CN102514282B - Protective coating suitable for CoSb3 base thermoelectric material and preparation method thereof - Google Patents

Protective coating suitable for CoSb3 base thermoelectric material and preparation method thereof Download PDF

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CN102514282B
CN102514282B CN201110417885.1A CN201110417885A CN102514282B CN 102514282 B CN102514282 B CN 102514282B CN 201110417885 A CN201110417885 A CN 201110417885A CN 102514282 B CN102514282 B CN 102514282B
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cosb
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layer
ysz
protective coating
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CN102514282A (en
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赵德刚
耿浩然
滕新营
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University of Jinan
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention discloses a protective coating suitable for CoSb3 base thermoelectric material. The protective coating comprises an upper layer and a lower layer; the lower layer is made of metal W, and the upper layer is a mixture of Y2O3 and ZrO2; and the Y2O3 accounts for 7-10 wt% of the mixture. The protective coating of the invention can substantially reduce Sb volatilization of CoSb3 base thermoelectric material during high temperature working, and has high coating density and good interface combination. Experiments have proved that the coating has a bonding strength with the matrix greater than 5Mpa; and after 30 day continuous experiment under 500 DEG C, the coating sample has unit area weight loss less than 2*10<-3> g / cm<2>, which is far smaller than 1.8*10<-2> / cm<2> of an uncoated sample. The invention employs an electron beam physical vapor deposition method to prepare the protective coating; the method is easily practical; and the obtained product has good performance and can effectively prevent Sb volatilization of CoSb3 during high temperature working.

Description

One is applicable to CoSb 3protective coating of base thermoelectricity material and preparation method thereof
Technical field
The present invention relates to a kind of protective coating that is applicable to skutterudite-base thermoelectrical material and preparation method thereof, belong to thermoelectric material and devices field.
Background technology
Thermoelectric material is to utilize the Seebeck effect of semi-conducting material heat energy to be directly converted to a kind of material of electric energy.Utilize thermo-electric device prepared by thermoelectric material not only can effectively the infrared light in solar energy be converted into electric energy, can also in the industries such as iron and steel, electrolytic aluminium, thermal power generation, industrial exhaust heat, effectively realize Waste Heat Recovery utilization, obtain the attention of world many countries at present.The Performance Characteristics of thermoelectric material is characterized by thermoelectric figure of merit (ZT), wherein ZT=S 2t/ ρ κ, S is Seebeck coefficient, and ρ is resistivity, and κ is thermal conductivity, and T is absolute temperature.
The CoSb that fills or adulterate 3base thermoelectricity material be considered to have most application prospect in one of warm electric electricity generation material, the new A of multiple high thermoelectric figure of merit yco 4sb 12the filling skutterudite thermoelectric material of (A=Ba, K, Na, Eu etc.) is in the news in succession, and its thermoelectric figure of merit is stable reaches 1.0.But fill CoSb 3base thermoelectricity material vacuum high-temperature when work framework atom Sb due to higher vapor pressure easily volatilization cause the Gradient Descent of material internal Sb concentration, and filling atom in lattice hole is very easy to escape, thereby makes the performance degradation of thermoelectric material; CoSb simultaneously 3when civilian thermo-electric device prepared by base thermoelectricity material is worked under hot conditions in air, because the affinity of Sb and O is large especially, very easily form bipolar diffusion and cause material surface form CoSb 2o 7deng oxide, under higher temperature, Sb even can be with Sb 4o 6form volatilization, greatly reduce the thermoelectricity capability of material thereby the omission of Sb atom very easily causes thermoelectric material to depart from its nominal component.
