CN107217218B - Calcium and magnesium copper amorphous alloy with hot pressing stability and preparation method thereof - Google Patents
Calcium and magnesium copper amorphous alloy with hot pressing stability and preparation method thereof Download PDFInfo
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- CN107217218B CN107217218B CN201710463617.0A CN201710463617A CN107217218B CN 107217218 B CN107217218 B CN 107217218B CN 201710463617 A CN201710463617 A CN 201710463617A CN 107217218 B CN107217218 B CN 107217218B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/001—Amorphous alloys with Cu as the major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D18/00—Pressure casting; Vacuum casting
- B22D18/06—Vacuum casting, i.e. making use of vacuum to fill the mould
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/11—Making amorphous alloys
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Abstract
The invention discloses a kind of calcium and magnesium copper amorphous alloy and preparation method thereof, the amorphous alloy component is Ca(75‑x)Mg25Cux, in formula, x is atomic percent, meets x=32 ~ 38%；The steps include: will be sufficiently mixed uniform raw material calcium, magnesium, copper powders in proportion pours into high-purity carbon crucible, it is first kept the temperature for 24 hours in 475 ~ 495 DEG C, 3 ~ 4 Gpa, is then slowly warming up to 595 ~ 605 DEG C, 0.5 ~ 1 Gpa heat preservation 4h, last unloading pressure, 705 ~ 715 DEG C are warming up to, 30 min are kept the temperature；After the completion of reaction-sintered, cavity is vacuumized repeatedly, is argon gas 3 ~ 5 times logical, finally under low argon atmosphere, the melt being placed in copper mold is quickly cooled down to obtain the amorphous alloy.In the invention preparation process; can be blocking by reaction-sintered under low temperature and inert gas shielding between three kinds of calcium, magnesium and copper elements, therefore obtained master alloy ingredient is accurate, simultaneously; the amorphous alloy has good biocompatibility, and specific strength with higher and specific modulus.
Description
Technical field
The invention belongs to amorphous alloy fields, are related to one kind near glass transformation temperature, certain pressure modified strip
With the amorphous alloy and preparation method thereof of structural stability under part.
Background technique
More than cold liquid temperature section, common glassy metal is easy to happen knot due to its limited hot pressing stability
Crystalline substance, so that process be made to stop.Traditional has Superstrength glass Forming ability glassy metal (palladium base), is beaten suitable for hot pressing
The potential material of print, but type is limited, manufacturing cost is higher.Therefore it verifies traditional bulk metallic glass Superstrength glass and forms energy
The secret of power, developing amorphous alloy material that is a kind of low in cost and being applicable in hot pressing printing is current area key urgently to be solved
Key problem.Calcium and magnesium base metal glass has excellent glass forming ability, but since calcium and magnesium elements activity are higher, directly
By the electric arc melting method that then copper mold is cast, the material composition of formation is more difficult to control, this is because the raw material of low melting point
It is volatile, cause the ingredient printed it is suitable for hot pressing and process conditions still to belong to blank.
Summary of the invention
The purpose of the present invention is being directed to above-mentioned analysis, providing one kind has structure under the conditions of certain pressure deformation and temperature
The preparation method of the calcium and magnesium copper metal glass of stability.Our low temperature reaction sintering and a copper mold cast-forming method is compared with electric arc
Melting is compared with secondary copper mold casting method, and preparation process is simple, casting temperature is controllable, and obtained amorphous alloy quality is higher, knot
Structure and performance are controllable.
Realize the technical solution of the object of the invention are as follows:
A kind of calcium and magnesium copper amorphous alloy, ingredient Ca(75-x)Mg25Cux, in formula, x is atomic percent, meets x=32 ~ 38.
3 ~ 10 mm of diameter range of the calcium and magnesium copper amorphous alloy has the pressure 60 between 126-140 DEG C
MPa or less keeps the temperature 2 hours characteristics for maintaining amorphous state not crystallize.
