交通大学 | A kind of quasi-crystalline substance reinforcing magnesium lithium alloy and preparation method thereof containing Er |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107541630A (en) * | 2016-06-29 | 2018-01-05 | 中国科学院金属研究所 | Effectively strengthen two-phase Mg Li Zn Y magnesium lithium alloys and preparation method using rare earth element y |
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| CN106856651A (en) * | 2016-12-20 | 2017-06-16 | 太仓市天丝利塑化有限公司 | A kind of environment-friendly type upper mealiness liquid crystal display metal shell high and electrostatic painting process |
| CN106756358B (en) * | 2016-12-20 | 2019-04-16 | 太仓市天丝利塑化有限公司 | A kind of high corrosion-resistant notebook magnesium lithium alloy shell and its spraying chemical synthesis technology |
| CN108456814A (en) * | 2018-01-24 | 2018-08-28 | 上海交通大学 | A kind of quasi-crystalline substance reinforcing magnesium lithium alloy and preparation method thereof containing Er |
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