CN104131204A - Magnesium alloy, magnesium alloy composite material and preparation method of composite material - Google Patents
Magnesium alloy, magnesium alloy composite material and preparation method of composite material Download PDFInfo
- Publication number
- CN104131204A CN104131204A CN201410409421.XA CN201410409421A CN104131204A CN 104131204 A CN104131204 A CN 104131204A CN 201410409421 A CN201410409421 A CN 201410409421A CN 104131204 A CN104131204 A CN 104131204A
- Authority
- CN
- China
- Prior art keywords
- magnesium alloy
- alloy
- composite material
- corrosion layer
- corrosion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
The invention provides a magnesium alloy composite material which comprises magnesium alloy and a corrosion-resistant layer compounded on the surface of the magnesium alloy, wherein the magnesium alloy comprises 0wt%-2wt% of Zn, 0wt%-2wt% of Ca, 0wt%-2wt% of Sm, 0wt%-6wt% of Y and the balance of Mg; the corrosion-resistant layer comprises hafnium carbide, tantalum carbide or zirconium carbide. The magnesium alloy is high in mechanical strength and good in corrosion resistance; the corrosion-resistant layer is high in hardness, good in corrosion resistance and good in adhesion to the magnesium alloy. An experimental result shows that according to the magnesium alloy composite material, the tensile strength is more than 400MPa, the yield strength is more than 280MPa, the elongation rate is more than 7%, the surface Vickers hardness Hv0.2 is more than 102, and the adhesive strength of the corrosion-resistant layer and the magnesium alloy reaches more than the level 5B (ASTM (American Society for Testing Material)).
Description
Technical field
The invention belongs to alloy field, relate in particular to a kind of magnesium alloy, composite material of magnesium alloy and preparation method thereof.
Background technology
Magnesium alloy is to take magnesium to add other elementary composition alloys as base, there is the advantages such as density is little, specific tenacity is high, damping and amortization is good, electromagnetic shielding ability strong, dimensional stabilizing, easy recovery, in fields such as aircraft industry, automobile, mechanical means, electronic products, there is boundless application prospect, be called as " green engineering material of 21 century ".
China is that former magnesium is produced and big export country, but the research of China's magnesium alloy and application and development relatively lag behind, and one of them important reason is that the Anticorrosion Problems of magnesium alloy is not solved well.Magnesium chemically reactive in all Industrial Metal materials is the highest, in damp atmosphere, sulfur-bearing atmosphere and marine atmosphere, all can suffer serious chemical corrosion.In addition, the standard potential of magnesium is only-2.37V to react as anode generation galvanic corrosion with the impurity in alloy.Therefore, expand the use range of magnesium alloy, give full play to its superior performance, just must improve the corrosion resistance nature of magnesium alloy.
In prior art, improve corrosion resistance of magnesium alloy can method be mainly divided into two kinds: (1) by adding alloy element to reduce the content of impurity in magnesium alloy, and utilize thermal distortion processing to improve the distribution of alloy structure and second-phase; (2) adopt the process of surface treatment such as differential arc oxidation, plating, electroless plating, surface-coated to prepare the protective coating of erosion resistance, this coating can avoid magnesium alloy substrate to contact with the direct of external environment, and then carries heavy alloyed corrosion resistance nature.But the corrosion resistance nature of the magnesium alloy of preparation is still poor at present.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of magnesium alloy, composite material of magnesium alloy and preparation method thereof, magnesium alloy provided by the invention and composite material of magnesium alloy have good corrosion resistance nature.
The invention provides a kind of magnesium alloy, comprise following component:
Be greater than 0 Zn that is less than or equal to 2wt%;
Be greater than 0 Ca that is less than or equal to 2wt%;
Be greater than 0 Sm that is less than or equal to 2wt%;
Be greater than 0 Y that is less than or equal to 6wt%;
The Mg of surplus.
Preferably, the Zn that comprises 0.2～1wt%.
Preferably, the Ca that comprises 0.2～1wt%.
Preferably, the Sm that comprises 0.2～1wt%.
Preferably, the Y that comprises 1～4wt%.
The invention provides a kind of composite material of magnesium alloy, comprising:
Magnesium alloy described in technique scheme;
Be compounded in the anti-corrosion layer of described Mg alloy surface;
Described anti-corrosion layer contains hafnium carbide, tantalum carbide or zirconium carbide.
Preferably, in described anti-corrosion layer, carbon content is 25～70at%.
The preparation method who the invention provides a kind of composite material of magnesium alloy, comprising:
Adopt magnetron sputtering method at the Mg alloy surface deposition anti-corrosion layer described in technique scheme, obtain composite material of magnesium alloy;
Described anti-corrosion layer contains hafnium carbide, tantalum carbide or zirconium carbide.
Preferably, the sputter gas using in the process of described deposition anti-corrosion layer is argon gas, and reactant gases is methane.
Preferably, the volume ratio of described methane and argon gas is 1～20:80.
Compared with prior art, the invention provides a kind of magnesium alloy, comprise following component: be greater than 0 Zn that is less than or equal to 2wt%; Be greater than 0 Ca that is less than or equal to 2wt%; Be greater than 0 Sm that is less than or equal to 2wt%; Be greater than 0 Y that is less than or equal to 6wt%; The Mg of surplus.Magnesium alloy provided by the invention contains zinc, calcium, yttrium and samarium element.In magnesium alloy, add appropriate zinc element and can improve intensity and the hardness of magnesium alloy; In magnesium alloy, add the corrosion resistance nature that appropriate calcium constituent can improve magnesium alloy; In magnesium alloy, add appropriate yttrium and samarium element can reinforced magnesium alloy carefully brilliant, reduce the cathodic process of detrimental impurity, improve mechanical property and the corrosion resistance nature of magnesium alloy.
