CN104152747B - A kind of Mg-Zn-Y magnesium alloy and preparation method thereof - Google Patents

A kind of Mg-Zn-Y magnesium alloy and preparation method thereof Download PDF

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CN104152747B
CN104152747B CN201410423441.2A CN201410423441A CN104152747B CN 104152747 B CN104152747 B CN 104152747B CN 201410423441 A CN201410423441 A CN 201410423441A CN 104152747 B CN104152747 B CN 104152747B
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滕新营
许敏
杨超平
耿继伟
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University of Jinan
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Abstract

The invention provides a kind of Mg-Zn-Y magnesium alloy, be made up of: 55.50 ~ 56.00%Zn, 11.50 ~ 13.00%Y the component of following mass percent, surplus is magnesium and micro impurity element, and described Mg-Zn-Y magnesium alloy quasicrystal integration number is 26.8 ~ 51.3%; Present invention also offers the preparation method of Mg-Zn-Y magnesium alloy, adopt rapid solidification injection method, simple, convenient, easy to utilize.The Mg-Zn-Y magnesium alloy that the present invention is prepared by quick setting method, increases Icosahedral phases volume fraction, solves the problems such as the accurate brilliant content of magnesium alloy in existing preparation method is lower, tissue distribution is uneven, its erosion resistance and Vickers' hardness are improved.

Description

A kind of Mg-Zn-Y magnesium alloy and preparation method thereof
Technical field
The present invention relates to high-performance magnesium-alloy technical field, be specifically related to a kind of Mg-Zn-Y magnesium alloy and preparation method thereof.
Background technology
Magnesium alloy has low density, high specific tenacity and specific rigidity, good damping property and magnetic shield performance etc., and stock number also relative abundance applies the lightest structural metallic materials in engineering, has broad application prospects in modern industrialization application.Wherein, in automobile component, emphasis is applied as again with magnesium alloy, in the last few years, the progress of manufacturing technology and technological process advantageously facilitates the application of magnesium alloy in automobile industry, obdurability, the high-temperature behavior of magnesium alloy are significantly promoted, but poor corrosion resistance nature is the principal element hindering magnesium alloy application, becomes magnesium alloy as the bottleneck of lighting structured material in industrial production volume production process.
Research shows, icosahedral quasicrystal (I phase) has significant corrosion resistance, high rigidity, low-friction coefficient, low interfacial energy, improves magnesium alloy corrosion resistance nature at a room temperature and a high temperature, improves its mechanical property simultaneously.Material supplier author is making great efforts by preparing accurate brilliant always, and especially the Icosahedral phases of large volume fraction improves erosion resistance and the mechanical property of magnesium alloy.Magnesium alloy is close under the conventional coagulation of equilibrium state, and microtexture is thicker and accurate brilliant content is lower, and rapid solidification can expand solid solubility and improve microtexture, thus significantly improves alloy corrosion resistance, is therefore more and more subject to the attention of material circle.But the processing parameter of existing rapid solidification prepare the problems such as the accurate brilliant content of magnesium alloy is lower, tissue distribution is uneven make its erosion resistance and mechanical property poor.These problems have become the bottleneck of restriction magnesium alloy materials development and application.
Summary of the invention
Low in order to solve above-mentioned magnesium alloy quasicrystal integration number, and adopt existing rapid solidification preparation technology to be difficult to obtain the problem of high corrosion resistance magnesium alloy, the invention provides a kind of Mg-Zn-Y magnesium alloy materials and rapid solidification preparation method thereof, optimize magnesium alloy composition proportion, the Icosahedral phases of generation is made to have larger volume fraction, and be uniformly distributed in the base, thus solve accurate brilliant content problem on the low side, the erosion resistance of magnesium alloy is significantly improved, meets magnesium alloy as high corrosion resistance lighting structured material application requiring in the industrial production.
Technical solution of the present invention is: a kind of Mg-Zn-Y magnesium alloy of the present invention, and be made up of the component of following mass percent: 55.50 ~ 56.00%Zn, 11.50 ~ 13.00%Y, surplus is magnesium and micro impurity element;
Described Mg-Zn-Y magnesium alloy, containing Icosahedral phases in alloy structure, quasicrystal integration number is 26.8 ~ 51.3%.
Mg-Zn-Y magnesium alloy preparation method provided by the invention is as follows: first by after Mg-Y master alloy, pure magnesium ingot and pure zinc ingot melting, make the female ingot of Mg-Zn-Y cast alloy, after female for Mg-Zn-Y cast alloy ingot fusing, adopt rapid solidification injection method, obtained Mg-Zn-Y magnesium alloy; Described rapid solidification injection method, adopt high vacuum single roller to revolve the system of quenching, the copper roller rotating speed that described high vacuum single roller revolves the system of quenching is 400 ~ 800rpm, and injection argon pressure is 0.04 ~ 0.09MPa.
