CN102383023B - Preparation method for ferro-silico-manganese alloy thermoelectric material - Google Patents
Preparation method for ferro-silico-manganese alloy thermoelectric material Download PDFInfo
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- CN102383023B CN102383023B CN 201110349856 CN201110349856A CN102383023B CN 102383023 B CN102383023 B CN 102383023B CN 201110349856 CN201110349856 CN 201110349856 CN 201110349856 A CN201110349856 A CN 201110349856A CN 102383023 B CN102383023 B CN 102383023B
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Abstract
The invention discloses a preparation method for a ferro-silico-manganese alloy thermoelectric material. The preparation method comprises the following steps of: grinding and mixing Mn powder, Fe powder and Si powder in a molar ratio of (Mn1-xFex): Si of 1: 1.74 (x=0.01-0.4), and pressing into blocks; melting the blocks under the protection of argon gas in an arc melting furnace to obtain an alloy clinker; breaking and grinding the obtained alloy clinker, and sieving with a 200-mesh sieve to obtain powder; performing ball milling under the protection of argon gas to obtain alloy powder with the average particle diameter of 1.5um; and thermally pressing and sintering the obtained alloy powder to obtain the bulky ferro-silico-manganese alloy thermoelectric material. The raw materials are low in cost; the technical process and equipment are simple; the technical parameters are easy to control; the obtained ferro-silico-manganese alloy bulky material is simple and pure; the maximum ZT value of the material reaches over 0.7; and the material has relatively good thermoelectric performance.
Description
Technical field
The present invention relates to a kind of preparation method of ferro-silico-manganese alloy thermoelectric material, belong to field of thermoelectric material technique.
Background technology
High manganese silicon compound (HMS) thermoelectric material is a kind of semi-conductor thermoelectric material of middle high temperature, and it is that Mn content is the silicide of 36.36at%～37at% (the Si/Mn atomic ratio is 1.70～1.75), therefore is also referred to as MnSi
1.7, be a kind of new semiconductor materials that has great prospects for development in the thermoelectricity field.It has that chemical stability is high, antioxidant property good, nontoxic pollution-free, low cost and other advantages.Because it has lower resistivity, larger Seebeck coefficient and thermostability preferably.But high manganese silicon compound is with respect to the ripe thermoelectric material SiGe of industry, PbTe and Bi
2Te
3Thermoelectric material, the lower (ZT=S of its thermoelectric figure of merit ZT
2σ T/ κ, in formula, S is Seebeck coefficient or the thermoelectric force of material, σ is specific conductivity, κ is thermal conductivity).The method that improves the ZT value has two kinds, is respectively doping and crystal grain thinning.Doping can make the material production lattice distortion, thereby affects thermal conductivity and the specific conductivity of material, to promote the ZT value.The Fe element add the crystalline network that has changed high manganese silicide, affected the lattice parameter of material, thereby the propagation of electronics and phonon all produced impact, adjust the content of Fe atom, thereby promote the thermoelectricity capability of material.
Mainly contain smelting process in present ferro-silico-manganese alloy thermoelectric material preparation technology, vapor phase deposition method and powder metallurgic method.Because there is respectively separately shortcoming in these methods, smelting process makes starting material fully reflect the alloy material of system, obtains pure single alloy phase, can access the virgin material product, but the resulting materials uneven components, insufficient formability.The vapor phase deposition method is mainly the thin-film material of system, can't to block materials, application is limited by very large.Powder metallurgic method can get material powder, for the good moulding of material provides sufficient condition.But can't obtain pure material, doped with a large amount of starting material impurity and other phase.Existing processing method all is difficult to obtain the pure ferro-silico-manganese thermoelectric block body material of homogeneous chemical composition.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of ferro-silico-manganese alloy thermoelectric material.The method process is simple, and the raw material abundance is with low cost, environmentally safe, prepared ferro-silico-manganese alloy thermoelectric material high conductivity, lower thermal conductivity and the high Seebeck coefficient of getting.