The present invention also provides a kind of composite material of magnesium alloy, comprising: the magnesium alloy described in technique scheme; Be compounded in the anti-corrosion layer of described Mg alloy surface; Described anti-corrosion layer contains hafnium carbide, tantalum carbide or zirconium carbide.Composite material of magnesium alloy provided by the invention is compounded with the fine and close anti-corrosion layer that contains hafnium carbide, tantalum carbide or zirconium carbide at Mg alloy surface, there is good physical strength, erosion resistance and wear resistance, the bonding strength of anti-corrosion layer and alloy substrate is high, difficult drop-off.Experimental result shows, the tensile strength of composite material of magnesium alloy provided by the invention is more than 400MPa, and yield strength is more than 280MPa, and unit elongation is greater than 7%, surface Vickers' hardness Hv0.2 is greater than 102, more than the bonding strength of anti-corrosion layer and magnesium alloy reaches 5B level (ASTM).The corrosion potential of this composite material of magnesium alloy in 3.5wt%NaCl solution is-1.3V that corrosion electric current density is 1.0～5.0 * 10
-6a/cm
2.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skills, do not paying under the prerequisite of creative work, other accompanying drawing can also be provided according to the accompanying drawing providing.
The composite material of magnesium alloy production technological process that Fig. 1 provides for the embodiment of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of magnesium alloy, comprise following component:
Be greater than 0 Zn that is less than or equal to 2wt%;
Be greater than 0 Ca that is less than or equal to 2wt%;
Be greater than 0 Sm that is less than or equal to 2wt%;
Be greater than 0 Y that is less than or equal to 6wt%;
The Mg of surplus.
Magnesium alloy provided by the invention comprises Zn, Ca, Sm, Y and Mg.Wherein, the content of described Zn in magnesium alloy is less than or equal to 2wt% for being greater than 0, is preferably 0.2～1wt%.Adding of Zn can form MgZn phase with Mg, improves intensity and the hardness of magnesium alloy.
The content of described Ca in magnesium alloy is less than or equal to 2wt% for being greater than 0, is preferably 0.2～1wt%.Ca adds the corrosion that can effectively slow down Mg in alloy, improves the corrosion resistance nature of magnesium alloy.
The content of described Sm in magnesium alloy is less than or equal to 2wt% for being greater than 0, is preferably 0.2～1wt%.The content of described Y in magnesium alloy is less than or equal to 6wt% for being greater than 0, is preferably 1～4wt%.Sm and Y join in magnesium alloy can purify alloy melt, and refinement alloy structure improves alloy mechanical property.Meanwhile, Sm and Y can reduce the cathodic process of detrimental impurity in magnesium alloy (iron, nickel etc.), thereby improve the erosion resistance of magnesium alloy substrate.In addition, adding of Sm and Y makes Mg alloy surface form finer and close corrosion products film, can effectively suppress the further corrosion of alloy.
Magnesium alloy provided by the present invention can prepare according to following steps:
First by Mg source, Zn source, Ca source, Sm source and Y source melting mixing, obtain alloy melt, then described alloy melt is passed through to casting, mechanical workout and press working successively, obtain magnesium alloy.
Described Mg source is preferably one or more in magnesium simple substance, Mg-Ca master alloy, Mg-Sm master alloy and Mg-Y master alloy, more preferably magnesium simple substance; Described Zn source is preferably zinc simple substance; Described Ca source is preferably calcium simple substance and/or Mg-Ca master alloy, Mg-Ca master alloy more preferably, and in described Mg-Ca master alloy, Ca content is preferably 20～40wt%, more preferably 25～35wt%; Described Sm source is preferably samarium simple substance and/or Mg-Sm master alloy, Mg-Sm master alloy more preferably, and in described Mg-Sm master alloy, Sm content is preferably 10～30wt%, more preferably 15～25wt%; Described Y source is preferably one or more in yttrium simple substance, Mg-Y master alloy and rich Y mishmetal, Mg-Y master alloy more preferably, and in described Mg-Y master alloy, Y content is preferably 10～30wt%, more preferably 15～25wt%.
The present invention preferably carried out removing surface to described Mg source, Zn source, Ca source, Sm source and Y source before preparing magnesium alloy, and the method for removing surface is specially with deionized water rinsing, dries.
By the Mg source after removing surface, Zn source, Ca source, Sm source and Y source melting mixing, this process is specially:
Under the effect of shielding gas, first, by Mg source heating and melting, obtain Mg melt, then in Mg melt, add Zn source, Ca source, Sm source and Y source, stir also standing, obtain alloy melt.Described shielding gas is preferably CO
2and SF
6mixed gas, described CO
2and SF
6volume ratio be preferably 30～50:1; The temperature of described melting is preferably 730～800 ℃, more preferably 740～760 ℃; The described standing time is preferably 10～30min.