The copper roller diameter that described high vacuum single roller revolves the system of quenching is 240mm;
Described Mg-Y master alloy, it forms content by mass percentage and is: 29.50 ~ 30.50%Y and 69.50 ~ 70.50%Mg.
Mg-Zn-Y magnesium alloy preparation method of the present invention, step is:
1) Regular casting methods prepares Mg-Y master alloy:
With weight proportion be 29.50 ~ 30.50%Y, 69.50 ~ 70.50%Mg for raw material, put into crucible heat fused and be warming up to 815 ~ 845 DEG C, casting metal type after stirring, obtained Mg-Y master alloy, passes into SF in fusion process 6: CO 2gas shield, obtains Mg-Y master alloy;
Mg-Y master alloy mass percentage content described in step 1) is Mg-29.50 ~ 30.50%Y;
2) the female ingot of Mg-Zn-Y cast alloy is prepared:
Take pure zinc ingot, Mg-Y master alloy and pure magnesium ingot raw material by weight ratio, at SF 6and CO 2under mixed gas protected, Mg-Y master alloy and pure magnesium ingot are put into the container being preheating to 200 ~ 300 DEG C, then 710 ~ 740 DEG C are warming up to, when Mg-Y master alloy and pure magnesium ingot melt completely, add pure zinc ingot, stir, the waste residue of removing molten surface, continue stirring 2 ~ 3 minutes, leave standstill 15 ~ 25 minutes; At SF 6and CO 2under mixed gas protected, room temperature leaves standstill 3 ~ 5 minutes, castable, the female ingot of obtained Mg-Zn-Y cast alloy;
Step 2) described in pure zinc ingot, Mg-Y master alloy and pure magnesium ingot raw material, weight proportion is: 55.50 ~ 56.00% pure zinc ingots, 38.50 ~ 43.00%Mg-Y master alloy, surplus are pure magnesium ingot.
3) high vacuum single roller revolves system rapid solidification of quenching and sprays preparation Mg-Zn-Y magnesium alloy:
By step 2) the obtained female ingot of Mg-Zn-Y cast alloy is broken, cleaning, put into the silica tube that high vacuum single roller revolves the system of quenching, be warming up to the female ingot of alloy under vacuum to melt completely, obtain liquation, under argon pressure is 0.04 ~ 0.09MPa condition, be the copper roller surface of 400 ~ 800rpm from silica tube lower end nozzle ejection to rotating speed by liquation, obtained Mg-Zn-Y magnesium alloy.
Step 1) and 2) described in SF 6and CO 2mixed gas, SF 6: CO 2volume ratio is 1:150.
Described high vacuum single roller revolves the copper roller rotating speed preferably 600 ~ 800rpm of the system of quenching, and most preferred copper roller rotating speed is 800rpm;
Described high vacuum single roller revolves the silica tube nozzle of the system of quenching and copper roller upper edge distance is 5 ~ 15mm;
Described high vacuum single roller revolves the system of quenching, and vacuum tightness is 3.0 × 10 -3pa, induction heating power 3KW, silica tube nozzle diameter is 0.6mm, and copper roller diameter is 240mm;
Described Mg-Zn-Y magnesium alloy, content is by mass percentage: 55.50 ~ 56.00%Zn, 11.50 ~ 13.00%Y, and all the other are magnesium and micro impurity element; Nominal composition is, by atomic percentage: Mg 57zn 37y 6.
Beneficial effect of the present invention:
(1) the Mg-Zn-Y magnesium alloy prepared by quick setting method of the present invention, on original icosahedral quasicrystal phase structure basis, increase Icosahedral phases volume fraction, overcome the problem that in the accurate crystal preparation method of prior art, quasicrystal integration number is on the low side, solve the problems such as the accurate brilliant content of magnesium alloy is lower, tissue distribution is uneven, its erosion resistance is significantly improved.
(2) Mg-Zn-Y magnesium alloy of the present invention, because icosahedral quasicrystal (I phase) has significant corrosion resistance, high rigidity, low-friction coefficient, low interfacial energy, makes Vickers' hardness be improved.On the other hand, dendrite and crystal grain in rapid solidification refinement alloy, expand Zn, Y solid solubility in Mg, play solution strengthening effect, these all contribute to the raising comprising the mechanical properties such as hardness.
