CN106319269A - Cubic phase Ca3Si alloy and preparation method thereof - Google Patents
Cubic phase Ca3Si alloy and preparation method thereof Download PDFInfo
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- CN106319269A CN106319269A CN201610935975.2A CN201610935975A CN106319269A CN 106319269 A CN106319269 A CN 106319269A CN 201610935975 A CN201610935975 A CN 201610935975A CN 106319269 A CN106319269 A CN 106319269A
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- 239000000956 alloy Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910045601 alloy Inorganic materials 0.000 title abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000010935 stainless steel Substances 0.000 claims abstract description 22
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 8
- 239000011812 mixed powder Substances 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- 229910000676 Si alloy Inorganic materials 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 238000005054 agglomeration Methods 0.000 claims description 5
- 230000002776 aggregation Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 36
- 125000004429 atom Chemical group 0.000 description 8
- 229910014458 Ca-Si Inorganic materials 0.000 description 5
- 229910004709 CaSi Inorganic materials 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910004706 CaSi2 Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910014526 Ca2Si Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000005619 thermoelectricity Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 238000009646 cryomilling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C24/00—Alloys based on an alkali or an alkaline earth metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Powder Metallurgy (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a cubic phase Ca3Si alloy and a preparation method thereof. The preparation method comprises the following steps of 1, uniformly mixing Ca powder and Si powder in proportion under Ar protective atmosphere, so that a mixture is obtained; 2, putting the mixture into a ball milling tank under the Ar protective atmosphere, and sealing the ball milling tank well to prevent oxygen from entering therein; 3, putting the ball milling tank prepared in step 2 into a ball mill, and conducting ball milling at certain rotating speed to make the powder be subjected to a reaction completely, so that uniform mixed powder is obtained; and 4, taking the uniform mixed powder obtained in step 3 out, putting the uniform mixed powder into a stainless steel die of the required specification, and conducting vacuum sintering and preforming in a vacuum plasma sintering manner, so that a cubic phase Ca3Si sheetlike or lumped alloy material is obtained. The preparation method of the cubic phase Ca3Si alloy has the beneficial effects of being simple in process, easy to operate, low in cost and the like; and the obtained cubic phase Ca3Si sheetlike or lumped alloy is high in product purity and compact in combination and has good industrialized prospect.
Description
Technical field
The present invention relates to Ca-Si alloy material system field, be specifically related to a kind of Emission in Cubic Ca3Si alloy and preparation side thereof
Method.
Background technology
The object being always widely studied from Ca-Si bianry alloy in 1863, the most stable Ca-
Si bianry alloy has: Ca2Si, Ca5Si3, CaSi, Ca3Si4, Ca14Si19, and CaSi2.But, applying external pressure is
A kind of a kind of effective ways that phase in version is stable phase making meta or instability.Test and shown, 10 ~
CaSi under the pressure of 15GPa3And CaSi6Alloy the most successfully synthesizes.Due to Ca and Si element be present in a large number in nature with
And avirulence, add the special electronic structure of Ca-Si bianry alloy, so Ca-Si bianry alloy is widely used in each
Field.Such as: Ca2Si and Ca3Si4Having the quasiconductor of direct band gap and indirect band gap respectively, its band gap magnitude is respectively as follows: 0.56
EV and 0.34 eV, semi-conducting material uses in thermoelectricity field and field of optoelectronic devices and has huge prospect.But,
CaSi has chromaking boron structure, and chromaking boron structure has hydrogen storage ability well, proves that CaSi has hydrogen storage well after deliberation
With release hydrogen function.CaSi2Also it is a kind of superconductor.
Owing to Ca atom has the highest vapour pressure, therefore Ca atom is easy to from silicon substrate evaporation thus is unfavorable for
The phase counterdiffusion of Ca and Si, forms the silicide of Ca.And the existence of the multiple phase of Ca-Si bianry alloy, Ca atomic deposition serves as a contrast at Si
Ca is grown at the end3During Si, Ca can be concurrently formed2Si, Ca5Si3, CaSi, CaSi2Deng the silicide of calcium, therefore in silicon face extension
Growth Ca3Si is extremely difficult.
Summary of the invention
Present invention aims to prior art not enough, it is provided that a kind of Emission in Cubic Ca3Si alloy and preparation method thereof.