The present invention preferably carried out preheating to Zn source, Ca source, Sm source and Y source before described Zn source, Ca source, Sm source and Y source add Mg melt, and did not need the preheating of Ca source when Ca source is calcium simple substance.The temperature of described preheating is preferably 250～350 ℃, more preferably 290～310 ℃; The time of described preheating is preferably 0.5～2h.
The present invention is not particularly limited the equipment of described melting mixing, can adopt well formula resistance furnace well known to those skilled in the art.
Obtain after alloy melt, the present invention casts described alloy melt, obtains alloy pig.The present invention is preferably first cooled to 710～725 ℃ by described alloy melt, then casts.
After casting, the alloy pig obtaining is carried out to mechanical workout, obtain sheet alloy.The present invention is not particularly limited the technique of described mechanical workout and parameter, adopts technique and the parameter of mechanical workout well known to those skilled in the art.
The present invention preferably before mechanical workout involutory ingot carry out homogenizing processing and shrend.The temperature that described homogenizing is processed is preferably 350～500 ℃, more preferably 400～450 ℃; The time that described homogenizing is processed is preferably 2～48h, more preferably 8～24h; The temperature of described shrend is preferably 60～80 ℃.
After mechanical workout, the sheet alloy obtaining is carried out to press working, further to strengthen the mechanical property of magnesium alloy.The present invention is not particularly limited the method for described press working, is preferably hot rolling or hot extrusion, more preferably hot rolling.The temperature of described hot rolling is preferably 360～400 ℃; The compacting speed of described hot rolling is preferably 50～300mm/s; The total reduction of described hot rolling is preferably 40～90%; The draught per pass of described hot rolling is preferably 8～10%; Annealing time between the adjacent passage of described hot rolling is preferably 10～20min.
After press working, obtain magnesium alloy.The present invention preferably carries out stress relief annealing to the magnesium alloy after press working, and the temperature of described stress relief annealing is preferably 100～300 ℃, more preferably 150～250 ℃; The time of described stress relief annealing is preferably 0.5～6h, more preferably 1～4h.
Magnesium alloy provided by the invention comprises Zn, Ca, Sm, Y and Mg, possesses excellent corrosion resistance nature and good mechanical property.
The invention provides a kind of composite material of magnesium alloy, comprising:
Magnesium alloy described in technique scheme;
Be compounded in the anti-corrosion layer of described Mg alloy surface;
Described anti-corrosion layer contains hafnium carbide, tantalum carbide or zirconium carbide.
Composite material of magnesium alloy provided by the invention be take magnesium alloy as base material, in its surface recombination, has anti-corrosion layer.Described anti-corrosion layer contains hafnium carbide, tantalum carbide or zirconium carbide.Described anti-corrosion layer is even, fine and close, can effectively improve erosion resistance and the surface hardness of magnesium alloy.
Composite material of magnesium alloy provided by the invention comprises the anti-corrosion layer that is compounded in described Mg alloy surface, contains hafnium carbide, tantalum carbide or zirconium carbide in described anti-corrosion layer, preferably contains hafnium carbide.In described anti-corrosion layer, carbon content is preferably 25～70at%, more preferably 40～60at%; The thickness of described anti-corrosion layer is preferably 1～10 μ m, more preferably 3～5 μ m.
Composite material of magnesium alloy provided by the invention comprises magnesium alloy and the anti-corrosion layer that is compounded in Mg alloy surface, and described magnesium alloy physical strength is high, and erosion resistance is strong; Described anti-corrosion layer hardness is high, and erosion resistance is strong, good with the associativity of magnesium alloy.Experimental result shows, the tensile strength of composite material of magnesium alloy provided by the invention is more than 400MPa, and yield strength is more than 280MPa, and unit elongation is greater than 7%, surface Vickers' hardness Hv0.2 is greater than 102, more than the bonding strength of anti-corrosion layer and magnesium alloy reaches 5B level (ASTM).This composite material of magnesium alloy corrosion potential in 3.5wt%NaCl solution is-1.3V that corrosion electric current density is 1.0～5.0 * 10
-6a/cm
2.
The preparation method who the invention provides a kind of composite material of magnesium alloy, comprising:
Adopt magnetron sputtering method at the Mg alloy surface deposition anti-corrosion layer described in technique scheme, obtain composite material of magnesium alloy;
Described anti-corrosion layer contains hafnium carbide, tantalum carbide or zirconium carbide.
The present invention adopts magnetron sputtering method to prepare composite material of magnesium alloy, and this process specifically comprises:
Described magnesium alloy is put into magnetron sputtering equipment as substrate, to the mixed gas that passes into sputter gas and reactant gases in magnetron sputtering equipment, take hafnium carbide, tantalum carbide, zirconium carbide, hafnium, tantalum or zirconium as sputtering target, at described substrate surface deposition anti-corrosion layer, obtain composite material of magnesium alloy.Described sputter gas is preferably argon gas; Described reactant gases is preferably methane; The volume ratio of described methane and argon gas is preferably 1～20:80.In magnetron sputtering process, sputtering pressure is preferably 0.2～2Pa; Biassing force is preferably-250～-100V; Sputtering current density is preferably 0.01～0.02A/cm
2; Target-substrate distance is preferably 50～80mm; Base reservoir temperature is preferably 25～250 ℃, more preferably 100～200 ℃.
Before deposition anti-corrosion layer, preferably described Mg alloy surface is carried out to degreasing and pickling, to remove the dirt of Mg alloy surface.
