CN1652369A - Laminated ceramic thermocouple and its preparing method - Google Patents
Laminated ceramic thermocouple and its preparing method Download PDFInfo
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- CN1652369A CN1652369A CN200510009641.4A CN200510009641A CN1652369A CN 1652369 A CN1652369 A CN 1652369A CN 200510009641 A CN200510009641 A CN 200510009641A CN 1652369 A CN1652369 A CN 1652369A
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Abstract
The thermocouple is composed of upper insulation base plate 1, positive pole plate 2 and 2-1, middle insulation base plate 3, negative pole plate 4 and 4-1, and low insulation base plate 5. A first through hole is positioned at right side of the upper insulation base plate 1, and conductive terminal is embedded in the hole. A third through hole is at right side of low insulation base plate 5, and conductive terminal is embedded in the hole. There is first through trough in plate 2, and 2-1 is embedded in the through trough. Through holes or troughs are also made up on components 3 and 4. Stacking components 1, 2, 3, 4, 5 in sequences and sintering the stacked components at 1500-2500 deg.C and 0.1-80MPa produce the thermocouple. The disclosed thermocouple is as constituent of a measuring system in use for measuring temperature in harsh environment under condition of inert or vacuum environment.
Description
Technical field:
The present invention relates to a kind of preparation technology who is used to measure thermocouple assembly and this device thereof of high temperature.
Background technology:
Thermocouple should possess following condition as measuring senser element: (1) is for the stability of time and temperature; (2) reproducibility of pyroelectricity; (3) increase of thermoelectric potential is with the sensitiveness of the proportional increase of temperature; (4) thermoelectric potential varies with temperature linear or the simple function relation; (5) resisting temperature changes and thermal shock; (6) erosion of medium corrosion-resistant, mechanical property is good; (7) preparation method is simple, and the product that makes different plant produced go out has identical performance.
The principle of thermoelectric device is from the discovery of thermoelectric effect, and essence is that the material that two kinds of different conductors are formed has different electromotive forces in the junction.In the closed circuit of forming by two or more different conductors, if two kinds of conductor temperature differences just have electric current and occur in the loop.Thermocouple commonly used is made up of the metal material thermode of two kinds of different materials: the application of temperature of copper-corronil (constantan) is at-200～+ 300 ℃, nickel chromium triangle-nickel silicon alloy thermocouple can use 1300 ℃, tungsten-molybdenum, tungsten-(tungsten-rhenium) can reach 2400 ℃ in vacuum and inert atmosphere, (platinum-rhodium)-platinum can reach 1800 ℃ in oxide isolation, iridium-rhodium can reach 2100 ℃ in vacuum, weak oxide environment.
Usually the active time of thermocouple was from 200 hours to 2000 hours.To such an extent as to the impurity of trace all can change the serious difference of alloying component thermoelectric potential generation under hot conditions.It is that the alloying element of the thermode material surface that physics chemical action caused between thermode material and the environment is oxidized and consume that the hot thermocouple electromotive force is exported one of unsettled reason, and another causes the thermocouple destabilizing factor to be because the variation of ambient temperature causes the thermode material structure to change causes.In order to prolong the active time of thermocouple, the guard electrode material is avoided the influence of corrosive medium, and thermocouple generally adds protective casing to be used.Any heat-resisting, erosion-resisting insulation or semi-conducting material can be used as shell material.But the interaction between thermode material and sleeve pipe or the environment is unavoidable when high temperature.Therefore, measuring the thermocouple assembly that high temperature uses just need be made by the noble metal or the insulating material of costliness.When high temperature, the change of any physical state of metal all can cause sizable change of thermoelectric potential, and this value also can increase because of the variation of matrix welding zone; The thermocouple made of useful refractory metal all must in inert gas or vacuum, use.In order to realize the application of this thermocouple in different medium, the sleeve pipe that just must use anti-thermal shock, insulation, can use at high temperature.