Preparation manipulation technique is simple, product component is easy to control for this, obtained Emission in Cubic Ca3Si alloy material is expected to application can be extensive
It is applied to every field.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of Ca3Si alloy, the component molar ratio of Ca and Si is 3:1, and space group is, lattice paprmeter is 4.8336；
Si atom occupies four summits, and Ca atom is in cubical 6 center of areas；Its preparation method comprises the following steps:
(1) Ca powder and Si powder are pressed mol ratio mix homogeneously under Ar protective atmosphere of 3.0 ~ 3.5:1, obtains mixture；
(2) step (1) gained mixture is transferred in ball grinder, by ball grinder good seal in Ar gas shielded atmosphere, it is to avoid oxygen
Gas enters；
(3) by ready ball grinder in step (2), put in ball mill with the rotating speed of 1000 ~ 2000 rpm carry out ball milling 30 ~
80 h, make powder fully react, and obtain uniform mixed powder；
(4) the uniform mixed powder obtained in step (3) is taken out, load in the stainless steel mould of required specification, use true
The mode of empty plasma agglomeration, is warming up to 100 ~ 500 DEG C under the pressure of 50 ~ 600 MPa, keeps 10 ~ 120 min to carry out very
Empty sintering tabletting, obtains Ca3Si lamellar or bulk alloy material.
In step (2), ball material mass ratio is: 5 ~ 20:1.
In step (2), the particle diameter of mill ball is 0.2 ~ 1.5 cm, uses acetone, ethanol to carry out ultrasound wave successively clear before using
Washing, ultrasonic waves for cleaning total time is 20 ~ 30 min.
In step (4), sintering heating rate is 10 ~ 30 DEG C/min.
The beneficial effects of the present invention is:
1) Cryomilling and plasma discharging vaccum sintering process are combined by the present invention, and technique is simple, processing ease, and
And reaction temperature is relatively low, it is difficult to oxidation reaction and the Ca that Ca atom occurs3The decomposition of Si phase, composition is controlled；
2) sintering process of the present invention supports the use into stainless steel mould, it is possible to bear higher sintering pressure at a lower temperature
Power, efficiently controls oxidation and the volatilization of Ca in general sintering process, and therefore product composition is purer, and density is higher, final thing phase
Structure is Emission in Cubic Ca3Si。
Accompanying drawing explanation
Fig. 1 is the XRD spectrum that invention is corresponding；
Fig. 2 is Ca3The structural representation of Si；
Fig. 3 is Ca3The conductivity versus temperature curve of Si；
Fig. 4 is Ca3Seebeck coefficient-the temperature curve of Si；
Fig. 5 is Ca3Power factor-the temperature curve of Si.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment 1
A kind of Emission in Cubic Ca3The preparation method of Si alloy material, comprises the following steps:
(1) Ca powder and Si powder are pressed the mol ratio of 3.0:1 mix homogeneously under Ar protective atmosphere, obtain mixture；
(2) step (1) gained mixture, mill ball and stainless steel jar mill and electronic balance are put into it is filled with an atmospheric pressure
In the glove box of Ar, wherein ball material mass ratio is 5:1 configuration, in glove box after accurate weighing, puts in ball grinder, by ball milling
Tank good seal, it is to avoid oxygen enters, then takes out ball grinder from glove box；
(3) by ready ball grinder in step (2), put in ball mill and carry out ball milling 30 h with the rotating speed of 2000 rpm, make
Powder fully reacts；
(4) being taken out by powder completely reacted in step (3), loading diameter of bore is in 10 mm stainless steel moulds, uses vacuum etc.
The mode of ion sintering, is warming up to 300 DEG C under the pressure of 300 MPa and keeps 120 min to carry out vacuum-sintering tabletting, heat up
Speed is 10 DEG C/min, obtains Emission in Cubic Ca3Si disc-shaped alloy material.
Using acetone, ethanol to carry out ultrasonic waves for cleaning successively before using in stainless-steel vacuum ball grinder, ultrasonic waves for cleaning is total
Time is 30 min.
Embodiment 2
A kind of Emission in Cubic Ca3The preparation method of Si alloy material, comprises the following steps:
(1) Ca powder and Si powder are pressed the mol ratio of 3.3:1 mix homogeneously under N protective atmosphere, obtain mixture；
(2) mixture, mill ball and stainless steel jar mill and the electronic balance of step (1) gained are put into and be filled with an air
In the glove box of pressure Ar, wherein ball material mass ratio is 16:1 configuration, in glove box after accurate weighing, puts in ball grinder, will
Ball grinder good seal, it is to avoid oxygen enters, then takes out ball grinder from glove box；
(3) by ready ball grinder in step (2), put in ball mill and carry out ball milling 80 h with the rotating speed of 1000 rpm, make
Powder fully reacts；
(4) powder completely reacted in step (3) is taken out, load in the stainless steel mould of hollow a size of 12 mm × 6 mm, adopt
By the mode of vacuum plasma sintering, under the pressure of 50 MPa, it is warming up to 500 DEG C keeps 20 min to carry out vacuum-sintering pressure
Sheet, heating rate is 10 DEG C/min, obtains Emission in Cubic Ca3Si bulk alloy material.