In general, thermoelectricity protective coating is except having good cohesive force, outside low interface resistance and the thermal coefficient of expansion that mates with thermoelectric material, the thermal shunt that protective coating itself produces thermoelectric material can not exceed 5%, electricity shunting can not exceed 1%, and the volatile quantity of the normal work of thermoelectric material after 1000 hours must be less than 1%.Because high-performance skutterudite-base thermoelectrical Materials history is shorter, about CoSb 3the protective coating preparation of base thermoelectricity material and the various electric heating that interface exists transport the research of the problem such as mechanism, flooding mechanism and report considerably less.The T. Caillat in current U.S.'s jet power laboratory (Jet Propulsion Laboratory) etc. are to CoSb 3base thermoelectric arm adopts the method for magnetron sputtering to carry out Mo coating (Tests results of skutterudite based thermoelectric unicouples in its temperature end deposition, Energ Convers Manage, 48,2007), but because Mo coating has the electrical conductivity higher than skutterudite thermoelectric material and thermal conductivity, thereby produced a large amount of electricity shunting and thermal shunt on Mo layer, reduced the conversion efficiency of thermo-electric device, and the thermal coefficient of expansion (5.5～6.5 × 10 of Mo -6/ K) be significantly less than the thermal coefficient of expansion (10～12 × 10 of skutterudite-base thermoelectrical material -6/ K), under long term high temperature condition, easily peel off; The people such as the Jeffrey of the U.S. once attempted adopting the method for plasma spraying at N-type CoSb 3on material, spray one deck MgAl 2o 4coating (spinelle) and Mg 2siO 4coating (US7480984B1), the 1 time-of-week inner boundary of entirely so working under 850K vacuum condition is in conjunction with good, but excess Temperature while forming coating due to plasma spraying has exceeded CoSb 3the volatilization temperature of material itself, thus the thermoelectricity capability of thermoelectric material itself reduced, and the protective coating density that plasma spraying forms is not high, and the hole that coating exists likely becomes volatilization " short circuit " passage of Sb atom in material.
Summary of the invention
The present invention is directed to deficiency of the prior art, provide one to be applicable to CoSb 3protective coating base thermoelectricity material, that can prevent Sb vaporization at high temperature, this coating is mated good with thermoelectric material matrix heat and bond strength is high, and volatilization has good protection effect to Sb.
The present invention also provides the preparation method of this protective coating, and the method preparation is simple, easy to operate, is easy to realize.
In order to solve better CoSb 3the problem of Sb volatilization in base thermoelectricity material use procedure, inventor has studied a kind of high efficient protected coating, and coating comprises two-layer, and bottom is metal W layer, and upper strata is that (composition of YSZ layer is Y to YSZ layer 2o 3and ZrO 2), wherein YSZ layer (Y 2o 3stable ZrO 2) thermal coefficient of expansion and CoSb 3material is comparatively approaching, and W layer can effectively be realized YSZ as intermediate connecting layer and is combined with the connection of matrix, and coating and substrate combinating strength are higher, and the lasting experimental result of heat shows that coating protection is respond well.Coating preparation utilizes the electro beam physics vapour deposition technology (EB-PVD) that film forming density is higher, reduces to greatest extent the thermal stress at protective coating interface, has ensured the protection effect of protective coating.
The present invention is achieved by the following measures:
One is applicable to CoSb 3the protective coating of base thermoelectricity material, is characterized in that: comprise two-layerly up and down, lower composition of layer is metal W, and upper component is Y 2o 3and ZrO 2mixture, wherein Y 2o 3for 7～10wt% of mixture.In addition, upper strata can be denoted as YSZ layer, lower same.
In above-mentioned protective coating, the thickness of lower floor is 5～20 μ m, and the thickness of upper strata (YSZ layer) is 20～100 μ m.
In above-mentioned protective coating, upper strata (YSZ layer) is 10～11 × 10 from the thermal coefficient of expansion between room temperature to 500 DEG C -6k -1.
On protective coating laying of the present invention and base material, its form is: lower floor's W metal level invests on matrix, and then YSZ layer invests on W metal level again, forms protective coating.Described base material is CoSb 3thermoelectric material or for filling or the CoSb of the different elements that adulterate 3thermoelectric material, fills or the element of doping is one or more elements in In, Ce, Ga, Eu, Yb, Nb, Pb, Te and Sn, also can be other element.In the present invention, the base material of above-mentioned two types is referred to as to CoSb 3no matter base thermoelectricity material is simple CoSb 3thermoelectric material, or with the CoSb of different elements 3thermoelectric material, its thermal coefficient of expansion is all close, and therefore protective materials of the present invention all can mate well with its heat, and bond strength is high, plays good protective action.
The present invention is applicable to CoSb 3the protective coating of base thermoelectricity material adopts electro beam physics vapour deposition method to make, and comprises the following steps:
(1) by CoSb 3base thermoelectricity material surface finish, cleans up, and is put on substrate, by Y after drying up 2o 3and ZrO 2mixture target and W metal targets are positioned over respectively in two crucibles, then vacuumize;
(2) by base plate heating to 500～550 DEG C, after temperature stabilization, regulate electronic beam current to 1.0～2.0A, substrate rotating speed is 10～20 revs/min, first evaporates W metal targets, being deposited into thickness is 5～20 μ m;
(3) after W lower floor deposition, keep substrate temperature constant, then to Y 2o 3and ZrO 2mixture target evaporates, wherein electronic beam current 2.0～3.0A, and being deposited into thickness is 20～100 μ m;
(4) after deposition, continue to keep vacuum state, in the time that substrate temperature is cooled to below 100 DEG C or 100 DEG C, opens vacuum chamber and take out sample, complete CoSb 3protective coating deposition process.