Summary of the invention:
The purpose of this invention is to provide and a kind ofly have anti-thermal shock, high thermoelectric potential, do not contain noble metal and the laminated ceramic thermocouple that can under high temperature and corrosive environment, work and preparation method thereof.Laminated ceramic thermocouple of the present invention is made up of last insulated substrate 1, positive plate 2, positive electrode 2-1, middle insulated substrate 3, negative plate 4, negative electrode 4-1, following insulated substrate 5; Have between the upper surface on last insulated substrate 1 right side and the lower surface in first through hole, 6, the first through holes 6 and be inlaid with conducting terminal 7, have third through-hole 11 between the upper surface on following insulated substrate 5 right sides and the lower surface, be inlaid with conducting terminal 7 in the third through-hole 11; Have first groove 8 between the upper surface of positive plate 2 and the lower surface, positive electrode 2-1 is embedded in first groove 8; Have between the upper surface in middle insulated substrate 3 left sides and the lower surface and be inlaid with conduction tie point 9 in second through hole, 10, the second through holes 10; Have second groove 12 between the upper surface of negative plate 4 and the lower surface, negative electrode 4-1 is embedded in second groove 12; Last insulated substrate 1, positive plate 2, middle insulated substrate 3, negative plate 4, the connection that superposes from top to bottom of following insulated substrate 5, the lower surface of conducting terminal 7 connects the upper surface of positive electrode 2-1 in the positive plate 2 in the last insulated substrate 1, the upper surface of conduction tie point 9 in the insulated substrate 3 during the lower surface of positive electrode 2-1 connects in the positive plate 2, the lower surface of conduction tie point 9 connects the upper surface of negative electrode 4-1 in the negative plate 4 in the middle insulated substrate 3, the upper surface of conducting terminal 7 in the insulated substrate 5 under the lower surface of negative electrode 4-1 connects in the negative plate 4, its method of attachment is: will go up insulated substrate 1, positive plate 2, middle insulated substrate 3, negative plate 4, following insulated substrate 5 is superimposed according to order from top to bottom, is 1500～2500 ℃ in temperature, pressure is that sintering forms under the condition of 0.1～80Mpa.
The bulk ceramics thermocouple of indication of the present invention specifically is meant to be distributed in successively by some insulating ceramics base bands and semiconductor band and other few component parts forms a kind of thermocouple device in the ceramic material matrix, this thermocouple device is made up of a series of ceramic materials with particular conductivity characteristic, highly heatproof and shockproof ability or environmental resistance.The stock that matrix uses comprises A Long, Sialon, boride etc., and they all have excellent thermal shock resistance and resistance to corrosion.High-flexural strength ceramic material (the Si that strengthens by the oxynitrides that uses the low-density low heat capacity
3Ni
4, SiC, B
4C) can realize the raising of its thermal shock resistance as the thermocouple basis material.The present invention uses laminar structure to make a kind of ceramic electric thermo-couple, and it has anti-thermal shock, high thermoelectric potential, do not contain noble metal and advantage such as can work under high temperature and corrosive environment.
The present invention is in order to prepare ceramic base slab band, use be the non-metallic refractory nitride that is mixed with the refractory material oxide addition, the bulk ceramics thermocouple that utilizes this pottery band to make has the ability of high anti-thermal shock ability and opposing corrosive medium.The thermode of laminated ceramic thermocouple is to be made by adjustable metalloid material of resistance or dielectric material, and the tie point between two thermodes must be in high temperature and high temperature operate as normal during to the low temperature transition, and lead end is used for connecting measuring equipment.Positive polarity that the present invention makes composite electric conductor and negative polarity thermode are accurately packed in the groove of reserving in the matrix base band, again mounted base strap clamp is tightly reached the tight contact between the adjacent plane, in sintering process subsequently, because the acting in conjunction of temperature and pressure, these coarctate base bands just have been transformed into the thermocouple unit of an integral body.
Thermocouple of the present invention has 10～200 μ V/ ℃ sensitivity, the part that can be used as test macro is used for the usefulness of the measurement of 20～2000 ℃ of interior temperature of scope under adverse circumstances, inertia or the vacuum environment condition, and the use field comprises food and light industry, Metal and Alloy manufacturing industry, chemical industry, auto industry, aeronautics and space and scientific research equipment.
Description of drawings:
Fig. 1 is the overall structure schematic diagram of laminated ceramic thermocouple, Fig. 2 is the A-A view of Fig. 1, Fig. 3 is the structural representation of last insulated substrate 1, Fig. 4 is the structural representation of positive plate 2, Fig. 5 is the structural representation of middle insulated substrate 3, Fig. 6 is the structural representation of negative plate 4, and Fig. 7 is the structural representation of following insulated substrate 5.
