CN103320663B - 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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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 field of magnesium alloy, be specially a kind of good corrosion resistance containing accurate grained magnesium alloy and its preparation method and application, particularly have in NaCl aqueous solution at ambient temperature better uniform corrosion and higher pitting corrosion resistant performance containing accurate brilliant ultralight magnesium alloy materials and the method preparing this alloy material.
Background technology
Magnesium lithium alloy is structural metallic materials the lightest in current engineer applied, and its density is at 1.35-1.65g/cm
3between, and there is 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, as strong in anti-high energy particle penetrativity, capability of electromagnetic shielding good, damping capacity good, machinability is excellent, be the desirable lightweight structural material in the fields such as space flight, aviation, electronics and military affairs, make Mg-Li alloy have potential wide application prospect at the high-technology field such as aerospace and automobile.But the erosion resistance extreme difference of magnesium lithium alloy, seriously constrains the application of alloy and further develops.The chemically reactive that document (Corrosion Science (corrosion science) 51 (2009) 1087) reports element Li is very strong, the corrosion resistance of the magnesium lithium alloy with it after alloying will be very poor, and corrosion can preferentially occur at α-Mg and β-Li phase interface place.
In recent years, the hot issue of magnesium alloy research has been become about the strengthening mechanism of accurate brilliant Forming Mechanism in the magnesium alloy and alloy.Accurate brilliant (i.e. quasi-periodicity crystal) is a kind of solid-state ordered phase simultaneously with long-range translational order quasi-periodicity and non-crystallographic rotational symmetry, and having typical five times and ten inferior special symmetry, is a kind of novel solid-state structure.Document (Science (science) 261 (1993) 737) reports accurate crystalline substance and has some performances superior especially 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) report Icosahedral phases effectively can reduce Mg-Zn-Y magnesium alloy erosion rate as second-phase.Can predict, by should contribute to the raising of alloy corrosion performance to self-generating Icosahedral phases in Mg-Li alloy, a kind of novel solution can be provided for performance under the actual Service Environment of raising magnesium lithium alloy and its range of application of expansion.
Summary of the invention
What the object of the present invention is to provide a kind of good corrosion resistance contains accurate grained magnesium alloy and its preparation method and application, solve the problem of Magnesium Anti-Corrosion extreme difference, by choose reasonable alloying element, Icosahedral phases is incorporated in magnesium alloy substrate, prepare in NaCl aqueous solution at ambient temperature have better uniform corrosion and higher pitting corrosion resistant performance containing accurate brilliant single-phase and two-phase ultralight magnesium alloy.
Technical scheme of the present invention is:
A kind of containing accurate brilliant improved corrosion performance magnesium alloy, magnesium alloy is the quasi crystal phase fortified magnesium alloy in α-Μ g single phase region or α-Μ g+ β-Li two-phase region, percentage, and its component and content thereof are: lithium content is 0-11.5%; Zn content is 5-10%; Yttrium content is 0.5-2%; Mg content is balance.
Described containing accurate brilliant improved corrosion performance magnesium alloy, the weight ratio Zn/Y of zinc and yttrium is 5-10.
Described containing accurate brilliant improved corrosion performance magnesium alloy, Zn 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; Lithium content preferable range is 6-8%.
The described preparation method containing accurate brilliant improved corrosion performance magnesium alloy, alloy melting and subsequent thermal extrusion processing deformation process as follows:
1) alloying element zinc and yttrium is taken out by zinc yttrium weight ratio Zn/Y=5-10 ratio;
2) when temperature is 720-740 DEG C, the pure magnesium of alloy raw material is added;
2) when temperature is 750-760 DEG C, alloying element zinc and magnesium yttrium master alloy Mg-24wt%Y is added;
3) when temperature is down to 730-740 DEG C, alloying element lithium is added; When lithium content is zero, omit this step;
4) when temperature is 720-730 DEG C, alloy carries out refining;
5) be 750-760 DEG C in temperature, cast;
6) by the ingot casting of casting, the Homogenization Treatments carried out at 350-400 DEG C 4-16 hour becomes goods.