In above-mentioned preparation method, in step (1), CoSb 3base thermoelectricity material is ultrasonic cleaning 3-5min in alcohol.
In above-mentioned preparation method, in step (1), be evacuated to 10 -3pa.
In above-mentioned preparation method, in step (3), substrate rotating speed is 10～20 revs/min.
In above-mentioned preparation method, metal W layer and YSZ layer are obtained by electronic beam current deposition, and the electronic beam current of deposition tungsten layer is 1-2A, electronic beam current can choose at random within the scope of this, the tungsten layer that obtains same thickness, electronic beam current is larger, and needed sedimentation time is shorter.The electronic beam current of deposition YSZ layer is 2-3A, and same electronic beam current can choose at random within the scope of this, obtain the YSZ layer of same thickness, and electronic beam current is larger, and needed sedimentation time is shorter.
Protective coating of the present invention has good protective action, and coating has two-layer, and lower floor is metal tungsten layer, and thickness is 5～20 μ m, and upper strata is YSZ layer, and thickness is 20～100 μ m.Wherein, tungsten layer and CoSb 3base thermoelectricity material is connected, and YSZ layer is connected with tungsten layer, because tungsten layer is very thin, therefore tungsten layer is equivalent to CoSb 3transition articulamentum between base thermoelectricity material and YSZ layer.The thermal coefficient of expansion of protective coating and CoSb 3material is comparatively approaching, and coating and substrate combinating strength are high, and coating itself is with respect to CoSb 3the electricity shunting and the thermal shunt that produce are less, reduce to greatest extent the thermal stress at protective coating interface, have ensured the protection effect of protective coating.
Protective coating of the present invention, can reduce CoSb greatly 3the volatilization of Sb when base thermoelectricity material hot operation, coating density is high, and interface is in conjunction with good.The experiment proved that, coating and substrate combinating strength are greater than 5Mpa, and the lasting experiment of coating sample heat under 500 DEG C of conditions is after 30 days, and unit are weightlessness is less than 2 × 10 -3g/cm 2, be far smaller than 1.8 × 10 of uncoated sample -2g/cm 2.
The present invention adopts the method for electro beam physics vapour deposition to prepare protective coating, and method is simple, and products obtained therefrom is functional, can effectively prevent the CoSb of hot operation 3sb volatilization.
Brief description of the drawings
The protective coating of Fig. 1 embodiment 1 and CoSb 3the thermal coefficient of expansion of material.
The SEM scanned photograph at the protective coating interface of Fig. 2 embodiment 1.
The thermal weight loss experimental result of the protective coating sample of embodiment 1 in the lasting experiment of Fig. 3 heat.
The SEM scanned photograph at the lasting experiment of Fig. 4 heat protective coating interface of embodiment 1 after 30 days.
Detailed description of the invention
Below by instantiation, the present invention will be further elaborated, and the effect of explanation is only played in following explanation, does not limit the scope of the invention.
embodiment 1
In YSZ layer, Y 2o 3mass percent is 8%, and surplus is ZrO 2, coating production is:
First by CoSb 3surface finish, in alcohol, ultrasonic 3 min, are put on substrate after drying up, and YSZ target and W target are placed in two crucibles, then main vacuum chamber are evacuated down to 10 -3pa; Heated substrates to 500 DEG C, regulates electronic beam current 2.0A, substrate rotating speed 20r/ min, evaporation W target, sedimentation time 10min, thickness approximately 5 μ m; At same substrate temperature, YSZ target is evaporated, adjusting electronic beam current is 3.0A again, sedimentation time 40min, thickness approximately 20 μ m; After treat that substrate temperature is cooled to 100 DEG C, open vacuum chamber take out sample, complete CoSb 3painting layer deposition process.
The protective coating of this example gained and the bond strength of matrix are 5.6Mpa, and method of testing is carried out (lower same) according to ASTM C-633-79 standard, and under 500 DEG C of conditions, the lasting experiment of heat is after 30 days, and unit are weightlessness is 1.8 × 10 -3g/cm 2.
embodiment 2
YSZ composition of layer (mass percent) is: 8.5%Y 2o 3, surplus is ZrO 2, coating production is: with Sn 0.2co 4sb 12for matrix, by its surface finish, in alcohol, ultrasonic 5 min, are put on substrate after drying up, and YSZ and W target are placed in two crucibles, are evacuated down to 10 -3pa; Heated substrates to 520 DEG C, regulates electronic beam current 1.0A, and substrate rotating speed is 10r/ min, evaporation W target, sedimentation time 20 min, thickness approximately 10 μ m; At same substrate temperature, YSZ target is evaporated, adjusting electronic beam current is 3.0A again, sedimentation time 80 min, thickness approximately 40 μ m; After in the time that substrate is cooled to 100 DEG C, open vacuum chamber take out sample, complete CoSb 3be coated with layer deposition process.