(3) preparation method of the present invention, adopts quick setting method, more adequately determines the corresponding relation that vacuum list roller revolves Icosahedral phases volume fraction in the processing parameters such as the copper roller rotating speed of the system of quenching and alloy, simple, convenient, easy to utilize.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the Mg-Zn-Y magnesium alloy of embodiment 1,2,3 preparation and the magnesium alloy of comparative example 1 preparation;
In Fig. 2, a figure, b figure are followed successively by SEM and the EDS analysis chart of magnesium alloy prepared by comparative example 1, and c figure, d figure are followed successively by SEM and the EDS analysis chart of Mg-Zn-Y magnesium alloy prepared by embodiment 3;
In Fig. 3, a figure is the high-resolution-ration transmission electric-lens (HRTEM) of Mg-Zn-Y magnesium alloy prepared by embodiment 3, b figure is that the electron diffraction (SAED) of choosing of scheming ' B ' part with a corresponding is analyzed, and c figure is that the EDS in corresponding ' A ' and ' B ' region of a figure analyzes;
In Fig. 4, a, b, c, d figure is followed successively by the SEM figure of the Mg-Zn-Y magnesium alloy of embodiment 1,2,3 preparation and the magnesium alloy of comparative example 1 preparation;
Fig. 5 is the Tafel collection of illustrative plates of the Mg-Zn-Y magnesium alloy of embodiment 1,2,3 preparation and the magnesium alloy of comparative example 1 preparation;
SEM after a, b, c, d figure is followed successively by the Mg-Zn-Y magnesium alloy of embodiment 1,2,3 preparation and the Corrosion Behaviors of Magnesium Alloys of comparative example 1 preparation in Fig. 6 schemes, and each little figure in the figure upper left corner is corresponding partial enlarged drawing.
Embodiment
Below in conjunction with accompanying drawing, by embodiment and comparative example, the superiority to high corrosion resistance magnesium alloy of the present invention and preparation method thereof is described further:
In the embodiment of the present invention, high vacuum single roller used revolves the system model of quenching and is: HVDS-II type.
Embodiment 1
Following steps are taked to obtain:
1) Regular casting methods prepares Mg-Y master alloy:
Take weight proportion as 30.00%Y, 70.00%Mg be raw material, put into crucible heat fused and be warming up to 830 DEG C, casting metal type after stirring, obtained Mg-Y master alloy, passes into SF in aforesaid operations process 6: CO 2volume ratio is the gas shield of 1:150, obtains Mg-Y master alloy;
2) the female ingot of Mg-Zn-Y cast alloy is prepared:
56.00% pure zinc ingot, 40%Mg-Y master alloy, surplus are that pure magnesium ingot takes raw material by weight ratio, in resistance furnace, pass into SF 6: CO 2volume ratio is the gas shield of 1:150; Mg-Y master alloy and pure magnesium ingot are put into the crucible being preheating to 200 DEG C; be warmed up to 710 DEG C; when Mg-Y master alloy and pure magnesium ingot melt completely; add pure zinc ingot, stir, the waste residue of removing molten surface; continue stirring 2 ~ 3 minutes, leave standstill 15 minutes.At SF 6: CO 2volume ratio is under the gas shield of 1:150, takes out crucible, and room temperature left standstill after 3 ~ 5 minutes, was poured into solidification forming in the mould being preheated to 200 DEG C, the female ingot of obtained Mg-Zn-Y cast alloy;
3) high vacuum single roller revolves system rapid solidification of quenching and sprays preparation Mg-Zn-Y magnesium alloy:
By step 2) the obtained female ingot of Mg-Zn-Y cast alloy is crushed to the bulk of 5 ~ 8g, cleaning, and choose the female ingot of the cast alloy after the fragmentation of 5g uniform composition, put into the silica tube that bottom is 0.6mm nozzle with diameter.Be evacuated to 3.0 × 10 - 3pa, heats up, after the female ingot of alloy melts completely, obtain liquation, liquation, to apart from copper roller upper edge 15mm, under injection argon pressure 0.09MPa, is the copper roller surface of 400rpm from silica tube lower end nozzle ejection to rotating speed by the height of rapid reduction silica tube, obtained Mg-Zn-Y magnesium alloy.Relevant high vacuum single roller revolves system process parameters of quenching: vacuum tightness 3.0 × 10 -3pa, induction heating power 3KW, copper roller diameter 240mm;
Obtained Mg-Zn-Y magnesium alloy, content is by mass percentage: 56.00%Zn, 12.00%Y, and all the other are magnesium and micro impurity element.
The volume fraction of software Lmage-ProPlus6.0 analytical calculation Icosahedral phases is now used to be about 26.8%, in table 1.
The Mg-Zn-Y corrosion resistance of magnesium alloy parameter recording the present embodiment 1 is: corrosion potential, corrosion current density, pitting potential are followed successively by-0.810V, 2.014 × 10 -4acm -2,-0.620V, in table 2; Vickers' hardness brings up to 203.86HV, in table 3.The erosion resistance of this alloy is significantly improved compared with comparative example magnesium alloy with Vickers' hardness.