The described preparation method containing accurate brilliant improved corrosion performance magnesium alloy, when 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; By volume per-cent, mixed gas is the CO of 99-99.5%
2or air, 0.5-1%SF6 mixing.
The described preparation method containing accurate brilliant improved corrosion performance magnesium alloy, in refining process, the crest of melt spreads refining agent LiBr alloy and carries out refining, consumption is the 0.5-2.5% of furnace charge gross weight.
The described preparation method containing accurate brilliant improved corrosion performance 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; By volume per-cent, mixed gas is 99-99.5%CO
2or air and 0.5-1%SF
6mixing.
The described preparation method containing accurate brilliant improved corrosion performance magnesium alloy, after refining terminates, 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 is stabilized in 760-780 DEG C, melt leaves standstill 20-30 minute; Then, by volume per-cent, at 99-99.5% air or CO
2, 0.5-1%SF6 mixed gas protected under draw slag.
The described preparation method containing accurate brilliant improved corrosion performance magnesium alloy, preferably, after having cast, carries out the Homogenization Treatments of 4-8 hour at 360-380 DEG C by the ingot casting of casting, to eliminate the segregation of alloying element, and fully MgZn low melting point phase is fallen in solid solution.
The described application containing accurate brilliant improved corrosion performance magnesium alloy, described is used for magnesium alloy in the lightweight magnesium alloy material with anticorrosive destructiveness, the corrosion potential E at ambient temperature in 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/ sky, density is 1.30-1.85g/cm
3.
Advantage of the present invention and beneficial effect are:
1, the present invention is by controlling zinc yttrium ratio (Zn/Y) in alloying element, is incorporated into by Icosahedral phases in the magnesium alloy substrate of Different L i content.
2, the present invention adopts the method to obtain to have the magnesium alloy of low density, 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 follow-up Homogenization Treatments, its processing technological operation is simple, convenient.
Accompanying drawing explanation
Fig. 1 contains and does not contain accurate grained magnesium alloy (embodiment 1, embodiment 2 and embodiment 3) the macro etch pattern photo at ambient temperature after 0.1M NaCl solution is soaked.
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 is not containing accurate brilliant Mg-6%Li magnesium alloy and containing the cross section erosion profile photo of accurate brilliant Mg-6%Li-6%Zn-1.2%Y magnesium alloy (embodiment 1) at ambient temperature after 0.1M NaCl solution is soaked.
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
Good corrosion resistance of the present invention containing accurate grained magnesium alloy, aluminum magnesium containing alloy materials is as the criterion brilliant reinforced magnesium alloy, the brilliant reinforced magnesium alloy of standard being magnesium alloy in 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%, or 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 surplus magnesium (Mg) composition, all percentage ratio is weight percentage.The introducing of Icosahedral phases and zinc, yttrium content are closely relevant, and the weight ratio (Zn/Y) of zinc and yttrium is preferably 6-7% for 5-10().
The technical indicator of magnesium alloy materials of the present invention is as follows:
Corrosion potential E at ambient temperature in 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/ sky, density is only 1.30-1.85g/cm
3.
The most important discovery of the present invention is: by choosing certain zinc yttrium ratio (Zn/Y=5-10), being incorporated into by Icosahedral phases in the matrix of different lithium content magnesium alloy material, making alloy obtain higher corrosion resistance.
Mechanism of the present invention is mainly: the good corrosion resistance that Icosahedral phases has, low interfacial energy, to have symbiosis and epibiosis and to features such as the raising effect of Corrosion Behaviors of Magnesium Alloys performance are remarkable, effectively can 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 determined like this:
Lithium of the present invention (Li) content is 0-11.5%, and due to the interpolation of Li, magnesium alloy has lower density and plasticity, and therefore the design of lithium content of the present invention is the erosion resistance magnesium alloy that will obtain different light-weight requirements.
Zinc of the present invention (Zn) and yttrium (Y) content are respectively 5-10% and 0.5-2%, and due to introducing and the zinc of Icosahedral phases, yttrium content is closely relevant.When the weight ratio (Zn/Y) of zinc and yttrium is for 5-10, zinc and yttrium will be present in alloy substrate with Icosahedral phases form.Therefore, in the present invention, the design of zinc and yttrium content fully ensures Icosahedral phases to be incorporated in alloy substrate, reaches the object improving alloy corrosion performance.
