CN101880840B - Preparation method of Mg-Li matrix Mg-Li-Cu-Ni-Y series bulk amorphous alloy - Google Patents
Preparation method of Mg-Li matrix Mg-Li-Cu-Ni-Y series bulk amorphous alloy Download PDFInfo
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Abstract
The invention provides a preparation method of Mg-Li matrix Mg-Li-Cu-Ni-Y series bulk amorphous alloy. The method comprises the following steps: mixing high purity magnesium block, lithium block, nickel block, high purity copper ingot and high purity yttrium block according to a nominal formulation-Mg65LixCu20-xNi5Y10 (0<x<5at.%), wherein firstly smelting by using the vacuum induction melting method to obtain Cu-Ni-Y ternary alloy, secondly polishing the Cu-Ni-Y alloy, grinding the alloy to mix with magnesium block and lithium block and then using the same smelting method to prepare Mg-Li-Cu-Ni-Y quinary master alloy; and (2) after grinding the Mg-Li-Cu-Ni-Y quinary master alloy prepared by smelting, and performing vacuum rapid quenching on an ultrafast quenching device to prepare the high-strength Mg-Li matrix Mg-Li-Cu-Ni-Y series bulk amorphous alloy. The preparation method of the invention avoids large ignition loss of Mg and Li and impurity elements and increases the purity of the amorphous alloy, and the obtained Mg-Li matrix amorphous alloy has high strength, low density and good corrosion resistance.
Description
Technical field
That invention relates to is a kind of preparation method of high strength amorphous alloy material.
Background technology
For decades recently, people have carried out the research deep than system to magnesium base amorphous alloy.The intensity of discovery magnesium base amorphous alloy can reach 2 to 3 times of general crystal alloy, and specific tenacity significantly improves, and insoluble solidity to corrosion problem also is improved originally, is considered to a kind of structured material that has the novel light high specific strength of potentiality.Magnesium lithium alloy has the multiple excellent properties identical with Magnuminium as a kind of ultralight alloy and important use is worth, but relates to less to the research of its amorphous alloy.Therefore, the research to magnesium lithium base noncrystal alloy will become one of important topic of material area research.Burn mistake seriously in composition design and improper magnesium or the lithium of causing of implementing measure in the tradition amorphous preparation process, very easily introduce impurity element simultaneously, make made amorphous alloy component bigger with original design deviation, purity is lower, and various aspects of performance is relatively poor.
Though number of patent application is 200810064803.8, name is called in the documents such as patent document of " a kind of Mg-Li-based Mg-Li-Al-Cu-Zn block amorphous alloy and preparation method thereof ", has proposed some preparation methods about magnesium lithium base large amorphous alloy.But, thereby seek the reasonable in design and simple and easy to do flash set technology of a kind of composition and reduce the burning mistake that temperature higher in the preparation process effectively reduces the magnesium lithium, improve non-crystaline amorphous metal purity, prepare the magnesium lithium base noncrystal alloy of large-size, mechanical property and excellent anti-corrosion performance, it is widely used as structural timber, becomes investigation of materials person's problem demanding prompt solution.
Summary of the invention
The object of the present invention is to provide a kind of purity that can guarantee non-crystaline amorphous metal, reduce the magnesium lithium and burn mistake, improve the preparation method of the Mg-Li matrix Mg-Li-Cu-Ni-Y series bulk amorphous alloy of amorphous formation ability.
The object of the present invention is achieved like this:
(1) preparation mother alloy: with purity is that 99.95% high-purity MAG block, purity are that 99.9% lithium piece, purity are that 99.5% nickel block, purity are that 99.8% high-purity copper ingot, purity are that 99.99% high-purity yttrium piece is by nominal composition Mg
65Li
xCu
20-xNi
5Y
10Wherein 0＜x＜5at.% batching is at first carried out the melting of Cu-Ni-Y ternary alloy with the method for vacuum induction melting; Subsequently,, pulverize back and purity and be 99.95% MAG block and purity and be 99.9% lithium piece and mix, prepare five yuan of mother alloys of Mg-Li-Cu-Ni-Y with identical melting method then Cu-Ni-Y alloy sanding and polishing;
(2) vacuum quick quenching of mother alloy: after five yuan of mother alloys of the Mg-Li-Cu-Ni-Y that melting is prepared are pulverized, on supper-fast liquid-quenching device, carry out vacuum quick quenching, make the series bulk amorphous alloy of high-strength magnesium lithium base Mg-Li-Cu-Ni-Y.