The present invention is realized by the following technical programs, a kind of preparation method of ferro-silico-manganese alloy thermoelectric material, and affiliated thermoelectric material is pressed Mn and Si
1-xFe
xMol ratio is 1: 1.74, and x=0.01～0.4 wherein is characterized in that comprising following process:
1) with Mn powder, Fe powder and Si powder (Mn in molar ratio
1-xFe
x): Si=1: 1.74 (x=0.01～0.4) ground and mixed, mixed powder is added in mould, be pressed into block under pressure 600～900MPa;
2) with step 1) melting under ar gas environment in arc-melting furnace of gained block, the melting electric current is 200A～250A, melt back 3 times obtains the alloy frit;
3) with step 2) the alloy frit that obtains crosses 200 mesh sieves through crushing grinding and obtains powder, the gained powder under argon shield in ball mill ball milling, ball milling condition is: ball material mass ratio is 1: 15～25, rotational speed of ball-mill 300～350 turns/min, Ball-milling Time 20～100 hours obtains the powdered alloy that median size is 1.5 μ m;
4) with step 3) the powdered alloy hot pressed sintering of gained: powdered alloy is added in graphite jig, and pressurization, be 5.0*10 in vacuum tightness take pressure as 30～70MPa
-3Under Pa, with 10 ℃/min of heat-up rate, be warming up to 950～1050 ℃, carry out the limit and add flanging sintering 45～75min, then be down to room temperature with 4 ℃/min of cooling rate, obtain the ferro-silico-manganese alloy thermoelectric material of block.
The invention has the advantages that: raw materials cost is cheap.The Mn powder, Si powder and Fe powder raw material source are sufficient, with low cost.Technical process and equipment are simple, processing parameter is easily controlled, because method provided by the invention is take Mn powder, Si powder and Fe powder as raw material, adopt arc melting method, make three kinds of elements fully participate in reaction, make Fe can participate in material and form reaction, be dissolved into completely in the lattice of high manganese silicide, greatly reduce Fe with the possibility that simple substance exists, improved the purity of ferro-silico-manganese, and control preparation process and change without metallographic, the ferro-silico-manganese block materials that obtains is pure.Adopt hot pressing and sintering technique, by controlling sintering pressure, temperature rise rate, sintering temperature and time and rate of temperature fall, sinter the ferro-silico-manganese micron powder of gained into fine and close block materials, the method is worth high compact block material, and the density height can reach 98%.Sintering temperature is low simultaneously, and sintering time is short.The maximum ZT value of material reaches more than 0.7, has higher thermoelectricity capability.
Description of drawings
The size distribution figure of Fig. 1 ferro-silico-manganese alloy thermoelectric material powder that to be embodiment make once ball milling.
Fig. 2 is the XRD figure spectrum of gained ferro-silico-manganese alloy thermoelectric material in embodiment one.
Fig. 3 is thermal conductivity and the thetagram of gained ferro-silico-manganese alloy thermoelectric material in embodiment one.
Fig. 4 is specific conductivity and the thetagram of gained ferro-silico-manganese alloy thermoelectric material in embodiment one.
Fig. 5 is Seebeck coefficient and the thetagram of gained ferro-silico-manganese alloy thermoelectric material in embodiment one.
Fig. 6 is ZT value and the temperature diagram of gained ferro-silico-manganese alloy thermoelectric material in embodiment one.