The preparation method of improved corrosion performance magnesium alloy of the present invention, comprises and introduce Icosahedral phases and follow-up Homogenization Treatments in alloy substrate.The concrete steps of its concrete metallurgy and foundry and follow-up Homogenization Treatments are as follows:
1) oven dry and preheating: the bake out temperature of customary adjuvant (insulating covering agent/refining agent) is 120-180 DEG C; The preheating temperature of various batching and casting die is 150-300 DEG C; Common tool (agitator, sludge ladle, bell cover, casting scoop etc.) cleaning and preheating in the molten state washing flux of 700-740 DEG C.
In 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% accounting for furnace charge gross weight.In addition, refining agent can be LiBr.
2) fusing of magnesium ingot: design temperature 720-740 DEG C, heats up; When crucible is preheated to garnet (400-500 DEG C), residue in cleaning crucible, passes into CO
2the air of gas displacement crucible inside, then sprinkles one deck insulating covering agent at crucible internal walls and bottom even; Add the magnesium ingot of preheating, and on furnace charge, sprinkle one deck insulating covering agent; In this process, insulating covering agent consumption accounts for the 0.1-1.0% of charging weight; Continue to heat up.
3) for preparing burden adds: when Serum Magnesium temperature reaches 750-760 DEG C, under insulating covering agent protection, add various preheated magnesium yttrium master alloy (Mg-24wt%Y) and spelter according to batching fusing point order from high to low; After batching all melts, stir 4-6 minute, to make uniform composition; Then, remove surperficial slag, bath surface spreads with insulating covering agent.Powered-down, treats that temperature is down to 730-740 DEG C, opening power, add Li, abundant stirring is melted, and (add LiCl and LiF insulating covering agent in the 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; And logical CO
2or air and SF6 shielding gas, by volume per-cent, at 99-99.5%CO
2or air+0.5-1%SF
6); In this operation, the add-on of insulating covering agent is not burnt with bath surface and is as the criterion.
4) refining of melt: when temperature is 720-730 DEG C, stir melt 7-10 minute, melt is rolled from bottom to top, must not splash, and constantly spread with refining agent (LiBr) on the crest of melt, its consumption is the 0.5-2.5% of furnace charge gross weight.
5) insulation of melt leaves standstill: after refining terminates, remove the slag at the place such as aluminium alloy surface, sidewall of crucible, by volume per-cent, 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 DEG C, and insulation leaves standstill 20-30 minute.
6) cast molding operation: melt is cooled to 750-760 DEG C, in 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 (by volume per-cent, at 99-99.5%CO
2or air+0.5-1%SF
6) cast under protection.
7) homogenizing operation: Homogenization Treatments ingot casting being carried out at 350-400 DEG C 4-16 hour, to eliminate the segregation of alloying element, and fully the low melting point phases such as MgZn are fallen in solid solution.
In the present invention, the difference of object alloy gross weight, alloy gross weight and furnace charge gross weight is: object alloy gross weight refers in particular to the gross weight of the alloying element of joining when certain is smelted, alloy gross weight refers to the gross weight of the alloying element of joining when smelting, and furnace charge gross weight refers to the weight sum of alloy smelting time institute addition element, insulating covering agent and refining agent.
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
I), alloy composition
Configuring by following proportioning each element taken out alleged by 15 kilograms of Mg-Li-Zn-Y magnesium lithium alloy materials is: the magnesium (Mg) of lithium (Li) 900 grams, 900 grams, zinc (Zn), 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 and resistance furnace of 15 kg capacity.Crucible and casting molds adopt low-carbon steel material.Below for embodiment 1, elaborate smelting and the casting technique of alloy.
1) setting crucible target temperature is 720 DEG C, starts heating; Then the various batchings such as pure magnesium, pure zinc, magnesium yttrium master alloy, pure lithium are put and be preheated to 150 DEG C in an oven, the insulating covering agent (insulating covering agent adopts the weight ratio of LiCl and LiF, LiCl and LiF to be 3:1) accounting for furnace charge gross weight 2% is put into baking oven simultaneously and toast; Casting mould is preheated to 300 DEG C in other box-type furnace.