Embodiment 2
Following steps are taked to obtain:
1) Regular casting methods prepares Mg-Y master alloy:
Take weight proportion as 29.50%Y, 70.50%Mg be raw material, put into crucible heat fused and be warming up to 840 DEG C, casting metal type after stirring, obtained Mg-Y master alloy, passes into SF in aforesaid operations process 6: CO 2volume ratio is the gas shield of 1:150, obtains Mg-Y master alloy;
2) the female ingot of Mg-Zn-Y cast alloy is prepared:
55.50% pure zinc ingot, 38.98%Mg-Y master alloy, surplus are that pure magnesium ingot takes raw material by weight ratio, in resistance furnace, pass into SF 6: CO 2volume ratio is the gas shield of 1:150; Mg-Y master alloy and pure magnesium ingot are put into the crucible being preheating to 300 DEG C; be warmed up to 740 DEG C; when Mg-Y master alloy and pure magnesium ingot melt completely; add pure zinc ingot, stir, the waste residue of removing molten surface; continue stirring 2 ~ 3 minutes, leave standstill 25 minutes.At SF 6: CO 2volume ratio is under the gas shield of 1:150, takes out crucible, and room temperature left standstill after 3 ~ 5 minutes, was poured into solidification forming in the mould being preheated to 300 DEG C, the female ingot of obtained Mg-Zn-Y cast alloy;
3) high vacuum single roller revolves system rapid solidification of quenching and sprays preparation Mg-Zn-Y magnesium alloy:
By step 2) the obtained female ingot of Mg-Zn-Y cast alloy is crushed to the bulk of 5 ~ 8g, cleaning, and choose the female ingot of the cast alloy after the fragmentation of 7g uniform composition, put into the silica tube that bottom is 0.6mm nozzle with diameter.Be evacuated to 3.0 × 10 - 3pa, heats up, after the female ingot of alloy melts completely, obtain liquation, liquation, to apart from copper roller upper edge 5mm, under injection argon pressure 0.04MPa, is the copper roller surface of 600rpm from silica tube lower end nozzle ejection to rotating speed by the height of rapid reduction silica tube, obtained Mg-Zn-Y magnesium alloy.Relevant high vacuum single roller revolves system process parameters of quenching: vacuum tightness 3.0 × 10 -3pa, induction heating power 3KW, copper roller diameter 240mm;
Obtained Mg-Zn-Y magnesium alloy, content is by mass percentage: 55.50%Zn, 11.50%Y, and all the other are magnesium and micro impurity element.
The volume fraction of software Lmage-ProPlus6.0 analytical calculation Icosahedral phases is now used to be about 33.1%, in table 1.
The Mg-Zn-Y corrosion resistance of magnesium alloy parameter recording the present embodiment 2 is: corrosion potential, corrosion current density, pitting potential are followed successively by-0.691V, 1.693 × 10 -4acm -2,-0.264V, in table 2; Vickers' hardness brings up to 237.05HV, in table 3.The erosion resistance of this alloy is significantly improved compared with comparative example magnesium alloy with Vickers' hardness.
Embodiment 3
Following steps are taked to obtain:
1) Regular casting methods prepares Mg-Y master alloy:
Take weight proportion as 30.00%Y, 70.00%Mg be raw material, put into crucible heat fused and be warming up to 820 DEG C, casting metal type after stirring, obtained Mg-Y master alloy, passes into SF in aforesaid operations process 6: CO 2volume ratio is the gas shield of 1:150, obtains Mg-Y master alloy;
2) the female ingot of Mg-Zn-Y cast alloy is prepared:
55.76% pure zinc ingot, 40.96%Mg-Y master alloy, surplus are that pure magnesium ingot takes raw material by weight ratio, in resistance furnace, pass into SF 6: CO 2volume ratio is the gas shield of 1:150; Mg-Y master alloy and pure magnesium ingot are put into the crucible being preheating to 250 DEG C; be warmed up to 730 DEG C; when Mg-Y master alloy and pure magnesium ingot melt completely; add pure zinc ingot, stir, the waste residue of removing molten surface; continue stirring 2 ~ 3 minutes, leave standstill 20 minutes.At SF 6: CO 2volume ratio is under the gas shield of 1:150, takes out crucible, and room temperature left standstill after 3 ~ 5 minutes, was poured into solidification forming in the mould being preheated to 250 DEG C, the female ingot of obtained Mg-Zn-Y cast alloy;
3) high vacuum single roller revolves system rapid solidification of quenching and sprays preparation Mg-Zn-Y magnesium alloy:
By step 2) the obtained female ingot of Mg-Zn-Y cast alloy is crushed to the bulk of 5 ~ 8g, cleaning, and choose the female ingot of the cast alloy after the fragmentation of 8g uniform composition, put into the silica tube that bottom is 0.6mm nozzle with diameter.Be evacuated to 3.0 × 10 - 3pa, heats up, after the female ingot of alloy melts completely, obtain liquation, liquation, to apart from copper roller upper edge 10mm, under injection argon pressure 0.06MPa, is the copper roller surface of 800rpm from silica tube lower end nozzle ejection to rotating speed by the height of rapid reduction silica tube, obtained Mg-Zn-Y magnesium alloy.Relevant high vacuum single roller revolves system process parameters of quenching: vacuum tightness 3.0 × 10 -3pa, induction heating power 3KW, copper roller diameter 240mm;
Obtained Mg-Zn-Y magnesium alloy, content is by mass percentage: 55.76%Zn, 12.29%Y, and all the other are magnesium and micro impurity element.