The method of described vacuum induction melting is: the alloy raw material for preparing is put into quartz container, be placed on the ruhmkorff coil center, avoid contacting with coil, close the fire door of medium frequency induction melting furnace, be evacuated to 10 then
-4Pa charges into 10
-2The argon gas of Pa, repeatedly after three times under argon shield molten alloy, with alloy melt back 3～5 times;
The method of the vacuum quick quenching of described mother alloy is: with the Mg-Li-Cu-Ni-Y mother alloy sanding and polishing that makes, remove the oxide skin on mother alloy surface, with ultrasonic oscillator it is cleaned, in the quartz container of packing into after the mother alloy pulverizing, be placed on the ruhmkorff coil center, avoid contacting with coil; Closing fire door, is P toward the quartz container upper end interior charged pressure of gas-holder
1=5 * 10
-2The high-purity argon gas of Pa charges into 5 * 10 behind the pumping high vacuum repeatedly with furnace chamber
-2The argon shield gas of Pa forms P
2Negative pressure, the above-mentioned mother alloy of remelting in the intermediate frequency vacuum induction melting furnace of argon gas atmosphere, with the molten state Mg-Li-Cu-Ni-Y mother alloy that obtains at pressure difference P=P
1+ P
2Effect under, spray into high speed in the die cavity of Quench copper mold, obtain the series bulk amorphous alloy of high-strength magnesium lithium base Mg-Li-Cu-Ni-Y.
The present invention adds and the alternate method by element, on the basis of the more intense M magnesium base block amorphous alloy of amorphous formation ability, adds Li and rare earth element, prepares magnesium lithium base noncrystal alloy by adopting the vacuum quick quenching technology.Because operation is to carry out under vacuum state, not only can obtain high cooling rate, obtain bulk amorphous alloys, and effectively avoided sneaking into of impurity element, guaranteed the purity of non-crystaline amorphous metal; Burn mistake for reducing the magnesium lithium, prepared the high-melting-point mischmetal in advance, rare earth element y has improved amorphous formation ability, and its oxidation-resistance and flame retardant properties have been avoided the on fire of magnesium lithium and reduced its loss on ignition simultaneously.For carry high spraying speed at first in the gas-holder of fast quartz test tube upper end charged pressure be P
1(5 * 10
-2Pa) high-purity argon gas charges into 5 * 10 behind the pumping high vacuum repeatedly with furnace chamber then
-2The argon shield gas of Pa forms P
2Negative pressure, at last at pressure difference P=P
1+ P
2Effect realize down the vacuum quick quenching of fusion mother alloy.The Mg-Li matrix Mg-Li-Cu-Ni-Y series bulk amorphous alloy of the present invention's preparation has possessed excellent mechanical property, wherein Mg
65Li
4Cu
16Ni
5Y
10Incompressible intensity reached 729MPa, not only be higher than the intensity of traditional crystalline state magnesium lithium alloy far away, and than the Mg of tool same diameter
65Cu
25Y
10The high 49MPa of non-crystaline amorphous metal sample, meanwhile the supercooling liquid phase region of this magnesium lithium non-crystaline amorphous metal reaches 50K, has shown stronger amorphous formation ability.