2) when crucible is warming up to 300 DEG C, CO is passed into
2carry out gas displacement in gas to crucible, then add the insulating covering agent toasted of about 1/2 in crucible bottom, more afterwards preheated pure magnesium batching is put into crucible.
3) pure magnesium batching fusing and after waiting crucible temperature to be stabilized in 750 DEG C, add the magnesium yttrium master alloy of preheating and pure zinc from high to low successively according to fusing point, then melt carries out stir about 8 minutes; In this process, take the circumstances into consideration to add the remaining insulating covering agent toasted, do not fire with surface and be as the criterion.
4) after crucible temperature is down to 730 DEG C, add Li and stir and melted, add LiCl and LiF insulating covering agent in the process, the weight ratio of LiCl and LiF is that the weight of 3:1, LiCl and LiF accounts for 2% of alloy gross weight; Further, by volume per-cent, passes through 99.5%CO
2+ 0.5%SF
6mixed gas is protected;
5) when crucible temperature is 720 DEG C, carry out refining to melt, stir melt about 10 minutes, melt is rolled from bottom to top, must not splash, and constantly spread with refining agent (LiBr) on the crest of melt, refining agent consumption is 1.5% of furnace charge gross weight.
6), after crucible temperature is stabilized in 750 DEG C, melt leaves standstill 20 minutes, and by volume per-cent, at 99.5%CO
2+ 0.5%SF
6slag is drawn under mixed gas protected;
7) draw after slag, maintain crucible temperature and be stabilized in 750 DEG C, by volume per-cent, 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 obtained be in α-Μ g and β-Li two-phase region containing accurate brilliant two-phase magnesium lithium alloy, percentage, its component and content thereof are: lithium content is 6%; Zn content is 6%; Yttrium content is 1.2%; Mg content is balance.
III), Homogenization Treatments
Ingot casting is carried out at 380 DEG C the Homogenization Treatments of 4 hours, to eliminate the segregation of alloying element, and fully the low melting point phases such as MgZn are fallen in solid solution.
IV), corrosive nature test
No. 1000 silicon carbide silicon carbide papers are adopted 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 carry out immersion test.After experiment terminates, with banister brush, the corrosion product of specimen surface is removed, claim the weight that it loses, calculate rate of weight loss.Utilize resin to be sealed by sample, only the sample in cross section exposing 10 × 10mm is carried out to the measurement of dynamic potential polarization curve, determine the corresponding parameters of electrochemical corrosion of alloy, its rate of weight loss is 1.32mg/cm
2/ sky, corrosion potential E
corr=-1.54V
sCE, corrosion current i
corr=16 μ A/cm
2, see Fig. 1 e.
V), the grand microscopic sdIBM-2+2q.p.approach of erosion profile
Macroscopical photo-optics is carried out to the macro morphology of the corrosion sample after cleaning; The cross section of corrosion sample is sampled, adopts No. 1000 silicon carbide silicon carbide papers to polish its surface, adopt the mechanical polishing of oil base diamond paste; Observe and observe in the distribution situation of Icosahedral phases of spot corrosion and/or position, the end, hole.Visible, the accurate brilliant main mechanism improving Mg-Li alloy corrosion performance is that it effectively can 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 cross section erosion profile photo comparison of accurate brilliant Mg-6%Li-6%Zn-1.2%Y magnesium alloy (embodiment 1) at ambient temperature after 0.1M NaCl solution is soaked, can find out: the brilliant eutectic born of the same parents of standard be distributed in around matrix and β phase can well hinder carrying out further of corrosion as barrier, thus effectively improve the resistance to corrosion containing accurate brilliant magnesium lithium alloy.
Embodiment 2
Difference from Example 1 is,
I), alloy composition
Configuring by following proportioning each element taken out alleged by 15 kilograms of Mg-Li-Zn-Y magnesium lithium alloy materials is: the magnesium (Mg) of lithium (Li) 1200 grams, 900 grams, zinc (Zn), 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 obtained be in α-Μ g and β-Li two-phase region containing accurate brilliant two-phase magnesium lithium alloy, percentage, its component and content thereof are: lithium content is 8%; Zn content is 6%; Yttrium content is 1.2%; Mg content is balance.