In stainless-steel vacuum ball grinder, the particle diameter of mill ball is 1.5 cm, uses acetone, ethanol to surpass before using successively
Sound wave cleans, and ultrasonic waves for cleaning total time is 20 min.
Embodiment 3
A kind of Emission in Cubic Ca3The preparation method of Si alloy material, comprises the following steps:
(1) Ca powder and Si powder are pressed mol ratio mix homogeneously under He gas shielded atmosphere of 3.5:1, obtains mixture；
(2) described mixture, mill ball and stainless steel jar mill and electronic balance are put into it is filled with the hands of an atmospheric pressure Ar
In casing, wherein ball material mass ratio is 8:1 configuration, in glove box after accurate weighing, puts in ball grinder, is sealed by ball grinder
Good, it is to avoid oxygen enters, from glove box, then take out ball grinder；
(3) by stainless-steel vacuum ball grinder ready in step (2), put in ball mill the rotating speed with 1500 rpm and carry out ball
Grind 50 h, make powder fully react；
(4) powder completely reacted in step (3) is taken out, load in the mm stainless steel mould of hollow 10 mm × 10, use vacuum
The mode of plasma agglomeration, is warming up to 100 DEG C under the pressure of 600 MPa and keeps 60 min to carry out vacuum-sintering tabletting, heat up
Speed is 12 DEG C/min, obtains the Emission in Cubic Ca that the length of side is 10mm3Si bulk alloy material.
In stainless-steel vacuum ball grinder, mill ball particle diameter is 1.0 cm, uses acetone, ethanol to carry out successively ultrasonic before using
Ripple cleans, and ultrasonic waves for cleaning total time is 20 min.
Embodiment 4
A kind of Emission in Cubic Ca3The preparation method of Si alloy material, comprises the following steps:
(1) Ca powder and Si powder are pressed mol ratio mix homogeneously under He gas shielded atmosphere of 3.2:1, obtains mixture；
(2) described mixture, mill ball and stainless steel jar mill and electronic balance are put into it is filled with the hands of an atmospheric pressure Ar
In casing, wherein ball material mass ratio is 20:1 configuration, in glove box after accurate weighing, puts in ball grinder, and ball grinder is close
Seal, it is to avoid oxygen enters, from glove box, then take out ball grinder；
(3) by stainless-steel vacuum ball grinder ready in step (2), put in ball mill the rotating speed with 1600 rpm and carry out ball
Grind 45 h, make powder fully react；
(4) powder completely reacted in step (3) is taken out, load in the mm stainless steel mould of hollow 10 mm × 10, use vacuum
The mode of plasma agglomeration, is warming up to 200 DEG C under the pressure of 400 MPa and keeps 30 min to carry out vacuum-sintering tabletting, heat up
Speed is 20 DEG C/min, obtains Emission in Cubic Ca3Si bulk alloy material.
In stainless-steel vacuum ball grinder, mill ball particle diameter is 0.2 cm, uses acetone, ethanol to carry out successively ultrasonic before using
Ripple cleans, and ultrasonic waves for cleaning total time is 20 min.
Embodiment 5
A kind of Emission in Cubic Ca3The preparation method of Si alloy material, comprises the following steps:
(1) Ca powder and Si powder are pressed mol ratio mix homogeneously under He gas shielded atmosphere of 3.4:1, obtains mixture；
(2) described mixture, mill ball and stainless steel jar mill and electronic balance are put into it is filled with the hands of an atmospheric pressure Ar
In casing, wherein ball material mass ratio is 12:1 configuration, in glove box after accurate weighing, puts in ball grinder, and ball grinder is close
Seal, it is to avoid oxygen enters, from glove box, then take out ball grinder；
(3) by stainless-steel vacuum ball grinder ready in step (2), put in ball mill the rotating speed with 1800 rpm and carry out ball
Grind 40 h, make powder fully react；
(4) powder completely reacted in step (3) is taken out, load in the mm stainless steel mould of hollow 10 mm × 10, use vacuum
The mode of plasma agglomeration, is warming up to 400 DEG C under the pressure of 500 MPa and keeps 10 min to carry out vacuum-sintering tabletting, heat up
Speed is 30 DEG C/min, obtains Emission in Cubic Ca3Si bulk alloy material.
In stainless-steel vacuum ball grinder, mill ball particle diameter is 0.5 cm, uses acetone, ethanol to carry out successively ultrasonic before using
Ripple cleans, and ultrasonic waves for cleaning total time is 25 min.