The volume fraction of software Lmage-ProPlus6.0 analytical calculation Icosahedral phases is now used to be about 51.3%, in table 1.
The Mg-Zn-Y corrosion resistance of magnesium alloy parameter recording the present embodiment 3 is: corrosion potential, corrosion current density, pitting potential are followed successively by-0.378V, 0.763 × 10 -4acm -2,-0.115V, in table 2; Vickers' hardness brings up to 277.33HV, in table 3.The erosion resistance of this alloy is significantly improved compared with comparative example magnesium alloy with Vickers' hardness.
Embodiment 4
Following steps are taked to obtain:
1) Regular casting methods prepares Mg-Y master alloy:
Take weight proportion as 30.50%Y, 69.50%Mg be raw material, put into crucible heat fused and be warming up to 820 DEG C, casting metal type after stirring, obtained Mg-Y master alloy, passes into SF in aforesaid operations process 6: CO 2volume ratio is the gas shield of 1:150, obtains Mg-Y master alloy;
2) the female ingot of Mg-Zn-Y cast alloy is prepared:
56.00% pure zinc ingot, 42.62%Mg-Y master alloy, surplus are that pure magnesium ingot takes raw material by weight ratio, in resistance furnace, pass into SF 6: CO 2volume ratio is the gas shield of 1:150; Mg-Y master alloy and pure magnesium ingot are put into the crucible being preheating to 250 DEG C; be warmed up to 730 DEG C; when Mg-Y master alloy and pure magnesium ingot melt completely; add pure zinc ingot, stir, the waste residue of removing molten surface; continue stirring 2 ~ 3 minutes, leave standstill 20 minutes.At SF 6: CO 2volume ratio is under the gas shield of 1:150, takes out crucible, and room temperature left standstill after 3 ~ 5 minutes, was poured into solidification forming in the mould being preheated to 250 DEG C, the female ingot of obtained Mg-Zn-Y cast alloy;
3) high vacuum single roller revolves system rapid solidification of quenching and sprays preparation Mg-Zn-Y magnesium alloy:
By step 2) the obtained female ingot of Mg-Zn-Y cast alloy is crushed to the bulk of 5 ~ 8g, cleaning, and choose the female ingot of the cast alloy after the fragmentation of 8g uniform composition, put into the silica tube that bottom is 0.6mm nozzle with diameter.Be evacuated to 3.0 × 10 - 3pa, heats up, after the female ingot of alloy melts completely, obtain liquation, liquation, to apart from copper roller upper edge 8mm, under injection argon pressure 0.05MPa, is the copper roller surface of 700rpm from silica tube lower end nozzle ejection to rotating speed by the height of rapid reduction silica tube, obtained Mg-Zn-Y magnesium alloy.Relevant high vacuum single roller revolves system process parameters of quenching: vacuum tightness 3.0 × 10 -3pa, induction heating power 3KW, copper roller diameter 240mm;
Obtained Mg-Zn-Y magnesium alloy, content is by mass percentage: 56.00%Zn, 13.00%Y, and all the other are magnesium and micro impurity element.
The volume fraction of software Lmage-ProPlus6.0 analytical calculation Icosahedral phases is now used to be about 46.5%, in table 1.
The Mg-Zn-Y corrosion resistance of magnesium alloy parameter recording the present embodiment 4 is: corrosion potential, corrosion current density, pitting potential are followed successively by-0.521V, 1.146 × 10 -4acm -2,-0.258V, in table 2; Vickers' hardness brings up to 251.17HV, in table 3.The erosion resistance of this alloy is significantly improved compared with comparative example magnesium alloy with Vickers' hardness.
Comparative example 1
With maximum embodiment 3 preparation method of the volume fraction of Icosahedral phases for reference, obtain routine casting with the accurate grained magnesium alloy of component, compare with Mg-Zn-Y magnesium alloy of the present invention.