III), Homogenization Treatments
Ingot casting is carried out at 360 DEG C the Homogenization Treatments of 6 hours, to eliminate the segregation of 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/ sky, corrosion potential E
corr=-1.56V
sCE, corrosion current i
corr=26 μ A/cm
2.
V), the grand microscopic sdIBM-2+2q.p.approach of erosion profile
The grand microscopic sdIBM-2+2q.p.approach of the erosion profile of reference example 1, is shown in accompanying drawing 2 and Fig. 1 f.
Embodiment 3
Difference from Example 1 is,
I), alloy composition
Configuring by following proportioning each element taken out alleged by 15 kilograms of Mg-Li-Zn-Y magnesium lithium alloy materials is: the magnesium (Mg) of lithium (Li) 750 grams, 900 grams, zinc (Zn), 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 obtained be in α-Μ g and β-Li two-phase region containing accurate brilliant two-phase magnesium lithium alloy, percentage, its component and content thereof are: lithium content is 5%; Zn content is 6%; Yttrium content is 1.2%; Mg content is balance.
III), Homogenization Treatments
Ingot casting is carried out at 380 DEG C the Homogenization Treatments of 8 hours, to eliminate the segregation of 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/ sky, corrosion potential E
corr=-1.55V
sCE, corrosion current i
corr=22 μ A/cm
2.
V), the grand microscopic sdIBM-2+2q.p.approach of erosion profile
The grand microscopic sdIBM-2+2q.p.approach of the erosion profile of reference example 1, is shown in accompanying drawing 1d.
Embodiment 4
Difference from Example 1 is,
I), alloy composition
Configuring by following proportioning each element taken out alleged by 15 kilograms of Mg-Zn-Y magnesium alloy materials is: the magnesium (Mg) of 1155 grams, zinc (Zn), 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 and add alloying element lithium step, the final Mg-Zn-Y alloy obtained be in α-Μ g single phase region containing accurate grained magnesium alloy, percentage, its component and content thereof are: Zn content is 7.7%; Yttrium content is 1.1%; Mg content is balance.
III), Homogenization Treatments
Ingot casting is carried out at 370 DEG C the Homogenization Treatments of 6 hours, to eliminate the segregation of 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/ sky, corrosion potential E
corr=-1.58V
sCE,corrosion current i
corr=20 μ A/cm
2.
V), the grand microscopic sdIBM-2+2q.p.approach of erosion profile
The grand microscopic sdIBM-2+2q.p.approach of the erosion profile of reference example 1.
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 macro etch pattern photo comparison of accurate grained magnesium alloy at ambient temperature after 0.1M NaCl solution is soaked, can find out: the brilliant eutectic born of the same parents of standard be distributed in around matrix and β phase can well hinder carrying out further of corrosion as barrier, thus effectively improve the resistance to corrosion containing accurate brilliant magnesium lithium alloy.
Embodiment result shows, good corrosion resistance of the present invention containing accurate brilliant single-phase and two-phase magnesium alloy and preparation method thereof, at ambient temperature there is in NaCl aqueous solution better uniform corrosion and higher pitting corrosion resistant performance, solve the problem of magnesium alloy resistance to corrosion extreme difference, by choose reasonable alloying element, Icosahedral phases is incorporated in magnesium alloy substrate, prepared have compared with improved corrosion performance containing accurate grained magnesium alloy.