Embodiment:
Embodiment one: referring to Fig. 1～7, the laminated ceramic thermocouple of present embodiment is made up of last insulated substrate 1, positive plate 2, positive electrode 2-1, middle insulated substrate 3, negative plate 4, negative electrode 4-1, following insulated substrate 5; Have between the upper surface on last insulated substrate 1 right side and the lower surface in first through hole, 6, the first through holes 6 and be inlaid with conducting terminal 7, have third through-hole 11 between the upper surface on following insulated substrate 5 right sides and the lower surface, be inlaid with conducting terminal 7 in the third through-hole 11; Have first groove 8 between the upper surface of positive plate 2 and the lower surface, positive electrode 2-1 is embedded in first groove 8; Have between the upper surface in middle insulated substrate 3 left sides and the lower surface and be inlaid with conduction tie point 9 in second through hole, 10, the second through holes 10; Have second groove 12 between the upper surface of negative plate 4 and the lower surface, negative electrode 4-1 is embedded in second groove 12; Last insulated substrate 1, positive plate 2, middle insulated substrate 3, negative plate 4, insulated substrate 5 connection that superposes from top to bottom down, the lower surface of conducting terminal 7 connects the upper surface of positive electrode 2-1 in the positive plate 2 in the last insulated substrate 1, the upper surface of conduction tie point 9 in the insulated substrate 3 during the lower surface of positive electrode 2-1 connects in the positive plate 2, the lower surface of conduction tie point 9 connects the upper surface of negative electrode 4-1 in the negative plate 4 in the middle insulated substrate 3, the upper surface of conducting terminal 7 in the insulated substrate 5 under the lower surface of negative electrode 4-1 connects in the negative plate 4, conducting terminal 7 connects measuring equipments.
The matrix of thermode positive plate 2 and negative plate 4 is and the identical ceramic material of basis material (going up insulated substrate 1, middle insulated substrate 3, following insulated substrate 5), so there is not tangible physical boundary between thermode and the matrix.Thermode, conduction tie point 9, lead terminal 7 are compared with basis material, have just added different conductivity ceramics particles therein, and these conductivity ceramics particles have formed " the netted ceramic electric conductor " of similar multicore cable.The quantity of the connection lead that forms in this " netted ceramic electric conductor " depends on size, thickness and the length of thermode and the ratio of thickness.If the thickness of thermode is too little, just can not form " the conducting band " that links up, can only form several parallel conducting regions.Under the bigger situation of thickness, two groups of thermodes " conducting band " could be formed thermocouple device.
Because the difference of the interpolation phase kind that comprises, thermode is different.In order to obtain " E's " thermode, use be to have the additive that weak beam is tied up the high concentration free carrier.Under Temperature Influence, the charge carrier on the positive electrode 2-1 is easy to be released, and looses to negative electrode 4-1 by conduction tie point 9.For stable diffusion potential is provided, the particle that adds phase should have strict distribution of sizes, that is: coarse granule (3～15 μ m): middle particle (1～3 μ m): fine particle (less than 1 μ m)=5: 4: 8.If fine particle is dominant, nonlinear change can take place in the relation of thermoelectric potential and temperature, and when relatively low and moderate temperature, this influence is just more remarkable, and when high temperature, the thermoelectric potential value will descend; If large-size particle is occupied an leading position, also non-linear phenomena can take place, but performance is opposite, under cryogenic conditions, the thermoelectric potential value is very little, but at high-temperature area, the thermoelectric potential value can produce the index increase with the rising of temperature.In both cases, all can run into obstacle, so just increase thermometric error the record of thermoelectric potential signal.The conductivity ceramics particle interpolation of adding in the basis material of positive electrode 2-1 comprises LaB mutually
6, NbN, C, ZrB
2, Mo
5Si
3, TiSi, Mo
2Si
5, VC, TiSi
2, SmB
6, VB
2, FeSi
2, VSi
2, TaSi
2, NbSi
2, Si, B
4C, ReSi
2In one or more.The resistance value and the thermoelectric potential value that depend on expection, the volume content that adds phase is between 2.5～98.5%.Have " being subjected to principal mode " and can from " positive " thermode, tie up the charge carrier semiconductor to the low concentration free carrier and the weak beam of this energy level in order to obtain " bearing " thermode, need to add by towing " capturing " a part of free carrier.2-1 is similar with positive electrode, the characteristic of negative electrode 4-1 also be by between the different size particle that adds clearly the ratio of definition characterize, thin, in, coarse grained ratio is 3: 4: 10.In order to prepare negative electrode 4-1, the interpolation of selection is CrN, ZrB mutually
6, YbB
6, SiC, WC, HfC, ZrC, TiC, TiN, TiB
2, TaC, VN, NbC, ZrN, TaB
2, NbB
2, TaB
6, WSi
2In one or more.The resistance value and the thermoelectric potential value that depend on selection, the volume content that adds phase is between 2.5～98.5%.Conduction tie point 9 between two kinds of different materials (thermode of positive polarity and negative polarity) is positioned among the ceramic material matrix, should form " conductive network that links up " at least at the area of join domain 25%.