The preparation method of above-mentioned calcium and magnesium copper amorphous alloy, the specific steps are as follows:
Low temperature and pressure reaction-sintered: the first step will be sufficiently mixed uniform raw material calcium, magnesium, copper powders in proportion and pour into
In high-purity carbon crucible, adjustment furnace temperature to predetermined temperature, in certain pressure, high-purity argon gas is protected and is sintered under atmosphere by step: first
475 ~ 495 DEG C, 3 ~ 4Gpa protect for 24 hours, be then slowly warming up to 595 ~ 605 DEG C, 0.5 ~ 1 Gpa heat preservation 4h, last unloading pressure,
705 ~ 715 DEG C are warming up to, 30min is kept the temperature；
Water cooled copper mould casting: second step after the completion of reaction-sintered, cavity is vacuumized repeatedly, is argon gas 3 ~ 5 times logical, most
Afterwards under low argon atmosphere, the melt in carbon crucible is drawn into be quickly cooled down in copper mold by opening copper mold bottom vacuum pump obtains calcium
Magnesium copper metal glass.
Preferably, in the first step, calcium, magnesium, copper powders partial size be 300 mesh.
Preferably, in second step, low argon gas is carried out in less than 0.5 normal atmosphere pressure of air pressure.
Compared with prior art, the invention has the advantages that
(1) can be blocking by reaction-sintered under low temperature and inert gas shielding between three kinds of calcium, magnesium and copper elements, because
The master alloy ingredient that this is obtained is accurate, can also obtain the controllable bulk of ingredient using copper mold casting based on obtained master alloy
Calcium and magnesium copper metal glass.
(2) calcium and magnesium copper metal may be implemented from the mechanism that technique, practical hot pressure reaction sintering and copper mold casting combine
The one-pass molding of glass, method is practical, meanwhile, calcium and magnesium base noncrystal alloy have good biocompatibility, and have compared with
High specific strength and specific modulus has huge application prospect in terms of bio-medical material, therefore develops practical preparation work
Skill has a very important significance.
Detailed description of the invention
Fig. 1 is calcium and magnesium copper amorphous alloy preparation flow schematic diagram of the present invention.
Fig. 2 is the DSC curve figure that the calcium and magnesium copper amorphous alloy differential scanning calorimetry that embodiment 1 obtains measures.
Fig. 3 is the x-ray diffraction pattern of the calcium and magnesium copper amorphous alloy that embodiment 1 obtains and hot pressing heat preservation front and back.
Fig. 4 is the transmission electron microscopy that 1 hot pressing of embodiment keeps the temperature the calcium and magnesium copper amorphous alloy amorphous alloy obtained after 2h
Microscopy mapping.
Specific embodiment
Below in conjunction with attached drawing and example, the invention will be described in further detail.
Embodiment 1
The example prepares calcium and magnesium copper metal glass using low temperature reaction sintering and a copper mold cast-forming method, and is penetrated with X
Line diffractometer, transmission electron microscope have carried out structural characterization:
1) alloying component Ca:Mg:Cu weighs raw material powder by atomic percent 8:5:7, is sufficiently mixed uniformly spare；
2) alloy powder mixed is uniformly poured into high purity graphite crucible (having a size of 20mm diameter, height 40mm),
And it is put into pressure head, add 10Mpa to preload 10min；
3) after the completion of preloading, system vacuum is evacuated to 10-5Pa, then passing to high-purity argon gas (99.999%) keeps system true
Until sky to half of atmospheric pressure, logical argon gas is vacuumized repeatedly 3-5 times, close valve；
4) after pressure being slowly raised 3.8Gpa, (1 DEG C/min) sintered crucible temperature is slowly increased to 485 DEG C, is kept the temperature
24h；
5) then slowly heating (about 1 DEG C/min) to 600 DEG C, 0.5-1Gpa keep the temperature 4h；
6) then slow unloading pressure is separated to pressure head with sample, is slowly heated up (1 DEG C/min) to 710 DEG C, is kept the temperature
20min；
7) after alloy melt is sufficiently kept the temperature, the vacuum valve of system copper mold bottom is opened, manufacture negative pressure sucks melt
In water cooled copper mould, copper mold interior groove size adjustable (3-10mm).Alloy melt forms glassy metal during rapid cooling.
8) thermodynamics information is measured with differential scanning calorimetry, as shown in Fig. 2, being Ca for alloying component40Mg25Cu35Gold
Belong to glass, under 20 DEG C/min heating rate, glass transformation temperature is about 126 DEG C, and crystallization temperature is 150 DEG C.Use X-ray
Diffraction characterizes calcium and magnesium copper metal glass structure, as a result as Fig. 3 blue curve is shown as typical wide diffusing scattering peak, it was demonstrated that its structure
For completely amorphous structure.