The advantage that the present invention has is:
Interpolation alternative method by element reduces the critical cooling rate of non-crystaline amorphous metal, improves its glass forming ability; Burn mistake for reducing the magnesium lithium, prepared the high-melting-point mischmetal in advance, rare earth element y has improved amorphous formation ability, and its oxidation-resistance and flame retardant properties have been avoided the on fire of magnesium lithium and reduced its loss on ignition simultaneously.Because vacuum quick quenching is to carry out under vacuum state, when obtaining high cooling rate, has effectively avoided sneaking into of impurity element, has guaranteed the purity of non-crystaline amorphous metal.Preparation is simple and cost is lower.Utilize the present invention can prepare the magnesium lithium base noncrystal alloy of large-size, have excellent mechanics and corrosion resistance, stronger amorphous formation ability.The structural timber that the present invention can be used as excellent property is widely used in fields such as Aeronautics and Astronautics, automobile, machinery, electronics, defense industry.
Description of drawings
Fig. 1 is the XRD diffracting spectrum of the prepared Mg-Li-Cu-Ni-Y block amorphous alloy of the present invention;
Fig. 2 is the DSC curve of the prepared Mg-Li-Cu-Ni-Y block amorphous alloy of the present invention;
Fig. 3 is the incompressible intensity curve of the prepared Mg-Li-Cu-Ni-Y block amorphous alloy of the present invention.
Embodiment
For example the present invention is done in more detail below and describes:
Embodiment 1
Select preparation x=2, be divided into Mg
65Li
2Cu
18Ni
5Y
10Block amorphous alloy, sample diameter is 2mm.
Step 1: the preparation of mother alloy: with purity is that 99.99% high-purity MAG block, purity are that 99.9% lithium piece, purity are that 99.5% nickel block, purity are that 99.8% high-purity copper ingot, purity are that 99.99% high-purity yttrium piece is by composition proportion Mg
65Li
2Cu
18Ni
5Y
10Take by weighing raw material; At first alloy raw material Cu, Ni, Y are put into quartz test tube, be placed on the ruhmkorff coil center, avoid contacting, close the fire door of medium frequency induction melting furnace, be evacuated to 10 then with coil
-4Pa charges into 10
-2The argon gas of Pa, repeatedly after three times under argon shield molten alloy, even for making alloying constituent, with alloy melt back 3～5 times, make the Cu-Ni-Y ternary alloy.Subsequently,, pulverize heel purity and be 99.95% MAG block and purity and be 99.9% lithium piece and mix, make five yuan of mother alloys of Mg-Li-Cu-Ni-Y with identical melting method then Cu-Ni-Y alloy sanding and polishing.
Step 2: the vacuum quick quenching of mother alloy: the Mg-Li-Cu-Ni-Y mother alloy sanding and polishing that step 1 is made, to remove the oxide skin on mother alloy surface, with ultrasonic oscillator it is cleaned, in the quartz test tube of packing into after the mother alloy pulverizing, be placed on the ruhmkorff coil center, avoid contacting with coil; Closing fire door, is P toward the quartz test tube upper end interior charged pressure of gas-holder
1(5 * 10
-2Pa) high-purity argon gas charges into 5 * 10 behind the pumping high vacuum repeatedly with furnace chamber
-2The argon shield gas of Pa forms P
2Negative pressure, the above-mentioned mother alloy of remelting in the intermediate frequency vacuum induction melting furnace of argon gas atmosphere, with the molten state Mg-Li-Cu-Ni-Y mother alloy that obtains at pressure difference P=P
1+ P
2Effect under, spray into high speed in the die cavity of Quench copper mold, obtain Mg
65Li
2Cu
18Ni
5Y
10The block amorphous alloy sample.
Step 3: adopt the weave construction of X-ray diffraction method sign gained sample, as Figure 1A; XRD diffractogram by this sample is as can be known general, and the typical non-crystal structure feature of the weave construction tool of gained sample illustrates that this alloy sample is a non-crystaline amorphous metal.
Step 4: adopt the amorphous formation ability of DSC curve sign gained sample, as Fig. 2 A; The DSC curve of analytic sample as can be known, the value of the glass transformation temperature Tg of gained sample, initial crystallization temperature Tx and supercooling liquid phase region Δ Tx (Δ Tx=Tx-Tg) is respectively 392.81K, 442.81K, 50K.Illustrate that the gained sample has stronger amorphous formation ability.