For the ceramic lead terminal that improves welding usefulness to the resistance of oxidizing process, so that the signal of telecommunication between the positive negative thermal electrode in accurate recording hot junction, except the conduction that comprises pairing positive electrode and negative electrode is added mutually, also be that 3: 1 ratio has added TaN and B by volume in the conducting terminal 7 employed ceramic electric conductors
4Si.
The ceramic matrix material of last insulated substrate 1, positive plate 2, middle insulated substrate 3, negative plate 4, following insulated substrate 5 is A Long, Sialon, boride etc., and they all have excellent thermal shock resistance and resistance to corrosion.High-flexural strength ceramic material (the Si that strengthens by the oxynitrides that uses the low-density low heat capacity
3Ni
4, SiC, B
4C) can realize the raising of its thermal shock resistance as the thermocouple basis material.
Embodiment two: present embodiment is to prepare laminated ceramic thermocouple like this: will go up insulated substrate 1, positive plate 2, middle insulated substrate 3, negative plate 4, insulated substrate 5 is superimposed according to from top to bottom order down, be that 1500～2500 ℃, sintering pressure are that sintering forms under the condition of 0.1～80Mpa in sintering temperature.Because the matrix of positive plate 2 and negative plate 4 is and last insulated substrate 1, middle insulated substrate 3, the identical ceramic material of insulated substrate 5 down, so the matter of utmost importance of present embodiment is the insulating ceramic materials matrix that the preparation thermocouple device is used, utilize this basis material manufacturing to have the ceramic base band that prefabricated especially installation positive electrode 2-1, negative electrode 4-1 use groove 8 and conducting terminal 7, conduction tie point 9 usefulness through holes 6 are installed.The ceramic base band of high strength, high tenacity can be made by compacting, rolling, injection moulding or other feasible method, the pottery tape thickness is 0.1～3mm, thickness commonly used is 0.8～1.25mm, and the relative density of pottery band is 0.51～0.64, is 0.52～0.56 generally speaking.Because the conductivity of the ceramic matrix of " netted ceramic electric conductor " and insulation is subjected to the influence of heterogeneous reaction in the sintering process, in order to control this process, the ratio that needs selection C: H: O is 22: 0: 3 to 19: 11: 4 binding agent and a plasticizer.In order to improve the interlayer adhesion between the ceramic base band, pre-sample preparation pottery base band needs to carry out saturated processing in advance under the condition that contains 2～25wt.% water vapour, carries out sintering after processing is closed in satiety again in argon gas, nitrogen or carbon dioxide atmosphere.The big I that groove is installed in the reservation of electric conductor account for this pottery belt body long-pending 10～80%, the size of installing hole should reach the thickness of the width of any location hole of base band and band ratio be not less than 2, be not more than 12.The position of the perforate of base belt surface depend on pottery " netted ceramic electric conductor " and between them crossing the district and with third party's conductor bonding pad (lead terminal) selected cabling scheme when being connected.According to the design of thermoelectric conversion body, the method for ceramic matrix layer by lamination that is embedded with the insulation of ceramic electric conductor in the hole is assembled together.Pressure (several newton) a little during lamination, and in steam, carry out saturated processing and connect so that obtain identical interlayer.According to the character of matrix ceramic material, sintering process can adopt hot pressed sintering, HIP sintering, gas pressure sintering or pressureless sintering, 1500～2500 ℃ of sintering temperatures, sintering pressure 0.1～80MPa.Sintering starting stage (reaching 1250 ℃ at least), the effect of intensification is for the bonding auxiliary agent in the part or all of prefabricated assembly of burn off.