Embodiment
Embodiment one:
Be analytically pure Mn powder with purity, Si powder and Fe powder are starting material, get Mn powder 8.094g, Si8g powder and Fe powder 0.914g, and ground and mixed is even in mortar, and mixed powder is added in mould, is pressed into block under 900MPa.The gained block in the arc-melting furnace ar gas environment, is used 230A melting electric current melt back 3 times, obtain the alloy frit.The alloy frit that obtains was ground 200 mesh sieves obtained powder through fragmentation in mortar; gained powder 10g under argon shield in ball mill ball milling; use zirconium oxide balls; quality 200g; rotational speed of ball-mill 350 turns/min; Ball-milling Time 100 hours obtains the powdered alloy that median size is 1.5 μ m.Powdered alloy is added in graphite jig, and pressurization, be 5.0*10 in vacuum tightness take pressure as 40MPa
-3Under Pa, with 10 ℃/min of heat-up rate, be warming up to 1000 ℃, carry out the limit and add flanging sintering 60min, then be down to room temperature with 4 ℃/min of cooling rate, obtain the ferro-silico-manganese alloy thermoelectric material of block.
Embodiment two:
Be analytically pure Mn powder with purity, Si powder and Fe powder are starting material, get Mn powder 6.295g, Si8g powder and Fe powder 2.743g, and ground and mixed is even in mortar, and mixed powder is added in mould, is pressed into block under 900MPa.The gained block in the arc-melting furnace ar gas environment, is used 230A melting electric current melt back 3 times, obtain the alloy frit.The alloy frit that obtains was ground 200 mesh sieves obtained powder through fragmentation in mortar; gained powder 10g under argon shield in ball mill ball milling; use zirconium oxide balls; quality 200g; rotational speed of ball-mill 350 turns/min; Ball-milling Time 100 hours obtains the powdered alloy that median size is 1.5 μ m.Powdered alloy is added in graphite jig, and pressurization, be 5.0*10 in vacuum tightness take pressure as 40MPa
-3Under Pa, with 10 ℃/min of heat-up rate, be warming up to 1000 ℃, carry out the limit and add flanging sintering 60min, then be down to room temperature with 4 ℃/min of cooling rate, obtain the ferro-silico-manganese alloy thermoelectric material of block.
Embodiment three:
Be analytically pure Mn powder with purity, Si powder and Fe powder are starting material, get Mn powder 8.633g, Si8g powder and Fe powder 0.366g, and ground and mixed is even in mortar, and mixed powder is added in mould, is pressed into block under 900MPa.The gained block in the arc-melting furnace ar gas environment, is used 230A melting electric current melt back 3 times, obtain the alloy frit.The alloy frit that obtains was ground 200 mesh sieves obtained powder through fragmentation in mortar; gained powder 10g under argon shield in ball mill ball milling; use zirconium oxide balls; quality 200g; rotational speed of ball-mill 350 turns/min; Ball-milling Time 100 hours obtains the powdered alloy that median size is 1.5 μ m.Powdered alloy is added in graphite jig, and pressurization, be 5.0*10 in vacuum tightness take pressure as 40MPa
-3Under Pa, with 10 ℃/min of heat-up rate, be warming up to 1000 ℃, carry out the limit and add flanging sintering 60min, then be down to room temperature with 4 ℃/min of cooling rate, obtain the ferro-silico-manganese alloy thermoelectric material of block.
Embodiment four:
Be analytically pure Mn powder with purity, Si powder and Fe powder are starting material, get Mn powder 5.396g, Si8g powder and Fe powder 3.657g, and ground and mixed is even in mortar, and mixed powder is added in mould, is pressed into block under 900MPa.The gained block in the arc-melting furnace ar gas environment, is used 230A melting electric current melt back 3 times, obtain the alloy frit.The alloy frit that obtains was ground 200 mesh sieves obtained powder through fragmentation in mortar; gained powder 10g under argon shield in ball mill ball milling; use zirconium oxide balls; quality 200g; rotational speed of ball-mill 350 turns/min; Ball-milling Time 100 hours obtains the powdered alloy that median size is 1.5 μ m.Powdered alloy is added in graphite jig, and pressurization, be 5.0*10 in vacuum tightness take pressure as 40MPa
-3Under Pa, with 10 ℃/min of heat-up rate, be warming up to 1000 ℃, carry out the limit and add flanging sintering 60min, then be down to room temperature with 4 ℃/min of cooling rate, obtain the ferro-silico-manganese alloy thermoelectric material of block.