At Mg alloy surface, complete after the deposition of anti-corrosion layer, the present invention preferably carries out vacuum annealing to it, thereby removes the interfacial stress between magnesium alloy and anti-corrosion layer, and the unrelieved stress in release portion anti-corrosion layer.The temperature of described vacuum annealing is preferably 130～170 ℃, more preferably 140～160 ℃; The time of described vacuum annealing is preferably 0.5～3h, more preferably 0.5～1.5h.
The preparation method of composite material of magnesium alloy provided by the invention can prepare the anti-corrosion layer that one deck has high corrosion resistance and excellent abrasive resistance concurrently at Mg alloy surface, and the bonding strength of this anti-corrosion layer and magnesium alloy is high, difficult drop-off.
Below in conjunction with accompanying drawing, the preparation method of composite material of magnesium alloy provided by the invention is described in detail, referring to Fig. 1, the composite material of magnesium alloy production technological process that Fig. 1 provides for the embodiment of the present invention, the steps include: first by Mg source, Zn source, Ca source, Sm source and Y source melting mixing, obtain magnesium alloy fused mass, then by described magnesium alloy fused mass ingot casting, obtain alloy pig, then described alloy pig is made to sheet material by mechanical workout, afterwards sheet material is carried out to hot rolling processing, finally by magnetron sputtering, the Mg alloy surface after hot rolling is processed deposits anti-corrosion layer, obtain composite material of magnesium alloy.
The source in described Mg source, Zn source, Ca source, Sm source and Y source and the concrete technology parameter of each step are consistent with technique scheme, do not repeat them here.
For the purpose of clearer, below by following examples, the present invention is described in detail.
Embodiment 1
With dehydrated alcohol, the Mg-20wt%Sm master alloy of the Mg-30wt%Ca master alloy of the Mg-20wt%Y master alloy of the Zn of the Mg of purity 99.6%, purity 99.5%, purity 98.0%, purity 98.0% and purity 98.0% is carried out to removing surface, and with deionized water rinsing, oven dry.
By the Mg-20wt%Y master alloy after above-mentioned oven dry, Mg-30wt%Ca master alloy, Mg-20wt%Sm master alloy and Zn preheating under 300 ℃ of conditions.
Mg 4700g after above-mentioned oven dry is put into well formula resistance furnace, pass into CO
2+ SF
6(40:1) mixed gas heats under 750 ℃ of conditions.After Mg melts completely, the above-mentioned Zn 10g, Mg-20wt%Y master alloy 250g, Mg-30wt%Ca master alloy 34g and the Mg-20wt%Sm master alloy 50g that add preheating 1h, stir, standing 20 minutes, be cooled to 720 ℃ and be cast in 45# steel permanent type mould, obtain cast alloy.
Cast alloy is processed 400 ℃ of homogenizing of carrying out 8h, and carried out 70 ℃ of shrends.Then by mechanical workout, prepare 200 * 300 * 10mm
3sheet material, at 360 ℃, sheet material is rolled, total reduction is 90%, draught per pass is 10%, rolling speed is 300mm/s, the annealing time between adjacent passage is 10 minutes.After rolling, alloy, 150 ℃ of stress relief annealings of carrying out 1h, obtains the magnesium alloy that composition is Mg-1wt%Y-0.2wt%Zn-0.2wt%Ca-0.2wt%Sm.
Above-mentioned magnesium alloy is carried out to surperficial degreasing, pickling, then described magnesium alloy is put into magnetron sputtering equipment as substrate, in magnetron sputtering equipment, pass into Ar+CH
4(95:5) mixed gas, it is 0.2Pa that sputtering pressure is set, bias voltage is-100V that sputtering current density is 0.01A/cm
2, base reservoir temperature is 100 ℃, target-substrate distance is 60mm, take hafnium carbide as sputtering target, at Mg alloy surface deposition anti-corrosion layer, obtains the composite material of magnesium alloy of anti-corrosion layer thickness 3 μ m, anti-corrosion layer C content 32at%.
The composite material of magnesium alloy obtaining is carried out to 1h vacuum annealing at 150 ℃, remove the interfacial stress of alloy and anti-corrosion layer, and the unrelieved stress in release portion anti-corrosion layer.
Composite material of magnesium alloy after above-mentioned vacuum annealing is carried out to performance test, result shows, room temperature tensile strength and the yield strength of this composite material of magnesium alloy are respectively 400～420MPa and 280～300MPa, unit elongation is 12～15%, more than the bonding strength of anti-corrosion layer and alloy reaches 5B level (ASTM), surperficial Vickers' hardness Hv0.2=102～103.The corrosion potential of this composite material of magnesium alloy in 3.5wt%NaCl solution is-1.3V that corrosion electric current density is 1.0～5.0 * 10
-6a/cm
2.
Embodiment 2
With dehydrated alcohol, the Mg-20wt%Sm master alloy of the Mg-30wt%Ca master alloy of the Mg-20wt%Y master alloy of the Zn of the Mg of purity 99.6%, purity 99.5%, purity 98.0%, purity 98.0% and purity 98.0% is carried out to removing surface, and with deionized water rinsing, oven dry.
By the Mg-20wt%Y master alloy after above-mentioned oven dry, Mg-30wt%Ca master alloy, Mg-20wt%Sm master alloy and Zn preheating under 300 ℃ of conditions.