Embodiment three: what present embodiment and embodiment two were different is, in heat-treatment process to blank, because the matrix composition of insulation and the chemical reaction of sintering environment have generated wild phase, material system mainly is oxynitrides phase AlON in the present embodiment, this compound be pre-sample preparation base in oxidizing atmosphere when 1500～1900 ℃ of pressureless sintering condition downforce sintering according to AlN-Al
2O
3-Si
2ON
2The result that system is reacted.In order to improve the intensity of oxynitrides, use be beta-silicon nitride with very high static bending strength, according to the Si that uses
3N
4: AlN: Al
2O
3: Si
2ON
2Volume ratio was from 1: 2: 14: 4 to 2: 1: 11: 6 difference, this composition comprise that 0.5～15vol.% silicon nitride and oxynitrides are mutually.Use this material can under oxidation and inert conditions, use 1400 ℃ as the thermocouple of matrix manufacturing.
Embodiment four: what present embodiment and embodiment two, three were different is, the beta-silicon nitride phase of the main component of basis material for strengthening mutually by the O-Sialon, and this composition is at La
2O
3As Si under the catalyst condition
3N
4And H
2The chemical reaction generation takes place in O.Sintering condition is reduction (carbon dioxide) or inertia (nitrogen or argon gas) atmosphere, and hot pressed sintering or gas pressure sintering, pressure are 1 to 80MPa.According to the difference of pressure, sintering temperature is selected between 1650～1950 ℃.The middle mutually Si of the oxynitrides phase that contains 0.25～25vol.% in this composition, this oxynitrides
3N
4: Al
2O
3: Si
2ON
2: La
2O
3The volume ratio of content was at 30: 1: 1: 1 to 23: 3: 5: between 2.Use this material can under rugged environment, (alkali or the aqueous slkali of oxidation, reduction, inertia, most of motlten metal, acid solution, fusion) use to 1400 ℃ as the thermocouple of matrix preparation.
Embodiment five: what present embodiment and embodiment two, three, four were different is that basis material is mainly by SiC: B
4C: B
4The boron nitride that Si: C strengthens.This material hot pressing or gas pressure sintering in weak reducing atmosphere form, 1900～2500 ℃ of sintering temperatures, sintering pressure 1 to 80MPa.This material principal phase is BN, and the composite material that contains 0.5～20vol.% is as binding agent.This composite material comprises following composition BN mutually: MgO: SiC: B
4C: B
4Si: C, its volume parts ratio is 21: 2: 2: 3: 1: 1 to 8: 2: 2: 3: 1: 4.Use this material can under rugged environment, (alkali or the aqueous slkali of oxidation, reduction, inertia, most of motlten metal, acid solution, fusion) use to 2000 ℃ as the thermocouple of matrix preparation.
Claims (10)
1, laminated ceramic thermocouple is characterized in that it is by last insulated substrate (1), positive plate (2), positive electrode (2-1), middle insulated substrate (3), negative plate (4), negative electrode (4-1), insulated substrate (5) is formed down; Have first through hole (6) between the upper surface on last insulated substrate (1) right side and the lower surface, be inlaid with conducting terminal (7) in first through hole (6), have third through-hole (11) between the upper surface on following insulated substrate (5) right side and the lower surface, be inlaid with conducting terminal (7) in the third through-hole (11); Have first groove (8) between the upper surface of positive plate (2) and the lower surface, positive electrode (2-1) is embedded in first groove (8); Have second through hole (10) between the upper surface in middle insulated substrate (3) left side and the lower surface, be inlaid with conduction tie point (9) in second through hole (10); Have second groove (12) between the upper surface of negative plate (4) and the lower surface, negative electrode (4-1) is embedded in second groove 12; Last insulated substrate (1), positive plate (2), middle insulated substrate (3), negative plate (4), following insulated substrate (5) connection that superposes from top to bottom, the lower surface of conducting terminal (7) connects the upper surface of positive electrode (2-1) in the positive plate (2) in the last insulated substrate (1), the upper surface of conduction tie point (9) in the insulated substrate (3) during the lower surface of positive electrode (2-1) connects in the positive plate (2), the upper surface of negative electrode (4-1) in the lower surface connection negative plate (4) of conduction tie point (9) in the middle insulated substrate (3), the lower surface of the middle negative electrode (4-1) of negative plate (4) connects the upper surface of the middle conducting terminal (7) of insulated substrate (5) down.