Step is:
1) Regular casting methods prepares Mg-Y master alloy:
Take weight proportion as 30.00%Y, 70.00%Mg be raw material, put into crucible heat fused and be warming up to 820 DEG C, casting metal type after stirring, obtained Mg-Y master alloy, passes into SF in aforesaid operations process 6: CO 2volume ratio is the gas shield of 1:150, obtains Mg-Y master alloy;
2) the female ingot of Mg-Zn-Y cast alloy is prepared:
55.76% pure zinc ingot, 40.96%Mg-Y master alloy, surplus are that pure magnesium ingot takes raw material by weight ratio, in resistance furnace, pass into SF 6: CO 2volume ratio is the gas shield of 1:150; Mg-Y master alloy and pure magnesium ingot are put into the crucible being preheating to 250 DEG C; be warmed up to 730 DEG C; when Mg-Y master alloy and pure magnesium ingot melt completely; add pure zinc ingot, stir, the waste residue of removing molten surface; continue stirring 2 ~ 3 minutes, leave standstill 20 minutes.At SF 6: CO 2volume ratio is under the gas shield of 1:150, takes out crucible, and room temperature left standstill after 3 ~ 5 minutes, was poured into solidification forming in the mould being preheated to 250 DEG C, the female ingot of obtained Mg-Zn-Y cast alloy; Be this comparative example 1 routine casting with the accurate grained magnesium alloy of component.
The volume fraction of software Lmage-ProPlus6.0 analytical calculation Icosahedral phases is now used to be about 18.6%, in table 1.
The routine casting recording comparative example 1 with component accurate grained magnesium alloy erosion resistance parameter is: corrosion potential, corrosion current density, pitting potential are followed successively by-1.408V, 3.389 × 10 -4acm -2,-1.180V, in table 2; Vickers' hardness is 157.85HV, in table 3.
Comparative example 2
Adopt quick setting method in prior art to obtain magnesium alloy, compare with Mg-Zn-Y magnesium alloy of the present invention.
Step is:
1) Regular casting methods prepares the female ingot of Mg-Zn-Y cast alloy:
Pure Mg and pure Zn raw material surface are carried out mechanical grinding with scale removal and dirt, and cleans with acetone and alcohol, prepare burden by preset blending ratio physical balance with Mg-47wt.%Y master alloy.In crucible electrical resistance furnace, be slowly warming up to about 750 DEG C carry out melting, load weighted pure Mg, pure Zn and Mg-47wt.%Y master alloy are added melting in crucible successively.CO is used in whole melting and casting process 2+ 0.3vol.%SF 6mixed gas protected liquation.After completing whole fusion process, liquation is poured in graphite casting mould, make and commonly solidify Mg-Zn-Y alloy sample.
Obtained commonly solidify Mg-Zn-Y alloy sample, content is by mass percentage: 16.90%Zn, 3.80%Y, and all the other are magnesium and micro impurity element.
2) high vacuum single roller revolve quench system rapid solidification spray prepare magnesium alloy:
Rapid solidification carries out on KND-II type list roller quick solidification apparatus, and experimental technique condition is as follows: argon gas spraying pressure is 0.05MPa; Roller speed is 900rpm; Roll surface and nozzle gap are 5mm; Vacuum tightness 2.5 × 10 -3pa, and protect with Ar gas, obtain magnesium alloy.
Obtained obtains magnesium alloy, and content is by mass percentage: 16.90%Zn, 3.80%Y, and all the other are magnesium and micro impurity element.
The volume fraction of software Lmage-ProPlus6.0 analytical calculation Icosahedral phases is now used to be about 25.0%, in table 1.
The corrosion resistance of magnesium alloy parameter recording this comparative example 2 is: corrosion potential, corrosion current density, pitting potential are followed successively by-1.359V, 2.409 × 10 -4acm -2,-1.052V, in table 2; Vickers' hardness is 187.16HV, in table 3.
Each shared volume fraction (%) mutually of table 1 embodiment of the present invention and comparative example
The erosion resistance parameter of table 2 embodiment of the present invention and comparative example
The Vickers' hardness of table 3 embodiment of the present invention and comparative example
Drawn by table 1,2 and 3 contrasts, embodiment magnesium alloy parameter is obviously better than comparative example, and it is maximum that embodiment 3 magnesium alloy contains Icosahedral phases volume fraction, and erosion resistance is best, and Vickers' hardness is the highest, shows as significantly excellent over-all properties.