9) by the glassy metal bar of acquisition (such as 3mm diameter bar), being cut into height is 6mm cylindrical sample, at 135 DEG C
Heat preservation, 10-3Under Pa vacuum, 50Mpa pressure, 10-5Compression experiment is carried out under/s strain rate, sample is penetrated using X- after 2h test
Line diffraction and high resolution transmission electron microscopy detection.
10) for the high resolution electron microscopy of Fig. 4 the result shows that alloy interior atoms are labyrinth-like pattern, structure is completely amorphous
State.Test result shows that prepared sample has excellent hot pressing structural stability can.
Embodiment 2
The example prepares calcium and magnesium copper metal glass using low temperature reaction sintering and a copper mold cast-forming method, and is penetrated with X
Line diffractometer, transmission electron microscope have carried out structural characterization:
1) alloying component Ca:Mg:Cu weighs raw material powder by atomic percent 42:25:33, is sufficiently mixed uniformly standby
With；
2) alloy powder mixed is uniformly poured into high purity graphite crucible (having a size of 20mm diameter, height 40mm),
And it is put into pressure head, add 10Mpa to preload 10min；
3) after the completion of preloading, system vacuum is evacuated to 10-5Pa, then passing to high-purity argon gas (99.999%) keeps system true
Until sky to half of atmospheric pressure, logical argon gas is vacuumized repeatedly 3-5 times, close valve；
4) after pressure being slowly raised 3.5Gpa, (1 DEG C/min) sintered crucible temperature is slowly increased to 480 DEG C, is kept the temperature
20h；
5) then slowly heating (1 DEG C/min) to 600 DEG C, 0.5-1Gpa keep the temperature 4h；
6) then slow unloading pressure is separated to pressure head with sample, is slowly heated up (1 DEG C/min) to 710 DEG C, is kept the temperature
20min；
7) after alloy melt is sufficiently kept the temperature, the vacuum valve of system copper mold bottom is opened, manufacture negative pressure sucks melt
In water cooled copper mould, copper mold interior groove size adjustable (3-10mm).Alloy melt forms glassy metal during rapid cooling.
8) thermodynamics information is measured with differential scanning calorimetry, characterizes calcium and magnesium copper metal glass structure with X-ray diffraction
9) by the glassy metal bar of acquisition (such as 3mm diameter bar), being cut into height is 6mm cylindrical sample, at 135 DEG C
Heat preservation, 10-3Under Pa vacuum, 50Mpa pressure, 10-5Compression experiment is carried out under/s strain rate, sample is penetrated using X- after 2h test
Line diffraction and high resolution transmission electron microscopy detection, the result measured are consistent with the conclusion in embodiment 1.
Embodiment 3
The example prepares calcium and magnesium copper metal glass using low temperature reaction sintering and a copper mold cast-forming method, and is penetrated with X
Line diffractometer, transmission electron microscope have carried out structural characterization:
1) alloying component Ca:Mg:Cu weighs raw material powder by atomic percent 38:25:37, is sufficiently mixed uniformly standby
With；
2) alloy powder mixed is uniformly poured into high purity graphite crucible (having a size of 20mm diameter, height 40mm),
And it is put into pressure head, add 10Mpa to preload 10min；
3) after the completion of preloading, system vacuum is evacuated to 10-5Pa, then passing to high-purity argon gas (99.999%) keeps system true
Until sky to half of atmospheric pressure, logical argon gas is vacuumized repeatedly 3-5 times, close valve；
4) after pressure being slowly raised 4Gpa, (1 DEG C/min) sintered crucible temperature is slowly increased to 490 DEG C, is kept the temperature
28h；
5) then slowly heating (1 DEG C/min) to 600 DEG C, 0.5-1Gpa keep the temperature 4h；
6) then slow unloading pressure is separated to pressure head with sample, is slowly heated up (1 DEG C/min) to 710 DEG C, is kept the temperature
20min；
7) after alloy melt is sufficiently kept the temperature, the vacuum valve of system copper mold bottom is opened, manufacture negative pressure sucks melt
In water cooled copper mould, copper mold interior groove size adjustable (3-10mm).Alloy melt forms glassy metal during rapid cooling.