2,, it is characterized in that in conducting terminal (7) 3: 1 by volume ratio adds TaN and B according to the described laminated ceramic thermocouple of claim 1
4S.
3, according to the described laminated ceramic thermocouple of claim 1, it is characterized in that positive electrode 2-1 is made up of ceramic matrix and the anodal particle that adds mutually, the volume content of anodal interpolation phase particle is 2.5～98.5%.
4, according to the described laminated ceramic thermocouple of claim 3, it is characterized in that described positive pole adds the phase particle and is made up of carse, medium and small three kinds of particles, wherein carse, medium and small size ratio is 5: 4: 8.
5,, it is characterized in that described anodal interpolation phase particle is LaB according to claim 3 or 4 described laminated ceramic thermocouples
6, NbN, C, ZrB
2, Mo
5Si
3, TiSi, Mo
2Si
5, VC, TiSi
2, SmB
6, VB
2, FeSi
2, VSi
2, TaSi
2, NbSi
2, Si, B
4C, ReSi
2In one or more.
6, according to the described laminated ceramic thermocouple of claim 1, it is characterized in that negative electrode 4-1 adds mutually particle by ceramic matrix and negative pole and forms, the volume content of negative pole interpolation phase particle is 2.5～98.5%.
7, according to the described laminated ceramic thermocouple of claim 6, it is characterized in that described negative pole adds the phase particle and is made up of carse, medium and small three kinds of particles, wherein carse, medium and small size ratio is 3: 4: 10.
8,, it is characterized in that it is CrN, ZrB mutually that described negative pole adds according to claim 6 or 7 described laminated ceramic thermocouples
6, YbB
6, SiC, WC, HfC, ZrC, TiC, TiN, TiB
2, TaC, VN, NbC, ZrN, TaB
2, NbB
2, TaB
6, WSi
2In one or more.
9,, it is characterized in that the ceramic matrix material of insulated substrate (1), positive plate (2), middle insulated substrate (3), negative plate (4), following insulated substrate (5) is A Long, Sialon or boride according to the described laminated ceramic thermocouple of claim 1.
10, the preparation method of the described laminated ceramic thermocouple of claim 1 is characterized in that last insulated substrate (1), positive plate (2), middle insulated substrate (3), negative plate (4), insulated substrate (5) is that 1500～2500 ℃, sintering pressure are to be sintered into one under the condition of 0.1～80Mpa according to from top to bottom order in sintering temperature down.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102156004A (en) * | 2011-03-10 | 2011-08-17 | 杨忠林 | Temperature measuring element |
| CN102584241A (en) * | 2012-02-24 | 2012-07-18 | 哈尔滨工业大学 | Zirconium boride based composite ceramic material thermocouple and preparation method thereof |
| CN107623067A (en) * | 2017-08-10 | 2018-01-23 | 南京航空航天大学 | A kind of miniature vertical structure thermo-electric device of portable high aspect ratio interlayer connection and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4437592B2 (en) * | 2000-04-24 | 2010-03-24 | いすゞ自動車株式会社 | Fast response thermocouple |
| CN2645245Y (en) * | 2003-07-15 | 2004-09-29 | 杜跃 | Thermocouple |
-
2005
- 2005-01-19 CN CNB2005100096414A patent/CN100372139C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102156004A (en) * | 2011-03-10 | 2011-08-17 | 杨忠林 | Temperature measuring element |
| CN102584241A (en) * | 2012-02-24 | 2012-07-18 | 哈尔滨工业大学 | Zirconium boride based composite ceramic material thermocouple and preparation method thereof |
| CN107623067A (en) * | 2017-08-10 | 2018-01-23 | 南京航空航天大学 | A kind of miniature vertical structure thermo-electric device of portable high aspect ratio interlayer connection and preparation method thereof |
| CN107623067B (en) * | 2017-08-10 | 2019-11-12 | 南京航空航天大学 | A kind of miniature vertical structure thermo-electric device and preparation method thereof of portable high aspect ratio interlayer connection |
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