Mg 3600g after above-mentioned oven dry is put into well formula resistance furnace, pass into CO
2+ SF
6(40:1) mixed gas heats under 750 ℃ of conditions.After Mg melts completely, the above-mentioned Zn 50g, Mg-20wt%Y master alloy 1000g, Mg-30wt%Ca master alloy 167g and the Mg-20wt%Sm master alloy 250g that add preheating 1h, stir, standing 20 minutes, be cooled to 720 ℃ and be cast in 45# steel permanent type mould, obtain cast alloy.
Cast alloy is processed 450 ℃ of homogenizing of carrying out 24h, and carried out 70 ℃ of shrends.Then by mechanical workout, prepare 200 * 300 * 10mm
3sheet material, at 400 ℃, sheet material is rolled, total reduction is 40%, draught per pass is 8%, rolling speed is 50mm/s, the annealing time between adjacent passage is 20 minutes.After rolling, alloy, 250 ℃ of stress relief annealings of carrying out 4h, obtains the magnesium alloy that composition is Mg-4wt%Y-1wt%Zn-1wt%Ca-1wt%Sm.
Above-mentioned magnesium alloy is carried out to surperficial degreasing, pickling, then described magnesium alloy is put into magnetron sputtering equipment as substrate, in magnetron sputtering equipment, pass into Ar+CH
4(92:8) mixed gas, it is 1.0Pa that sputtering pressure is set, bias voltage is-200V that sputtering current density is 0.02A/cm
2, base reservoir temperature is 200 ℃, target-substrate distance is 80mm, take hafnium carbide as sputtering target, at Mg alloy surface deposition anti-corrosion layer, obtains the composite material of magnesium alloy of anti-corrosion layer thickness 5 μ m, anti-corrosion layer C content 58at%.
The composite material of magnesium alloy obtaining is carried out to 4h vacuum annealing at 250 ℃, remove the interfacial stress of alloy and anti-corrosion layer, and the unrelieved stress in release portion anti-corrosion layer.
Composite material of magnesium alloy after above-mentioned vacuum annealing is carried out to performance test, result shows, room temperature tensile strength and the yield strength of this composite material of magnesium alloy are respectively 440～450MPa and 340～350MPa, unit elongation is 7～8%, more than the bonding strength of anti-corrosion layer and alloy reaches 5B level (ASTM), surperficial Vickers' hardness Hv0.2=102～103.The corrosion potential of this composite material of magnesium alloy in 3.5wt%NaCl solution is-1.3V that corrosion electric current density is 1.0～5.0 * 10
-6a/cm
2.
Embodiment 3
With dehydrated alcohol, the Mg-20wt%Sm master alloy of the Mg-30wt%Ca master alloy of the Mg-20wt%Y master alloy of the Zn of the Mg of purity 99.6%, purity 99.5%, purity 98.0%, purity 98.0% and purity 98.0% is carried out to removing surface, and with deionized water rinsing, oven dry.
By the Mg-20wt%Y master alloy after above-mentioned oven dry, Mg-30wt%Ca master alloy, Mg-20wt%Sm master alloy and Zn preheating under 300 ℃ of conditions.
Mg 4270g after above-mentioned oven dry is put into well formula resistance furnace, pass into CO
2+ SF
6(40:1) mixed gas heats under 750 ℃ of conditions.After Mg melts completely, the above-mentioned Zn 25g, Mg-20wt%Y master alloy 500g, Mg-30wt%Ca master alloy 84g and the Mg-20wt%Sm master alloy 125g that add preheating 1h, stir, standing 20 minutes, be cooled to 720 ℃ and be cast in 45# steel permanent type mould, obtain cast alloy.
Cast alloy is processed 430 ℃ of homogenizing of carrying out 16h, and carried out 70 ℃ of shrends.Then by mechanical workout, prepare 200 * 300 * 10mm
3sheet material, at 380 ℃, sheet material is rolled, total reduction is 60%, draught per pass is 10%, rolling speed is 150mm/s, the annealing time between adjacent passage is 15 minutes.After rolling, alloy, 200 ℃ of stress relief annealings of carrying out 2h, obtains the magnesium alloy that composition is Mg-2wt%Y-0.5wt%Zn-0.5wt%Ca-0.5wt%Sm.
Above-mentioned magnesium alloy is carried out to surperficial degreasing, pickling, then described magnesium alloy is put into magnetron sputtering equipment as substrate, in magnetron sputtering equipment, pass into Ar+CH
4(85:15) mixed gas, it is 0.2Pa that sputtering pressure is set, bias voltage is-100V that sputtering current density is 0.01A/cm
2, base reservoir temperature is 100 ℃, target-substrate distance is 60mm, take hafnium carbide as sputtering target, at Mg alloy surface deposition anti-corrosion layer, obtains the composite material of magnesium alloy of anti-corrosion layer thickness 3 μ m, anti-corrosion layer C content 67at%.
The composite material of magnesium alloy obtaining is carried out to 2h vacuum annealing at 200 ℃, remove the interfacial stress of alloy and anti-corrosion layer, and the unrelieved stress in release portion anti-corrosion layer.
Composite material of magnesium alloy after above-mentioned vacuum annealing is carried out to performance test, result shows, room temperature tensile strength and the yield strength of this composite material of magnesium alloy are respectively 420～430MPa and 310～330MPa, unit elongation is 10～12%, more than the bonding strength of anti-corrosion layer and alloy reaches 5B level (ASTM), surperficial Vickers' hardness Hv0.2=102～103.The corrosion potential of this composite material of magnesium alloy in 3.5wt%NaCl solution is-1.3V that corrosion electric current density is 1.0～5.0 * 10
-6a/cm
2.