Step 5: utilize the incompressible intensity of Instron 4505 type electronic universal tester test samples to characterize its mechanical property, as Fig. 3 A.The incompressible intensity of gained sample is 729MPa, is higher than the intensity of traditional crystalline state magnesium lithium alloy far away, and than the Mg of tool same diameter
65Cu
25Y
10The high 49MPa of non-crystaline amorphous metal sample has shown the mechanical property of magnesium lithium block amorphous alloy excellence proposed by the invention.
Select preparation x=4, be divided into Mg
65Li
4Cu
16Ni
5Y
10Block amorphous alloy, sample diameter is 2mm.
Step 1: the preparation of mother alloy: with purity is that 99.99% high-purity MAG block, purity are that 99.9% lithium piece, purity are that 99.5% nickel block, purity are that 99.8% high-purity copper ingot, purity are that 99.99% high-purity yttrium piece is by composition proportion Mg
65Li
4Cu
16Ni
5Y
10Take by weighing raw material; At first alloy raw material Cu, Ni, Y are put into quartz test tube, be placed on the ruhmkorff coil center, avoid contacting, close the fire door of medium frequency induction melting furnace, be evacuated to 10 then with coil
-4Pa charges into 10
-2The argon gas of Pa, repeatedly after three times under argon shield molten alloy, even for making alloying constituent, with alloy melt back 3～5 times, make the Cu-Ni-Y ternary alloy.Subsequently,, pulverize heel purity and be 99.95% MAG block and purity and be 99.9% lithium piece and mix, make five yuan of mother alloys of Mg-Li-Cu-Ni-Y with identical melting method then Cu-Ni-Y alloy sanding and polishing.
Step 2: the vacuum quick quenching of mother alloy: the Mg-Li-Cu-Ni-Y mother alloy sanding and polishing that step 1 is made, to remove the oxide skin on mother alloy surface, with ultrasonic oscillator it is cleaned, in the quartz test tube of packing into after the mother alloy pulverizing, be placed on the ruhmkorff coil center, avoid contacting with coil; Closing fire door, is P toward the quartz test tube upper end interior charged pressure of gas-holder
1(5 * 10
-2Pa) high-purity argon gas charges into 5 * 10 behind the pumping high vacuum repeatedly with furnace chamber
-2The argon shield gas of Pa forms P
2Negative pressure, the above-mentioned mother alloy of remelting in the intermediate frequency vacuum induction melting furnace of argon gas atmosphere, with the molten state Mg-Li-Cu-Ni-Y mother alloy that obtains at pressure difference P=P
1+ P
2Effect under, spray into high speed in the die cavity of Quench copper mold, obtain Mg
65Li
4Cu
16Ni
5Y
10The block amorphous alloy sample.
Step 3: adopt the weave construction of X-ray diffraction method sign gained sample, as Figure 1B;
XRD diffractogram by this sample is as can be known general, and the typical non-crystal structure feature of the weave construction tool of gained sample illustrates that this alloy sample is a non-crystaline amorphous metal.
Step 4: adopt the amorphous formation ability of DSC curve sign gained sample, as Fig. 2 B
The DSC curve of analytic sample as can be known, the value of the glass transformation temperature Tg of gained sample, initial crystallization temperature Tx and supercooling liquid phase region Δ Tx (Δ Tx=Tx-Tg) is respectively 389.44K, 438.44K, 49K.Illustrate that it has stronger amorphous formation ability.
Step 5: utilize the incompressible intensity of Instron 4505 type electronic universal tester test samples to characterize its mechanical property, as Fig. 3 B.The incompressible intensity of gained sample is 616MPa, far above the intensity of traditional crystalline state magnesium lithium alloy.