The protective coating of this example gained and the bond strength of matrix are 5.9Mpa, and under 500 DEG C of conditions, the lasting experiment of heat is after 30 days, and unit are weightlessness is 1.6 × 10 -3g/cm 2.
embodiment 3
YSZ composition of layer (mass percent) is: 10%Y 2o 3, surplus is ZrO 2.Coating production is: with In 0.1co 4sb 12for matrix, by its surface finish, ultrasonic cleaning 5 min in alcohol, are put into after drying up on the substrate in operating room, and YSZ and W target are placed in respectively in two crucibles, are evacuated down to 10 -3pa; Then heated substrates to 550 DEG C, regulates electronic beam current 2.0A, and substrate rotating speed is 15r/min, evaporation W target, sedimentation time 40 min, thickness approximately 20 μ m; At same substrate temperature, YSZ target is evaporated, adjusting electronic beam current is 3.0A again, sedimentation time 200min, thickness approximately 100 μ m; After keep vacuum state, in the time that temperature is cooled to 100 DEG C, open vacuum chamber take out sample, complete CoSb 3be coated with layer deposition process.
The protective coating of this example gained and the bond strength of matrix are 6.1Mpa, and under 500 DEG C of conditions, the lasting experiment of heat is after 30 days, and unit are weightlessness is 1.5 × 10 -3g/cm 2.
embodiment 4
YSZ composition of layer (mass percent) is: 9%Y 2o 3, surplus is ZrO 2, with Ce 0.1co 4sb 12for matrix, preparation technology of coating is with embodiment 1.
The protective coating of this example gained and the bond strength of matrix are 5.4Mpa, and under 500 DEG C of conditions, the lasting experiment of heat is after 30 days, and unit are weightlessness is 1.7 × 10 -3g/cm 2.
embodiment 5
YSZ composition of layer (mass percent) is: 7%Y 2o 3, surplus is ZrO 2, with Co 4sb 11.7te 0.3for matrix, preparation technology of coating is with embodiment 1.Coating production is:
First by CoSb 3surface finish, in alcohol, ultrasonic 3 min, are put on substrate after drying up, and YSZ target and W target are placed in two crucibles, then main vacuum chamber are evacuated down to 10 -3pa; Heated substrates to 500 DEG C, regulates electronic beam current 2.0A, substrate rotating speed 20r/ min, evaporation W target, sedimentation time 10min, thickness approximately 5 μ m; At same substrate temperature, YSZ target is evaporated, adjusting electronic beam current is 3.0A again, sedimentation time 40min, thickness approximately 20 μ m; After treat that substrate temperature is cooled to 100 DEG C, open vacuum chamber take out sample, complete CoSb 3painting layer deposition process.
The protection of this example gained and the bond strength of matrix are 5.9Mpa; Under 500 DEG C of conditions, the lasting experiment of heat is after 30 days, and unit are weightlessness is 1.9 × 10 -3g/cm 2.

Claims (5)

1. one kind is applicable to CoSb 3the protective coating of base thermoelectricity material, is characterized in that: by upper and lower two-layer composition, lower composition of layer is metal W, and upper component is Y 2o 3and ZrO 2mixture, be designated as YSZ layer, lower floor and CoSb 3base thermoelectricity material connects, wherein Y 2o 3mass percent in upper strata is 8%, and surplus is ZrO 2, coating production is: first by CoSb 3surface finish, in alcohol, ultrasonic 3 min, are put on substrate after drying up, and YSZ target and W target are placed in two crucibles, then main vacuum chamber are evacuated down to 10 -3pa; Heated substrates to 500 DEG C, regulates electronic beam current 2.0A, substrate rotating speed 20r/ min, evaporation W target, sedimentation time 10min, thickness approximately 5 μ m; At same substrate temperature, YSZ target is evaporated, adjusting electronic beam current is 3.0A again, sedimentation time 40min, thickness approximately 20 μ m; After treat that substrate temperature is cooled to 100 DEG C, open vacuum chamber take out sample, complete CoSb 3painting layer deposition process.