Obtain magnesium alloy for embodiment 1,2,3 and comparative example 1 below, by reference to the accompanying drawings, Mg-Zn-Y magnesium alloy of the present invention, Icosahedral phases and each parameter made a concrete analysis of:
1, Icosahedral phases and Icosahedral phases volume fraction:
Fig. 1 is X ray diffracting spectrum (XRD), draws according to Jade software analysis, and embodiment 1,2,3 and comparative example 1 interalloy all only have α-Mg phase and I-phase (Mg 3zn 6y) two kinds of things are identified mutually.EDS analysis is carried out to embodiment 3 and comparative example 1 alloy, see a figure and b figure in Fig. 2, obtaining Mg content range in petal-shaped phase (second-phase) is 22.12 ~ 36.28 (at.%), Zn content range is 54.87 ~ 63.75 (at.%), Y content range is 8.86 ~ 14.14 (at.%), calculate petal-shaped mutually in the atomic ratio of Mg:Zn:Y be approximately equal to 3:6:1, these results nominal composition Mg brilliant in the standard reported 30zn 60y 10(at.%) closely, thus, in preliminary judgement embodiment 1,2,3 and comparative example 1, magnesium alloy is by identical two kinds of thing phase composites, and second-phase is Icosahedral phases.
Choose excellent performance and representative embodiment 3Mg-Zn-Y magnesium alloy is analyzed further, see Fig. 3, wherein a figure is the light field pattern photo of HRTEM in alloy, and b figure is electron diffraction analysis, and c figure is that EDS analyzes.Analyze according to the EDS under HRTEM and determine that in a figure, comparatively dark-part (A) is matrix, bright areas (B) preliminary judgement is I-phase.B figure is the compound selected area electron diffraction style of embodiment 3 alloy sample, can find out that its structure has typical fivefold symmetry (5-f), and fivefold symmetry axle and [111] mgzone axis parallels, i.e. 5-f//[111] mg.Quasi-periodic structure cannot describe by Bravais lattice, under its TEM, electron diffraction shows as five times, eight times, ten times and ten secondary rotating symmetrical structures, compare analyte phase from microscopic feature and composition, it is accurate brilliant unique characteristic that electron diffraction shows fivefold symmetry.Therefore, illustrate that composition is close to Mg in the alloy 30zn 60y 10(at.%) Icosahedral phases is belonged to mutually.
In embodiment 1,2,3 and comparative example 1, the volume fraction of Icosahedral phases is calculated the displaing micro tissue topography's map analysis as Fig. 4 by Lmage-ProPlus6.0 and obtains, and the displaing micro tissue topography figure of often kind of alloy is to 10 figure should being had by Lmage-ProPlus6.0 analytical calculation and averaging.
Can be drawn by above analysis, in embodiment 1,2,3 and comparative example 1, magnesium alloy all only has α-Mg phase and I-phase (Mg 3zn 6y) two kinds of things are formed mutually, and in alloy composition close to Mg 30zn 60y 10(at.%) belong to Icosahedral phases mutually, namely I-phase is Icosahedral phases.The Mg-Zn-Y magnesium alloy that the present invention is prepared by quick setting method, on original icosahedral quasicrystal phase structure basis, increases Icosahedral phases volume fraction, overcomes the problem that in the accurate crystal preparation method of prior art, quasicrystal integration number is on the low side; Solve the problems such as the accurate brilliant content of magnesium alloy is lower, tissue distribution is uneven, its erosion resistance is significantly improved.
2, erosion resistance analysis:
In the Tafel collection of illustrative plates that embodiment 1,2,3 and comparative example 1 are corroded, see Fig. 5, dynamic potential polarization curve obtains corresponding erosion resistance parameter by straight-line extrapolation method, and corrosion potential, corrosion current density, pitting potential, in table 2.The NaCl solution of corrosive medium to be concentration be 3.5% (wt.%), sweep voltage is from-2.0V to 1.0V, and sweep velocity is 0.01V/S, and sensitivity is 10mA/V, 10 minutes rest times.Corrosion potential is larger, and corrosion current density is less, and its corrosion resistance is stronger, and the larger reaction passive film of pitting potential protects alloy and not breakdown ability is stronger.By table 2 data presentation, corrosion potential is descending to be followed successively by: embodiment 3, embodiment 4, embodiment 2, embodiment 1, comparative example 2, comparative example 1; Corrosion current density is ascending to be followed successively by: embodiment 3, embodiment 4, embodiment 2, embodiment 1, comparative example 2, comparative example 1; Pitting potential is descending to be followed successively by: embodiment 3, embodiment 4, embodiment 2, embodiment 1, comparative example 2, comparative example 1.Comprehensive erosion resistance parameter draws, in the present invention, the erosion resistance of the magnesium alloy of embodiment 1,2,3 is all better than comparative example 1, and the erosion resistance of embodiment 3 significantly improves.
In Fig. 6, a, b, c, d figure is followed successively by Mg-Zn-Y magnesium alloy prepared by embodiment 1,2,3 and routine casting prepared by comparative example 1 with the SEM figure after the corrosion of component accurate grained magnesium alloy, and each little figure in the figure upper left corner is corresponding partial enlarged drawing.Comparing embodiment 1,2,3, comparative example 1 magnesium alloy is corroded degree more seriously, and surface is corroded completely and corrodes darker.The area that is corroded in embodiment 1,2,3 Corrosion Behaviors of Magnesium Alloys pattern reduces successively and depth of corrosion weakens, and embodiment 3 shows as good erosion resistance.