Claims (3)
1. the preparation method of a Mg-Li matrix Mg-Li-Cu-Ni-Y series bulk amorphous alloy is characterized in that:
(1) preparation mother alloy: with purity is that 99.95% high-purity MAG block, purity are that 99.9% lithium piece, purity are that 99.5% nickel block, purity are that 99.8% high-purity copper ingot, purity are that 99.99% high-purity yttrium piece is by nominal composition Mg
65Li
xCu
20-xNi
5Y
10Wherein 0＜x＜5at.% batching is at first carried out the melting of Cu-Ni-Y ternary alloy with the method for vacuum induction melting; Subsequently,, pulverize back and purity and be 99.95% MAG block and purity and be 99.9% lithium piece and mix, prepare five yuan of mother alloys of Mg-Li-Cu-Ni-Y with identical melting method then Cu-Ni-Y alloy sanding and polishing;
(2) vacuum quick quenching of mother alloy: after five yuan of mother alloys of the Mg-Li-Cu-Ni-Y that melting is prepared are pulverized, on supper-fast liquid-quenching device, carry out vacuum quick quenching, make the series bulk amorphous alloy of high-strength magnesium lithium base Mg-Li-Cu-Ni-Y.
2. the preparation method of Mg-Li matrix Mg-Li-Cu-Ni-Y series bulk amorphous alloy according to claim 1, the method that it is characterized in that described vacuum induction melting is: the alloy raw material for preparing is put into quartz container, be placed on the ruhmkorff coil center, avoid contacting with coil, close the fire door of medium frequency induction melting furnace, be evacuated to 10 then
-4Pa charges into 10
-2The argon gas of Pa, repeatedly after three times under argon shield molten alloy, with alloy melt back 3～5 times.
3. the preparation method of Mg-Li matrix Mg-Li-Cu-Ni-Y series bulk amorphous alloy according to claim 1 and 2, the method that it is characterized in that the vacuum quick quenching of described mother alloy is: with the Mg-Li-Cu-Ni-Y mother alloy sanding and polishing that makes, remove the oxide skin on mother alloy surface, with ultrasonic oscillator it is cleaned, in the quartz container of packing into after the mother alloy pulverizing, be placed on the ruhmkorff coil center, avoid contacting with coil; Closing fire door, is P toward the quartz container upper end interior charged pressure of gas-holder
1=5 * 10
-2The high-purity argon gas of Pa charges into 5 * 10 behind the pumping high vacuum repeatedly with furnace chamber
-2The argon shield gas of Pa forms P
2Negative pressure, the above-mentioned mother alloy of remelting in the intermediate frequency vacuum induction melting furnace of argon gas atmosphere, with the molten state Mg-Li-Cu-Ni-Y mother alloy that obtains at pressure difference P=P
1+ P
2Effect under, spray into high speed in the die cavity of Quench copper mold, obtain the series bulk amorphous alloy of high-strength magnesium lithium base Mg-Li-Cu-Ni-Y.
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| CN103952647A (en) * | 2011-08-09 | 2014-07-30 | 安泰科技股份有限公司 | Magnesium base hydrogen storage nanometer.amorphous alloy preparation method |
| CN103173699A (en) * | 2013-03-22 | 2013-06-26 | 哈尔滨工程大学 | Zn-containing Mg-Cu-Gd bulk amorphous alloy and preparation method thereof |
| CN103184394A (en) * | 2013-03-26 | 2013-07-03 | 哈尔滨工程大学 | Mg-Cu-Ti-Y block amorphous alloy and preparation method thereof |
| CN103252496B (en) * | 2013-05-03 | 2015-06-17 | 中国人民解放军装甲兵工程学院 | High-entropy alloy powder containing amorphous nanocrystalline and fabrication method thereof |
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| CN101016606A (en) * | 2007-02-08 | 2007-08-15 | 上海交通大学 | Magnesium-base massive non-crystalline material and preparing method thereof |
| CN100554483C (en) * | 2008-06-25 | 2009-10-28 | 哈尔滨工程大学 | A kind of Mg-Li-based Mg-Li-Al-Cu-Zn block amorphous alloy and preparation method thereof |
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