Embodiment 4
With dehydrated alcohol, the Ca of the Sm of the Y of the Zn of the Mg of purity 99.6%, purity 99.5%, purity 99.0%, purity 99.0% and purity 99.0% is carried out to removing surface, and with deionized water rinsing, oven dry.
By the Zn after above-mentioned oven dry, Y and Sm preheating under 300 ℃ of conditions.
Mg 4920g after above-mentioned oven dry is put into well formula resistance furnace, pass into CO
2+ SF
6(40:1) mixed gas heats under 750 ℃ of conditions.After Mg melts completely, add Ca 10g after above-mentioned oven dry and above-mentioned Zn 10g, Y 50g, the Sm 10g of preheating 1h, stir, standing 20 minutes, be cooled to 720 ℃ and be cast in 45# steel permanent type mould, obtain cast alloy.
Cast alloy is processed 400 ℃ of homogenizing of carrying out 8h, and carried out 70 ℃ of shrends.Then by mechanical workout, prepare 200 * 300 * 10mm
3sheet material, at 360 ℃, sheet material is rolled, total reduction is 90%, draught per pass is 10%, rolling speed is 300mm/s, the annealing time between adjacent passage is 10 minutes.After rolling, alloy, 150 ℃ of stress relief annealings of carrying out 1h, obtains the magnesium alloy that composition is Mg-1wt%Y-0.2wt%Zn-0.2wt%Ca-0.2wt%Sm.
Above-mentioned magnesium alloy is carried out to surperficial degreasing, pickling, then described magnesium alloy is put into magnetron sputtering equipment as substrate, in magnetron sputtering equipment, pass into Ar+CH
4(95:5) mixed gas, it is 0.2Pa that sputtering pressure is set, bias voltage is-100V that sputtering current density is 0.01A/cm
2, base reservoir temperature is 100 ℃, target-substrate distance is 60mm, take hafnium carbide as sputtering target, at Mg alloy surface deposition anti-corrosion layer, obtains the composite material of magnesium alloy of anti-corrosion layer thickness 3 μ m, anti-corrosion layer C content 32at%.
The composite material of magnesium alloy obtaining is carried out to 1h vacuum annealing at 150 ℃, remove the interfacial stress of alloy and anti-corrosion layer, and the unrelieved stress in release portion anti-corrosion layer.
Composite material of magnesium alloy after above-mentioned vacuum annealing is carried out to performance test, result shows, room temperature tensile strength and the yield strength of this composite material of magnesium alloy are respectively 400～420MPa and 280～300MPa, unit elongation is 12～15%, more than the bonding strength of anti-corrosion layer and alloy reaches 5B level (ASTM), surperficial Vickers' hardness Hv0.2=102～103.The corrosion potential of this composite material of magnesium alloy in 3.5wt%NaCl solution is-1.3V that corrosion electric current density is 1.0～5.0 * 10
-6a/cm
2.
Embodiment 5
With rich yttrium mixed rare earth (Ymm), the Mg-30wt%Ca master alloy of purity 98% and the Mg-20wt%Sm master alloy of purity 98% that dehydrated alcohol is greater than 80wt% to the Zn of the Mg of purity 99.0%, purity 99.5%, Y content, carry out removing surface, and with deionized water rinsing, oven dry.
By the preheating under 300 ℃ of conditions of the Zn after above-mentioned oven dry, mishmetal, Mg-30wt%Ca master alloy and Mg-20wt%Sm master alloy.
Mg 4860g after above-mentioned oven dry is put into well formula resistance furnace, pass into CO
2+ SF
6(40:1) mixed gas heats under 750 ℃ of conditions.After Mg melts completely, the above-mentioned Zn 10g, rich yttrium mixed rare earth 50g, Mg-30wt%Ca master alloy 34g and the Mg-20wt%Sm master alloy 50g that add preheating 1h, stir, standing 20 minutes, be cooled to 720 ℃ and be cast in 45# steel permanent type mould, obtain cast alloy.
Cast alloy is processed 400 ℃ of homogenizing of carrying out 8h, and carried out 70 ℃ of shrends.Then by mechanical workout, prepare 200 * 300 * 10mm
3sheet material, at 360 ℃, sheet material is rolled, total reduction is 90%, draught per pass is 10%, rolling speed is 300mm/s, the annealing time between adjacent passage is 10 minutes.After rolling, alloy, 150 ℃ of stress relief annealings of carrying out 1h, obtains the magnesium alloy that composition is Mg-1wt%Ymm-0.2wt%Zn-0.2wt%Ca-0.2wt%Sm.
Above-mentioned magnesium alloy is carried out to surperficial degreasing, pickling, then described magnesium alloy is put into magnetron sputtering equipment as substrate, in magnetron sputtering equipment, pass into Ar+CH
4(95:5) mixed gas, it is 0.2Pa that sputtering pressure is set, bias voltage is-100V that sputtering current density is 0.01A/cm
2, base reservoir temperature is 100 ℃, target-substrate distance is 60mm, take hafnium carbide as sputtering target, at Mg alloy surface deposition anti-corrosion layer, obtains the composite material of magnesium alloy of anti-corrosion layer thickness 3 μ m, anti-corrosion layer C content 32at%.