8) thermodynamics information is measured with differential scanning calorimetry, characterizes calcium and magnesium copper metal glass structure with X-ray diffraction
9) by the glassy metal bar of acquisition (such as 3mm diameter bar), being cut into height is 6mm cylindrical sample, 135
DEG C heat preservation, 10-3Under Pa vacuum, 50Mpa pressure, 10-5Compression experiment is carried out under/s strain rate, sample utilizes X- after 2h test
X ray diffraction and high resolution transmission electron microscopy detection, the result measured are consistent with the conclusion in embodiment 1.
Claims (4)
1. calcium and magnesium copper amorphous alloy, which is characterized in that its ingredient Ca(75-x)Mg25Cux, in formula, x is atomic percent, meet x=
32 ~ 38, the diameter range of the amorphous alloy is 3 ~ 10 mm, has the heat preservation 2 below 126-140 DEG C, 60 MPa pressure small
When maintain the characteristic that does not crystallize of amorphous state, the amorphous alloy preparation step is as follows:
The first step will be sufficiently mixed uniform raw material calcium, magnesium, copper powders in proportion and pour into high-purity carbon crucible, first 475 ~
495 DEG C, 3 ~ 4 GPa heat preservation for 24 hours, be then slowly warming up to 595 ~ 605 DEG C, 0.5 ~ 1 GPa heat preservation 4h, last unloading pressure, rise
Temperature keeps the temperature 30 min to 705 ~ 715 DEG C；
Cavity is vacuumized repeatedly after the completion of reaction-sintered, is argon gas 3 ~ 5 times logical by second step, finally under low argon atmosphere,
Melt in carbon crucible is drawn into be quickly cooled down in copper mold by opening copper mold bottom vacuum pump obtains the amorphous alloy.
2. the preparation method of amorphous alloy as described in claim 1, which is characterized in that specific step is as follows:
The first step will be sufficiently mixed uniform raw material calcium, magnesium, copper powders in proportion and pour into high-purity carbon crucible, first 475 ~
495 DEG C, 3 ~ 4 GPa heat preservation for 24 hours, be then slowly warming up to 595 ~ 605 DEG C, 0.5 ~ 1 GPa heat preservation 4h, last unloading pressure, rise
Temperature keeps the temperature 30 min to 705 ~ 715 DEG C；
Cavity is vacuumized repeatedly after the completion of reaction-sintered, is argon gas 3 ~ 5 times logical by second step, finally under low argon atmosphere,
Melt in carbon crucible is drawn into be quickly cooled down in copper mold by opening copper mold bottom vacuum pump obtains the amorphous alloy.
3. method according to claim 2, which is characterized in that in the first step, calcium, magnesium, copper powders partial size be 300 mesh.
4. method according to claim 2, which is characterized in that in second step, low argon gas refers in less than 0.5 standard of air pressure
Atmospheric pressure.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095764A (en) * | 1993-05-25 | 1994-11-30 | 中国科学院金属研究所 | A kind of preparation method of bulk amorphous material |
| CN102115854A (en) * | 2009-12-31 | 2011-07-06 | 比亚迪股份有限公司 | Calcium-based amorphous alloy and preparation method thereof |
| CN102321857A (en) * | 2011-06-09 | 2012-01-18 | 济南大学 | Zirconium-based amorphous composite material and preparation process thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160021579A (en) * | 2014-08-18 | 2016-02-26 | 서울대학교산학협력단 | flexible metallic glass substrate with high resilience, manufacturing methode of the same and electronic device by using the same |
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2017
- 2017-06-19 CN CN201710463617.0A patent/CN107217218B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095764A (en) * | 1993-05-25 | 1994-11-30 | 中国科学院金属研究所 | A kind of preparation method of bulk amorphous material |
| CN102115854A (en) * | 2009-12-31 | 2011-07-06 | 比亚迪股份有限公司 | Calcium-based amorphous alloy and preparation method thereof |
| CN102321857A (en) * | 2011-06-09 | 2012-01-18 | 济南大学 | Zirconium-based amorphous composite material and preparation process thereof |
Non-Patent Citations (2)
| Title |
|---|
| Composition range and glass forming ability of ternary Ca–Mg–Cu bulk metallic glasses;O.N. Senkov et al.;《Journal of Alloys and Compounds》;20061231;第424卷;第394页右栏第2段,第2部分 Experiments，表1 * |
| Effect of free electron concentration on glass-forming ability of Ca–Mg–Cu system;W. Jiao et al.;《Journal of Non-Crystalline Solids》;20121231;第358卷;第2部分 Experiments，表1 * |
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