Claims (1)
1. the preparation method of a ferro-silico-manganese alloy thermoelectric material, described thermoelectric material is pressed Mn
1-xFe
xWith the Si mol ratio be 1: 1.74, x=0.01～0.4 wherein is characterized in that comprising following process:
1) with Mn powder, Fe powder and Si powder (Mn in molar ratio
1-xFe
x): Si=1: 1.74, x=0.01～0.4, ground and mixed adds mixed powder in mould, is pressed into block under pressure 600～900MPa;
2) with step 1) melting under ar gas environment in arc-melting furnace of gained block, the melting electric current is 200A～250A, melt back 3 times obtains the alloy frit;
3) with step 2) the alloy frit that obtains crosses 200 mesh sieves through crushing grinding and obtains powder, the gained powder under argon shield in ball mill ball milling, ball milling condition is: ball material mass ratio is 1: 15～25, rotational speed of ball-mill 300～350 turns/min, Ball-milling Time 20～100 hours obtains the powdered alloy that median size is 1.5 μ m;
4) with step 3) the powdered alloy hot pressed sintering of gained: powdered alloy is added in graphite jig, and pressurization, be 5.0*10 in vacuum tightness take pressure as 30～70MPa
-3Under Pa, with 10 ℃/min of heat-up rate, be warming up to 950～1050 ℃, carry out the limit and add flanging sintering 45～75min, then be down to room temperature with 4 ℃/min of cooling rate, obtain the ferro-silico-manganese alloy thermoelectric material of block.
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| CN102820457A (en) * | 2012-08-30 | 2012-12-12 | 上海锦众信息科技有限公司 | Preparation method of negative pole of power battery |
| CN105415053A (en) * | 2015-11-25 | 2016-03-23 | 宁波市鄞州唯达汽车配件厂（普通合伙） | Cutter claw used for machining of machine tool |
| CN109309155B (en) * | 2017-07-28 | 2022-04-19 | 丰田自动车株式会社 | High-manganese-silicon-based telluride thermoelectric composite material and preparation method thereof |
| CN109950388B (en) * | 2019-03-27 | 2023-04-07 | 中国人民大学 | Novel thermoelectric material |
| CN112374894B (en) * | 2020-04-11 | 2022-06-10 | 湖北中烟工业有限责任公司 | Metal silicide based heating material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1554580A (en) * | 2003-12-22 | 2004-12-15 | 华中科技大学 | Method and its device for preparing beta-FeSi2 thermoelectric material by laser cintering |
| CN101692479A (en) * | 2009-09-29 | 2010-04-07 | 武汉理工大学 | Method for preparing P-type high manganese-silicon thermoelectric material |
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| CN100459201C (en) * | 2002-11-28 | 2009-02-04 | 住友电气工业株式会社 | Thermoelectric material and method for producing same |
| JP4809691B2 (en) * | 2006-02-24 | 2011-11-09 | ヤンマー株式会社 | Iron alloy thermoelectric material |
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| CN1554580A (en) * | 2003-12-22 | 2004-12-15 | 华中科技大学 | Method and its device for preparing beta-FeSi2 thermoelectric material by laser cintering |
| CN101692479A (en) * | 2009-09-29 | 2010-04-07 | 武汉理工大学 | Method for preparing P-type high manganese-silicon thermoelectric material |
Non-Patent Citations (3)
| Title |
|---|
| JP特开2007-227756A 2007.09.06 |
| 含C、Ge的Fe-Si-Mn基热电材料的电学性能;李伟文等;《功能材料》;20031231;第34卷(第3期);第306-307和第310页 * |
| 李伟文等.含C、Ge的Fe-Si-Mn基热电材料的电学性能.《功能材料》.2003,第34卷(第3期),第306-307和第310页. |
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