The composite material of magnesium alloy obtaining is carried out to 1h vacuum annealing at 150 ℃, remove the interfacial stress of alloy and anti-corrosion layer, and the unrelieved stress in release portion anti-corrosion layer.
Composite material of magnesium alloy after above-mentioned vacuum annealing is carried out to performance test, result shows, room temperature tensile strength and the yield strength of this composite material of magnesium alloy are respectively 400～420MPa and 280～300MPa, unit elongation is 12～15%, more than the bonding strength of anti-corrosion layer and alloy reaches 5B level (ASTM), surperficial Vickers' hardness Hv0.2=102～103.The corrosion potential of this composite material of magnesium alloy in 3.5wt%NaCl solution is-1.3V that corrosion electric current density is 1.0～5.0 * 10
-6a/cm
2.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a magnesium alloy, comprises following component:
Be greater than 0 Zn that is less than or equal to 2wt%;
Be greater than 0 Ca that is less than or equal to 2wt%;
Be greater than 0 Sm that is less than or equal to 2wt%;
Be greater than 0 Y that is less than or equal to 6wt%;
The Mg of surplus.
2. magnesium alloy according to claim 1, is characterized in that, comprises the Zn of 0.2～1wt%.
3. magnesium alloy according to claim 1, is characterized in that, comprises the Ca of 0.2～1wt%.
4. magnesium alloy according to claim 1, is characterized in that, comprises the Sm of 0.2～1wt%.
5. magnesium alloy according to claim 1, is characterized in that, comprises the Y of 1～4wt%.
6. a composite material of magnesium alloy, comprising:
Magnesium alloy described in claim 1～5 any one;
Be compounded in the anti-corrosion layer of described Mg alloy surface;
Described anti-corrosion layer contains hafnium carbide, tantalum carbide or zirconium carbide.
7. composite material of magnesium alloy according to claim 6, is characterized in that, in described anti-corrosion layer, carbon content is 25～70at%.
8. a preparation method for composite material of magnesium alloy, comprising:
Adopt magnetron sputtering method at the Mg alloy surface deposition anti-corrosion layer described in claim 1～5 any one, obtain composite material of magnesium alloy;
Described anti-corrosion layer contains hafnium carbide, tantalum carbide or zirconium carbide.
9. preparation method according to claim 8, is characterized in that, the sputter gas using in the process of described deposition anti-corrosion layer is argon gas, and reactant gases is methane.
10. preparation method according to claim 9, is characterized in that, the volume ratio of described methane and argon gas is 1～20:80.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410409421.XA CN104131204B (en) | 2014-08-19 | 2014-08-19 | Magnesium alloy, magnesium alloy composite material and preparation method of composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410409421.XA CN104131204B (en) | 2014-08-19 | 2014-08-19 | Magnesium alloy, magnesium alloy composite material and preparation method of composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104131204A true CN104131204A (en) | 2014-11-05 |
| CN104131204B CN104131204B (en) | 2017-01-25 |
Family
ID=51804052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410409421.XA Active CN104131204B (en) | 2014-08-19 | 2014-08-19 | Magnesium alloy, magnesium alloy composite material and preparation method of composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104131204B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016161565A1 (en) * | 2015-04-08 | 2016-10-13 | Baoshan Iron & Steel Co., Ltd. | Formable magnesium based wrought alloys |
| WO2016161566A1 (en) * | 2015-04-08 | 2016-10-13 | Baoshan Iron & Steel Co., Ltd. | Strain-induced age strengthening in dilute magnesium alloy sheets |
| CN106191587A (en) * | 2016-08-16 | 2016-12-07 | 中国科学院长春应用化学研究所 | Magnesium-rare earth and the preparation method of magnesium-rare earth suspended ceiling pinch plate |
| CN106906404A (en) * | 2017-03-17 | 2017-06-30 | 黄河科技学院 | A kind of preparation method of closed-cell foam composite material of magnesium alloy |
| CN108728792A (en) * | 2017-06-14 | 2018-11-02 | 南京佑天金属科技有限公司 | The preparation method of hafnium carbide film and the mold for including the hafnium carbide film |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0941065A (en) * | 1994-03-23 | 1997-02-10 | Takeshi Masumoto | High strength magnesium alloy and its production |
| WO2006036033A1 (en) * | 2004-09-30 | 2006-04-06 | Yoshihito Kawamura | High-strength and high-toughness metal and process for producing the same |
| CN1965099A (en) * | 2004-06-15 | 2007-05-16 | 株式会社东京大学Tlo | High toughness magnesium-base alloy, drive component using same, and method for producing high toughness magnesium-base alloy material |
| CN101468538A (en) * | 2007-12-24 | 2009-07-01 | 比亚迪股份有限公司 | Coating material and preparation method thereof |
| WO2009147861A1 (en) * | 2008-06-05 | 2009-12-10 | 独立行政法人産業技術総合研究所 | Easily formable magnesium alloy sheet and process for production thereof |
| CN102534612A (en) * | 2010-12-30 | 2012-07-04 | 鸿富锦精密工业（深圳）有限公司 | Magnesium alloy surface anticorrosive treatment method and magnesium product thereof |
| EP2481825A1 (en) * | 2011-02-01 | 2012-08-01 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Magnesium alloy containing rare earth metals |