Fig. 1 is the Ca obtained by the preparation method of the present invention3The XRD figure spectrum of Si alloy material, as can be seen from the figure
Ca3Several diffraction maximums of Si are the most clear, illustrate that the method for the present invention is obtained in that the Ca of well-crystallized3Si thin film.
Fig. 2 is the Ca derived from the XRD of Fig. 13The crystal structure of Si, as can be seen from the figure Ca atom occupies cubical
Six center of areas, Si atom occupies cubical eight summits；Table 1 is Ca3The structure of Si alloy, space group is, its lattice
Constant is 4.8336.
Table 1 is Ca3The atom site of Si
Fig. 3-Fig. 5 is the Emission in Cubic Ca that the present invention prepares3The index parameter that the thermoelectricity capability of Si alloy material is relevant becomes with temperature
The curve chart changed, as can be seen from the figure along with the increase of temperature, the electrical conductivity of material declines, and Seebeck coefficient increases, power
The factor raises, and illustrates have preferable thermoelectric applications prospect.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modify, all should belong to the covering scope of the present invention.
Claims (5)
1. an Emission in Cubic Ca3The preparation method of Si alloy, it is characterised in that: described Ca3The Component molar of Ca and Si of Si alloy
Ratio is 3 ~ 3.5:1, and space group is, lattice paprmeter is 4.8336, and Si atom occupies four summits, and Ca atom is vertical
6 center of areas of cube, its preparation method specifically includes following steps:
(1) mix homogeneously under Ar protective atmosphere by Ca powder and Si powder 3.0 ~ 3.5:1 in molar ratio, obtains mixture；
(2) step (1) gained mixture is transferred in ball grinder, by ball grinder good seal in Ar gas shielded atmosphere, it is to avoid oxygen
Gas enters；
(3) by ready ball grinder in step (2), put in ball mill with the rotating speed of 1000 ~ 2000 rpm carry out ball milling 30 ~
80 h, make powder fully react, and obtain uniform mixed powder；
(4) the uniform mixed powder obtained in step (3) is taken out, load in the stainless steel mould of required specification, use true
The mode of empty plasma agglomeration, is warming up to 100 ~ 500 DEG C under the pressure of 50 ~ 600 MPa, keeps 10 ~ 120 min to carry out very
Empty sintering tabletting, obtains Ca3Si lamellar or bulk alloy material.
Emission in Cubic Ca the most according to claim 13The preparation method of Si alloy, it is characterised in that: ball material matter in step (2)
Amount ratio is: 5 ~ 20:1.
Emission in Cubic Ca the most according to claim 13The preparation method of Si alloy, it is characterised in that: mill ball in step (2)
Particle diameter be 0.2 ~ 1.5 cm, use acetone, ethanol to carry out ultrasonic waves for cleaning before using successively, ultrasonic waves for cleaning total time is 20
~30 min。
Emission in Cubic Ca the most according to claim 13The preparation method of Si alloy, it is characterised in that: in step (4), sintering rises
Temperature speed is 10 ~ 30 DEG C/min.
5. the Emission in Cubic Ca that a preparation method as described in any one of claim 1-4 prepares3Si alloy material.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002289627A (en) * | 2001-03-23 | 2002-10-04 | Univ Shizuoka | Method of growing calcium-silicide thin film |
| CN101792144A (en) * | 2009-10-28 | 2010-08-04 | 无锡润鹏复合新材料有限公司 | Face-centred cubic structure Ti3Si nano particles and preparation method thereof |
| CN104004935A (en) * | 2014-05-27 | 2014-08-27 | 武汉理工大学 | Method for super-rapidly preparing high-performance high-silicon-manganese thermoelectric material |
| CN105932148A (en) * | 2016-06-22 | 2016-09-07 | 福州大学 | Ag-doped cubic-phase Ca2Si thermoelectric material |
-
2016
- 2016-11-01 CN CN201610935975.2A patent/CN106319269B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002289627A (en) * | 2001-03-23 | 2002-10-04 | Univ Shizuoka | Method of growing calcium-silicide thin film |
| CN101792144A (en) * | 2009-10-28 | 2010-08-04 | 无锡润鹏复合新材料有限公司 | Face-centred cubic structure Ti3Si nano particles and preparation method thereof |
| CN104004935A (en) * | 2014-05-27 | 2014-08-27 | 武汉理工大学 | Method for super-rapidly preparing high-performance high-silicon-manganese thermoelectric material |
| CN105932148A (en) * | 2016-06-22 | 2016-09-07 | 福州大学 | Ag-doped cubic-phase Ca2Si thermoelectric material |
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