2. one kind is applicable to CoSb 3the protective coating of base thermoelectricity material, is characterized in that: by upper and lower two-layer composition, lower composition of layer is metal W, and upper component is Y 2o 3and ZrO 2mixture, be designated as YSZ layer, lower floor and CoSb 3base thermoelectricity material connects, wherein Y 2o 3mass percent in upper strata is 8.5%, and surplus is ZrO 2, coating production is: with Sn 0.2co 4sb 12for matrix, by its surface finish, in alcohol, ultrasonic 5 min, are put on substrate after drying up, and YSZ and W target are placed in two crucibles, are evacuated down to 10 -3pa; Heated substrates to 520 DEG C, regulates electronic beam current 1.0A, and substrate rotating speed is 10r/ min, evaporation W target, sedimentation time 20 min, thickness approximately 10 μ m; At same substrate temperature, YSZ target is evaporated, adjusting electronic beam current is 3.0A again, sedimentation time 80 min, thickness approximately 40 μ m; After in the time that substrate is cooled to 100 DEG C, open vacuum chamber take out sample, complete CoSb 3be coated with layer deposition process.
3. one kind is applicable to CoSb 3the protective coating of base thermoelectricity material, is characterized in that: by upper and lower two-layer composition, lower composition of layer is metal W, and upper component is Y 2o 3and ZrO 2mixture, be designated as YSZ layer, lower floor and CoSb 3base thermoelectricity material connects, wherein Y 2o 3mass percent in upper strata is 10%, and surplus is ZrO 2, coating production is: with In 0.1co 4sb 12for matrix, by its surface finish, ultrasonic cleaning 5 min in alcohol, are put into after drying up on the substrate in operating room, and YSZ and W target are placed in respectively in two crucibles, are evacuated down to 10 -3pa; Then heated substrates to 550 DEG C, regulates electronic beam current 2.0A, and substrate rotating speed is 15r/min, evaporation W target, sedimentation time 40 min, thickness approximately 20 μ m; At same substrate temperature, YSZ target is evaporated, adjusting electronic beam current is 3.0A again, sedimentation time 200min, thickness approximately 100 μ m; After keep vacuum state, in the time that temperature is cooled to 100 DEG C, open vacuum chamber take out sample, complete CoSb 3be coated with layer deposition process.
4. one kind is applicable to CoSb 3the protective coating of base thermoelectricity material, is characterized in that: by upper and lower two-layer composition, lower composition of layer is metal W, and upper component is Y 2o 3and ZrO 2mixture, be designated as YSZ layer, lower floor and CoSb 3base thermoelectricity material connects, wherein Y 2o 3mass percent in upper strata is 9%, and surplus is ZrO 2, coating production is: with Ce 0.1co 4sb 12for matrix, first by Ce 0.1co 4sb 12surface finish, in alcohol, ultrasonic 3 min, are put on substrate after drying up, and YSZ target and W target are placed in two crucibles, then main vacuum chamber are evacuated down to 10 -3pa; Heated substrates to 500 DEG C, regulates electronic beam current 2.0A, substrate rotating speed 20r/ min, evaporation W target, sedimentation time 10min, thickness approximately 5 μ m; At same substrate temperature, YSZ target is evaporated, adjusting electronic beam current is 3.0A again, sedimentation time 40min, thickness approximately 20 μ m; After treat that substrate temperature is cooled to 100 DEG C, open vacuum chamber take out sample, complete CoSb 3painting layer deposition process.
5. one kind is applicable to CoSb 3the protective coating of base thermoelectricity material, is characterized in that: by upper and lower two-layer composition, lower composition of layer is metal W, and upper component is Y 2o 3and ZrO 2mixture, be designated as YSZ layer, lower floor and CoSb 3base thermoelectricity material connects, wherein Y 2o 3mass percent in upper strata is 7%, and surplus is ZrO 2, coating production is: with Co 4sb 11.7te 0.3for matrix, first by Co 4sb 11.7te 0.3surface finish, in alcohol, ultrasonic 3 min, are put on substrate after drying up, and YSZ target and W target are placed in two crucibles, then main vacuum chamber are evacuated down to 10 -3pa; Heated substrates to 500 DEG C, regulates electronic beam current 2.0A, substrate rotating speed 20r/ min, evaporation W target, sedimentation time 10min, thickness approximately 5 μ m; At same substrate temperature, YSZ target is evaporated, adjusting electronic beam current is 3.0A again, sedimentation time 40min, thickness approximately 20 μ m; After treat that substrate temperature is cooled to 100 DEG C, open vacuum chamber take out sample, complete CoSb 3painting layer deposition process.
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