-
2014
- 2014-08-19 CN CN201410409421.XA patent/CN104131204B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0941065A (en) * | 1994-03-23 | 1997-02-10 | Takeshi Masumoto | High strength magnesium alloy and its production |
| CN1965099A (en) * | 2004-06-15 | 2007-05-16 | 株式会社东京大学Tlo | High toughness magnesium-base alloy, drive component using same, and method for producing high toughness magnesium-base alloy material |
| WO2006036033A1 (en) * | 2004-09-30 | 2006-04-06 | Yoshihito Kawamura | High-strength and high-toughness metal and process for producing the same |
| CN101468538A (en) * | 2007-12-24 | 2009-07-01 | 比亚迪股份有限公司 | Coating material and preparation method thereof |
| WO2009147861A1 (en) * | 2008-06-05 | 2009-12-10 | 独立行政法人産業技術総合研究所 | Easily formable magnesium alloy sheet and process for production thereof |
| CN102534612A (en) * | 2010-12-30 | 2012-07-04 | 鸿富锦精密工业（深圳）有限公司 | Magnesium alloy surface anticorrosive treatment method and magnesium product thereof |
| EP2481825A1 (en) * | 2011-02-01 | 2012-08-01 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Magnesium alloy containing rare earth metals |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016161565A1 (en) * | 2015-04-08 | 2016-10-13 | Baoshan Iron & Steel Co., Ltd. | Formable magnesium based wrought alloys |
| WO2016161566A1 (en) * | 2015-04-08 | 2016-10-13 | Baoshan Iron & Steel Co., Ltd. | Strain-induced age strengthening in dilute magnesium alloy sheets |
| CN107532249A (en) * | 2015-04-08 | 2018-01-02 | 宝山钢铁股份有限公司 | Formable magnesium-based wrought alloy |
| US10570490B2 (en) | 2015-04-08 | 2020-02-25 | Baoshan Iron & Steel Co., Ltd. | Strain-induced age strengthening in dilute magnesium alloy sheets |
| CN106191587A (en) * | 2016-08-16 | 2016-12-07 | 中国科学院长春应用化学研究所 | Magnesium-rare earth and the preparation method of magnesium-rare earth suspended ceiling pinch plate |
| CN106906404A (en) * | 2017-03-17 | 2017-06-30 | 黄河科技学院 | A kind of preparation method of closed-cell foam composite material of magnesium alloy |
| CN106906404B (en) * | 2017-03-17 | 2018-05-11 | 黄河科技学院 | A kind of preparation method of closed-cell foam composite material of magnesium alloy |
| CN108728792A (en) * | 2017-06-14 | 2018-11-02 | 南京佑天金属科技有限公司 | The preparation method of hafnium carbide film and the mold for including the hafnium carbide film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104131204B (en) | 2017-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104131204A (en) | Magnesium alloy, magnesium alloy composite material and preparation method of composite material | |
| CN104561878A (en) | High-entropy alloy powder for spray coating and preparation method thereof, as well as composite material and preparation method thereof | |
| CN102345034B (en) | Method for preparing multielement corrosion-resistant hot-dipping alloy coating layer and raw materials | |
| CN103590008B (en) | One is coated with interlayer in TiAl alloy and MCrAlY and prepares Al 2o 3the method of diffusion barrier | |
| CN107937879A (en) | A kind of method of neodymium iron boron magnetic body and neodymium iron boron magnetic body overlay coating | |
| CN103572217B (en) | A kind of Neodymium-iron-boronpermanent permanent magnetic material surface protection layer and preparation method thereof | |
| Song et al. | Synthesis of Ni-TiC composite powder electrochemically in molten chlorides | |
| CN110935864B (en) | Preparation method of surface-treated ZTA particle-reinforced steel-based composite grinding roller | |
| CN104988466A (en) | Method for preparing alpha-Al2O3 coating by using double-glow plasma diffusion metalizing technology at low temperature | |
| CN102392278B (en) | Al-Ni alloy electroplating method in low-temperature salt melting system | |
| CN108130505B (en) | Method for preparing high-entropy alloy coating by plasma beam alloying | |
| CN104775039A (en) | Purification method of copper/copper alloy liquid | |
| CN102312237A (en) | Laser strengthening method for steam turbine titanium alloy blade | |
| CN106591761B (en) | Method for preparing composite coating resisting molten metal erosion | |
| CN102632237A (en) | Method for manufacturing pure copper/ copper-chromium alloy composite contact material by spray deposition | |
| CN102676877B (en) | Iron white copper alloy and preparation method thereof | |
| CN114672755B (en) | Non-wetting coating suitable for resisting high-temperature aluminum permeation and preparation method thereof | |
| CN107243641A (en) | Brilliant high-entropy alloy powder of a kind of high-activity nano and preparation method thereof | |
| CN104388992B (en) | The method of Al Zn alloy layers is co-deposited in ion liquid system | |
| CN104149415B (en) | A kind of magnesium-rare earth and preparation method thereof | |
| CN100575535C (en) | The metallic surface forms TiB 2The method of ceramic composite | |
| CN106514039B (en) | A kind of copper and tin titanium solder and preparation method thereof | |
| Wei et al. | Preparation of Mg-Li-Sm alloys by electrocodeposition in molten salt | |
| CN112725751B (en) | Preparation method of surface protective coating of ultrathin neodymium-iron-boron permanent magnet | |
| CN104419926A (en) | Magnet surface treatment method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |