CN108950347A - A kind of preparation method of MgAgSb pyroelectric material - Google Patents
A kind of preparation method of MgAgSb pyroelectric material Download PDFInfo
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- CN108950347A CN108950347A CN201810708757.4A CN201810708757A CN108950347A CN 108950347 A CN108950347 A CN 108950347A CN 201810708757 A CN201810708757 A CN 201810708757A CN 108950347 A CN108950347 A CN 108950347A
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Abstract
The invention discloses a kind of preparation methods of MgAgSb pyroelectric material, this method is specifically includes the following steps: (1) proportion raw material powder is fitted into graphite crucible, it is placed in vacuum microwave sintering furnace, microwave melting is carried out in 950 DEG C~1000 DEG C heat preservation at least 20min, obtains initial melted ingot after cooling；(2) alloy powder obtained after grinding melted ingot is fitted into mold, and progress hot pressed sintering is compact formed, and sintering temperature is 450 DEG C~500 DEG C and obtains compact formed block；(3) block is handled to progress microwave sintering annealing at least 5 days at 543K~573K, single-phase α-MgAgSb pyroelectric material can be obtained.The present invention is improved by the overall flow technological design to preparation method key, MgAgSb pyroelectric material is prepared using microwave melting combination microwave sintering process, and conditional parameter used by microwave melting and microwave sintering process is optimized, α-MgAgSb pyroelectric material can be prepared.
Description
Technical field
The invention belongs to the preparation technical fields of thermoelectric material, more particularly, to a kind of MgAgSb pyroelectric material
Preparation method.
Background technique
Increasingly prominent with energy environment issues, MgAgSb pyroelectric material is rich due to its component earth's crust reserves
Richness gradually receives significant attention, and is considered as one of most potential nearly room temperature thermoelectric material.MgAgSb has complicated phase transformation, from
Room temperature is respectively present high-temperature-phase the γ-MgAgSb, Cu of half-heusler structure to high temperature2The medium temperature phase β-of Sb structure
MgAgSb, the α-MgAgSb of tetragonal, but only room temperature phase α-MgAgSb shows good thermoelectricity capability.For α-
MgAgSb material, two component fusing point of Mg, Ag differ greatly, and there are certain difficulties for existing smelting preparation method, in addition,
Required α-MgAgSb material can be obtained by also needing prolonged soak to handle after melting 14 days.α-MgAgSb system thermoelectricity
The preparation of material generally use high melt method and mechanical alloying method (see 1. Ying, P., Liu, X., Fu, C., Yue, X.,
Xie, H., Zhao, X., et al.Chemistry of Materials, 2015,27 (3): 909-913；②Liu,Z.,Mao,
J., Sui, J., et al, Energy&Environmental Science, 2018.), but both tradition preparations α-MgAgSb
There is currently following main problems for method and α-MgAgSb material itself: (1) high melt method long preparation period, energy consumption it is high, at
This height.(2) in mechanical alloying method preparation process, powder is easily sticked to inside abrading-ball or ball grinder, is easy that there are the first steps
The miscellaneous phases such as the MgAg in ball milling are unfavorable for the specific component content of Control Assay.(3) in the high energy conditions of mechanical alloying method
Under, superfine alloy powder is easy to that violent chemical reaction occurs, and generates threat to the person and property safety.Therefore, seek
A kind of efficient, energy conservation, inexpensive preparation process are extremely important.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the purpose of the present invention is to provide a kind of MgAgSb system thermoelectricity
The preparation method of material, wherein being improved by the overall flow technological design to preparation method key, using microwave melting
MgAgSb pyroelectric material is prepared in conjunction with microwave sintering process, and to condition used by microwave melting and microwave sintering process
Parameter (such as treatment temperature and time) optimizes, and α-MgAgSb pyroelectric material can be prepared, and this method can be reduced
Energy consumption shortens α-MgAgSb compound preparation time to 5 days, while obtaining the preparation method of single-phase α-MgAgSb compound.
To achieve the above object, it is proposed, according to the invention, provide a kind of preparation method of MgAgSb pyroelectric material, feature
It is, specifically includes the following steps:
(1) Mg elemental powders, Ag elemental powders and the Sb elemental powders by purity not less than 99.9% press atomic ratio Mg: Ag
: Sb=(1+x): (0.97+0.5x): (0.99+0.5x) proportion is fitted into graphite crucible, is placed in vacuum microwave sintering furnace,
It is filled with inertia mobility atmosphere, 950 DEG C~1000 DEG C heat preservation at least 20min is then heated to and carries out microwave melting, obtained after cooling
Obtain initial melted ingot；
Wherein, 0≤x≤0.02；
(2) alloy powder that the initial melted ingot for obtaining the step (1) obtains after grinding is fitted into mold,
Progress hot pressed sintering is compact formed under the protection of inert gas in vacuum sintering funace, and sintering temperature is 450 DEG C~500
DEG C, soaking time is not less than 30min, and the pressure of holding stage is not less than 120MPa, thus obtain it is compact formed after block；
(3) block that the step (2) obtains is placed in vacuum microwave sintering furnace, is passed through inert gas guarantor
Shield, progress microwave sintering annealing at least 5 days is then handled at 270 DEG C~300 DEG C, MgAgSb pyroelectric material can be obtained.
As present invention further optimization, in the step (1), the MgAgSb pyroelectric material is specially single-phase α-
MgAgSb pyroelectric material.
As present invention further optimization, in the step (1), atomic ratio Mg: Ag: Sb is preferably 1: 0.97:
0.99, the microwave melting preferably keeps the temperature 40min at 950 DEG C.
As present invention further optimization, in the step (2), sintering used by the hot pressed sintering is compact formed
Temperature is 450 DEG C, soaking time 30min, and holding stage pressure is 240Mpa.
As present invention further optimization, in the step (3), the microwave sintering annealing is specifically at 270 DEG C
Isothermal annealing 5 days.
As present invention further optimization, in the step (1), heating rate used by the heating be 20 DEG C/
min；
In the step (2), heating rate used by the hot pressed sintering is compact formed is 10 DEG C/min.
As present invention further optimization, inert gas employed in the step (1) and the step (2) is
Argon gas；
The step (1) is specifically to make vacuum degree not higher than 10 vacuum microwave sintering stove evacuation-3Pa, then again
It is filled with inertia mobility atmosphere.
Contemplated above technical scheme through the invention, it is compared with prior art, micro- due to being combined using microwave melting
Wave sintering process prepares α-MgAgSb pyroelectric material, can take compared with existing high melt and mechanical alloying method
It is following the utility model has the advantages that
(1) the microwave preparation process that the present invention uses is based on using microwave technology principle, utilizes graphite, semiconductor absorber microwave
Characteristic, microwave particle and α-MgAgSb material generate frictional wear, to heat in material internal, are different from traditional smelting process
External temperature heating process.
(2) the microwave preparation process that uses of the present invention by conventional high temperature smelting time by shortening to 2h for 24 hours, by moving back for later period
The fiery time was foreshortened to 5 days by 14 days, and single-phase α-MgAgSb is prepared.
(3) present invention process stock utilization is high, and whole preparation process energy consumption greatly reduces, and the preparation cost of material can be big
Amplitude reduction has good industrialized production and application prospect.
Further, since its treatment temperature of microwave melting used in the present invention is 950 DEG C~1000 DEG C, the present invention also passes through
The atomic ratio proportion for controlling Mg elemental powders, Ag elemental powders and Sb elemental powders, will be by atomic ratio Mg: Ag: Sb=(1+x):
(0.97+0.5x): (0.99+0.5x) Mg elemental powders, Ag elemental powders and Sb elemental powders are matched (0≤x≤
0.02), by using slight excess of Mg, the volatilization of Mg in subsequent processes can be made up, it is ensured that MgAgSb system thermoelectricity material
Expect its thermoelectricity capability.
To sum up, the present invention can prepare Mg-Ag-Sb pyroelectric material, especially can get high-purity room temperature phase α-MgAgSb.
Detailed description of the invention
Fig. 1 is α-MgAgSb alloy preparation flow figure.
Fig. 2 is the X-ray diffractogram of the material after microwave melting and microwave melting combination microwave annealing, wherein (a) is micro-
The X-ray diffractogram of the alloy of wave melting (MH) different time (b) is annealed 5 days for microwave melting 40min combination microwave sintering and is tried
The X-ray diffractogram of sample.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The preparation method of MgAgSb pyroelectric material in the present invention mainly includes in short that microwave melting and microwave are burnt
Knot two material processings of annealing.First by carrying out microwave melting to original composition material, then caused by hot pressed sintering
Densification molding, then the block of Thermocompressed sintering and forming is subjected to microwave annealing processing, eventually form single-phase α-MgAgSb compound.
Implementation process is as shown in Figure 1, specifically can be such that each metal simple-substance raw material powder of high-purity (>=99.9%)
It is matched by atomic ratio Mg: Ag: Sb=1: 0.97: 0.99, is fitted into high purity graphite crucible, is placed in vacuum microwave sintering furnace,
It is filled with inertia mobility atmosphere, is rapidly heated to 950 DEG C, heating rate 20 DEG C/min, soaking time 40min, at the beginning of the cold acquisition of furnace
Beginning melted ingot.Alloy powder after above-mentioned melted ingot is ground is packed into dedicated powder metallurgy steel die or sintered-carbide die
(for example, concussion ball mill grinding can be carried out the ingot casting of acquisition, powder is then put into stainless steel mould, the shape of mold can be with
Adjust according to actual needs, such as can be for disk mold etc.), carried out in vacuum sintering funace hot pressed sintering densification at
Type, keeps the temperature 30min, holding stage pressure 240MPa, entire sintering process argon by 450 DEG C of sintering temperature, 10 DEG C/min of heating rate
Gas atmosphere protection.
Block (such as block disk) after will be compact formed is placed in vacuum microwave sintering furnace, is passed through inert gas guarantor
Shield, 270 DEG C (i.e. 543K) isothermal annealing 5 days, obtain single-phase α-MgAgSb compound.
The present invention is carried out example verifying, each implementation with regard to different microwave smelting times (20min~40min) respectively
The operating condition of example is as shown in table 1.
Table 1
Alloy powder and microwave melting combine the X-ray diffractogram of sintering annealed sample to see in Fig. 2 respectively after microwave melting
(a) and (b).
The present invention is also carried out with regard to Parameter Conditions employed in different raw material proportionings, microwave melting, sintering annealing respectively
Embodiment verifying, the operating condition of each embodiment are as shown in table 2.
Table 2
Inert atmosphere of the present invention can also use other inert gases other than argon gas.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (7)
1. a kind of preparation method of MgAgSb pyroelectric material, which is characterized in that specifically includes the following steps:
(1) Mg elemental powders, Ag elemental powders and the Sb elemental powders by purity not less than 99.9% press atomic ratio Mg: Ag: Sb
=(1+x): (0.97+0.5x): (0.99+0.5x) proportion is fitted into graphite crucible, is placed in vacuum microwave sintering furnace, fills
Enter inertia mobility atmosphere, then heats to 950 DEG C~1000 DEG C heat preservation at least 20min and carry out microwave melting, obtained after cooling
Initial melted ingot；
Wherein, 0≤x≤0.02；
(2) alloy powder that the initial melted ingot for obtaining the step (1) obtains after grinding is fitted into mold, in vacuum
Progress hot pressed sintering is compact formed under the protection of inert gas in hot-pressed sintering furnace, and sintering temperature is 450 DEG C~500 DEG C, protects
The warm time is not less than 30min, and the pressure of holding stage is not less than 120MPa, thus obtain it is compact formed after block；
(3) block that the step (2) obtains is placed in vacuum microwave sintering furnace, is passed through inert gas shielding, so
Progress microwave sintering annealing at least 5 days is handled at 270 DEG C~300 DEG C afterwards, MgAgSb pyroelectric material can be obtained.
2. the preparation method of MgAgSb pyroelectric material as described in claim 1, which is characterized in that described in the step (1)
MgAgSb pyroelectric material is specially single-phase α-MgAgSb pyroelectric material.
3. the preparation method of MgAgSb pyroelectric material as described in claim 1, which is characterized in that described in the step (1)
Atomic ratio Mg: Ag: Sb is preferably 1: 0.97: 0.99, and the microwave melting preferably keeps the temperature 40min at 950 DEG C.
4. the preparation method of MgAgSb pyroelectric material as described in claim 1, which is characterized in that described in the step (2)
Sintering temperature used by hot pressed sintering is compact formed is 450 DEG C, soaking time 30min, and holding stage pressure is 240Mpa.
5. the preparation method of MgAgSb pyroelectric material as described in claim 1, which is characterized in that described in the step (3)
Microwave sintering annealing is specifically isothermal annealing 5 days at 270 DEG C.
6. the preparation method of MgAgSb pyroelectric material as described in claim 1, which is characterized in that described in the step (1)
Heating rate used by heating up is 20 DEG C/min；
In the step (2), heating rate used by the hot pressed sintering is compact formed is 10 DEG C/min.
7. the preparation method of MgAgSb pyroelectric material as described in claim 1, which is characterized in that the step (1) and described
Inert gas employed in step (2) is argon gas；
The step (1) is specifically to make vacuum degree not higher than 10 vacuum microwave sintering stove evacuation-3Then Pa is re-filled with
Inertia mobility atmosphere.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110218888A (en) * | 2019-06-20 | 2019-09-10 | 电子科技大学 | A kind of novel Zintl phase thermoelectric material and preparation method thereof |
| CN112310268A (en) * | 2020-10-30 | 2021-02-02 | 中国电子科技集团公司第十八研究所 | Preparation method of novel medium-temperature thermoelectric material |
| CN113073220A (en) * | 2021-03-25 | 2021-07-06 | 中国科学院重庆绿色智能技术研究院 | Preparation method and product of room temperature magnesium-based thermoelectric material |
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Cited By (4)
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|---|---|---|---|---|
| CN110218888A (en) * | 2019-06-20 | 2019-09-10 | 电子科技大学 | A kind of novel Zintl phase thermoelectric material and preparation method thereof |
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| CN112310268A (en) * | 2020-10-30 | 2021-02-02 | 中国电子科技集团公司第十八研究所 | Preparation method of novel medium-temperature thermoelectric material |
| CN113073220A (en) * | 2021-03-25 | 2021-07-06 | 中国科学院重庆绿色智能技术研究院 | Preparation method and product of room temperature magnesium-based thermoelectric material |
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