Claims (1)
1., containing an accurate brilliant improved corrosion performance magnesium alloy, it is characterized in that:
I), alloy composition
Configuring by following proportioning each element taken out alleged by 15 kilograms of Mg-Zn-Y magnesium alloy materials 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 alloy is carried out in the crucible and resistance furnace of 15 kg capacity; Crucible and casting molds adopt low-carbon steel material;
1) setting crucible target temperature is 720 DEG C, starts heating; Then pure magnesium, pure zinc, the various batching of magnesium yttrium master alloy are put and be preheated to 150 DEG C in an oven, will account for the insulating covering agent of furnace charge gross weight 2% simultaneously, put into baking oven and toast, insulating covering agent adopts the weight ratio of LiCl and LiF, LiCl and LiF to be 3:1; Casting mould is preheated to 300 DEG C in other box-type furnace;
2) when crucible is warming up to 300 DEG C, CO is passed into
2carry out gas displacement in gas to crucible, then add the insulating covering agent toasted of 1/2 in crucible bottom, more afterwards preheated pure magnesium batching is put into crucible;
3) pure magnesium batching fusing and after waiting crucible temperature to be stabilized in 750 DEG C, add the magnesium yttrium master alloy of preheating and pure zinc from high to low successively according to fusing point, then melt carries out stirring 8 minutes; In this process, take the circumstances into consideration to add the remaining insulating covering agent toasted, do not fire with surface and be as the criterion;
4) when crucible temperature is 720 DEG C, carry out refining to melt, stir melt 10 minutes, melt is rolled from bottom to top, must not splash, and constantly spread on the crest of melt with refining agent LiBr, refining agent consumption is 1.5% of furnace charge gross weight;
5), after crucible temperature is stabilized in 750 DEG C, melt leaves standstill 20 minutes, and by volume per-cent, at 99.5%CO
2+ 0.5% SF
6slag is drawn under mixed gas protected;
6) draw after slag, maintain crucible temperature and be stabilized in 750 DEG C, by volume per-cent, at 99.5%CO
2+ 0.5% SF
6mixed gas protected lower cast molding;
The Mg-Zn-Y alloy of final acquisition be in α-Mg single phase region containing accurate grained magnesium alloy, percentage, its component and content thereof are: Zn content is 7.7%; Yttrium content is 1.1%; Mg content is balance;
III), Homogenization Treatments
Ingot casting is carried out at 370 DEG C the Homogenization Treatments of 6 hours, to eliminate the segregation of alloying element, and fully MgZn low melting point phase is fallen in solid solution;
IV), corrosive nature test
Adopt No. 1000 silicon carbide silicon carbide papers polish long × 20 mm of 20 mm wide × each surface of the thick sample of 5mm; Then at ambient temperature sample is put into 0.1M NaCl solution and carry out immersion test; After experiment terminates, with banister brush, the corrosion product of specimen surface is removed, claim the weight that it loses, calculate rate of weight loss; Utilize resin to be sealed by sample, only the sample in cross section exposing 10 × 10mm is carried out to the measurement of dynamic potential polarization curve, determine the corresponding parameters of electrochemical corrosion of alloy, its rate of weight loss is 1.86mg/cm
2/ sky, corrosion potential E
corr=-1.58V
sCE, corrosion current i
corr=20 μ A/cm
2.
Priority Applications (1)
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| CN201310214206.XA CN103320663B (en) | 2013-05-31 | 2013-05-31 | Quasicrystal-containing magnesium alloy with high corrosion resistance and preparation method and application thereof |
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| CN201310214206.XA CN103320663B (en) | 2013-05-31 | 2013-05-31 | Quasicrystal-containing magnesium alloy with high corrosion resistance and preparation method and application thereof |
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| 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 |
| 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 |
| CN108456814B (en) * | 2018-01-24 | 2020-09-04 | 上海交通大学 | Er-containing quasi-crystal reinforced magnesium-lithium alloy and preparation method thereof |
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| CN1948532A (en) * | 2006-11-01 | 2007-04-18 | 中国科学院金属研究所 | Quasi crystal phase fortified magnesium lithium alloy and its preparation method |
| CN102618766A (en) * | 2012-04-23 | 2012-08-01 | 华东交通大学 | Quasi-crystal enhanced high-strength magnesium-zinc-yttrium (Mg-Zn-Y) alloy and preparation method thereof |
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| CN1948532A (en) * | 2006-11-01 | 2007-04-18 | 中国科学院金属研究所 | Quasi crystal phase fortified magnesium lithium alloy and its preparation method |
| CN102618766A (en) * | 2012-04-23 | 2012-08-01 | 华东交通大学 | Quasi-crystal enhanced high-strength magnesium-zinc-yttrium (Mg-Zn-Y) alloy and preparation method thereof |
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