Synthesizing map 5, Fig. 6 analysis further demonstrate that, in the present invention, the erosion resistance of Mg-Zn-Y magnesium alloy prepared by embodiment 1,2,3 is all better than comparative example alloy, and especially the erosion resistance of embodiment 3 is significantly improved.
3, Vickers' hardness analysis
By comparing the embodiment of the present invention and comparative example Vickers' hardness, in table 3, can find out that Vickers' hardness is descending and being followed successively by embodiment 3, embodiment 4, embodiment 2, embodiment 1, comparative example 2, comparative example 1; Because icosahedral quasicrystal (I phase) has significant corrosion resistance, high rigidity, low-friction coefficient, low interfacial energy, Vickers' hardness is improved.On the other hand, dendrite and crystal grain in rapid solidification refinement alloy, expand Zn, Y solid solubility in Mg, play solution strengthening effect, these all contribute to the raising comprising the mechanical properties such as hardness.

Claims (8)

1. a Mg-Zn-Y magnesium alloy, is characterized in that, is made up of: 55.50 ~ 56.00%Zn, 11.50 ~ 13.00%Y the component of following mass percent, and surplus is magnesium and micro impurity element; Described Mg-Zn-Y magnesium alloy, containing Icosahedral phases in alloy structure, quasicrystal integration number is 26.8 ~ 51.3%.
2. the preparation method of a Mg-Zn-Y magnesium alloy according to claim 1, it is characterized in that, preparation method comprises: first by after Mg-Y master alloy, pure magnesium ingot and pure zinc ingot melting, make the female ingot of Mg-Zn-Y cast alloy, after female for Mg-Zn-Y cast alloy ingot fusing, adopt rapid solidification injection method, obtained Mg-Zn-Y magnesium alloy; Described rapid solidification injection method, adopt high vacuum single roller to revolve the system of quenching, the copper roller rotating speed that described high vacuum single roller revolves the system of quenching is 400 ~ 800rpm, and injection argon pressure is 0.04 ~ 0.09MPa;
Described preparation method, step comprises:
1) the female ingot of Mg-Zn-Y cast alloy is prepared:
Take pure zinc ingot, Mg-Y master alloy and pure magnesium ingot raw material by weight ratio, at SF 6and CO 2under mixed gas protected, Mg-Y master alloy and pure magnesium ingot are put into the container being preheating to 200 ~ 300 DEG C, then 710 ~ 740 DEG C are warming up to, when Mg-Y master alloy and pure magnesium ingot melt completely, add pure zinc ingot, stir, the waste residue of removing molten surface, continue stirring 2 ~ 3 minutes, leave standstill 15 ~ 25 minutes; At SF 6and CO 2under mixed gas protected, room temperature leaves standstill 3 ~ 5 minutes, castable, the female ingot of obtained Mg-Zn-Y cast alloy;
2) high vacuum single roller revolves system rapid solidification of quenching and sprays preparation Mg-Zn-Y magnesium alloy:
By broken for female for Mg-Zn-Y cast alloy obtained for step 1) ingot, cleaning, put into the silica tube that high vacuum single roller revolves the system of quenching, be warming up to the female ingot of alloy under vacuum to melt completely, obtain liquation, under argon pressure is 0.04 ~ 0.09MPa condition, be the copper roller surface of 400 ~ 800rpm from silica tube lower end nozzle ejection to rotating speed by liquation, obtained Mg-Zn-Y magnesium alloy.
3. preparation method according to claim 2, is characterized in that: described Mg-Y master alloy, and it forms content by mass percentage and is: 29.50 ~ 30.50%Y and 69.50 ~ 70.50%Mg.
4. preparation method according to claim 2, is characterized in that: the SF described in step 1) 6and CO 2mixed gas, SF 6: CO 2volume ratio is 1:150.
5. preparation method according to claim 2, is characterized in that: described copper roller rotating speed is 600 ~ 800rpm.
6. preparation method according to claim 5, is characterized in that: described copper roller rotating speed is 800rpm.
7. preparation method according to claim 2, is characterized in that: it is 5 ~ 15mm that described high vacuum single roller revolves quench system silica tube nozzle and copper roller upper edge distance.
8. preparation method according to claim 2, is characterized in that: described high vacuum single roller revolves the system of quenching, and vacuum tightness is 3.0 × 10 -3pa, induction heating power 3kW, silica tube nozzle diameter is 0.6mm, and copper roller diameter is 240mm.
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