CN107445621A - A kind of Cu Te are nanocrystalline/Cu2SnSe3Thermoelectric composite material and preparation method thereof - Google Patents
A kind of Cu Te are nanocrystalline/Cu2SnSe3Thermoelectric composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to field of thermoelectric material technique, and in particular to and a kind of Cu Te are nanocrystalline/Cu2SnSe3Thermoelectric composite material and preparation method thereof, the nanocrystalline volume ratios in the composite of Cu Te are 0.2 1.2% in the composite.Cu Te prepared by the present invention are nanocrystalline/Cu2SnSe3Type thermoelectric composite material shows preferable thermoelectricity capability, greatly improves Cu2SnSe3The ZT values of matrix；Technological operation needed for preparation is simple, parameter is controllable, suitable for fairly large production.
Description
Technical field
The invention belongs to field of thermoelectric material technique, and in particular to and a kind of Cu-Te is nanocrystalline/Cu2SnSe3Thermoelectricity composite wood
Material and preparation method thereof.
Background technology
Thermoelectric material is a kind of energy sexual function material that can be realized heat energy and directly be converted with electric energy, is had wide
Design for development, especially under the present situation of current energy resources shortage, the selection in the undoubtedly epoch of arising at the historic moment of thermoelectric material.
Its application field being related to can be that the application of Aero-Space generates electricity, and can also be the wrist-watch that body temperature generates electricity.Examined from realistic meaning
Consider, thermoelectric material may apply in the recycling of industrial exhaust heat, and can additionally be prepared from the point of view of thermoelectric cooling
The refrigeration plants such as environment-friendly type refrigerator, air-conditioning.In it environmental protection, high accuracy, noiseless the advantages that make it have huge development
Potentiality.
Thermoelectric figure of merit ZT is an essence parameter of the conversion efficiency for influenceing thermoelectric material, and its formula is expressed as ZT=σ
S2T/ κ, wherein S, σ, κ, T are respectively Seebeck coefficient, electrical conductivity, thermal conductivity and absolute temperature.For current application field,
Mainly there is the material such as bismuth telluride-type alloy and filled-type skutterudite compound to be widely used.Visited however as further
Rope, various types of thermoelectric material are found and transformed, although traditional thermoelectric material has good thermoelectricity capability,
Its expensive Cost Problems that prepare has turned into the power of Development of Novel thermoelectric material.
Cu2SnSe3It is a kind of compound with diamond-like, Cu-Se keys are advantageous to electronics existing for its inside
Transport, and the complicated lattice structure that the presence of itself largely distorts can effectively scatter phonon, so as to reduce the thermal conductivity of material
Rate, improve its ZT value.Therefore Cu2SnSe3Great development potentiality in terms of the raising of thermoelectricity capability be present in compound.Document
（Acta Materialia, 2013, 61: 4297-4304; J. Alloys. Compd, 2010, 506: 18-21; J.
Elect. Mater, 2012, 41: 1554-1557）It is to concentrate on doping to improve its thermoelectricity capability Deng, also achieves good
Good progress, but the regulatable difficulty of doping itself is relatively large, and doping concentration is relatively very limited, and use nanocrystalline multiple
The mode of conjunction can be very good solve problem above.
Binary copper-based compound Cu2X (X=S, Se or Te) is a kind of complicated compound of crystal structure.However, close
It is not widely deployed also in Cu-Te binary systems, is not related to also as the second mutually compound aspect.This patent utilizes melt
Rotation gets rid of that to prepare Cu-Te nanocrystalline, and using Cu-Te it is nanocrystalline as the second phase preparation Cu-Te it is nanocrystalline/Cu2SnSe3Type thermoelectricity
Composite, substantially increase matrix Cu2SnSe3Thermoelectric figure of merit, preparation method is novel, has good application prospect.
The content of the invention
Present invention aims at provide a kind of Cu-Te it is nanocrystalline/Cu2SnSe3Thermoelectric composite material, base can be significantly improved
Body Cu2SnSe3Thermoelectricity capability.
Present invention also offers a kind of Cu-Te it is nanocrystalline/Cu2SnSe3The preparation method of thermoelectric composite material, this method work
Skill is simple and easy to control, relative low price, to matrix Cu2SnSe3The improvement of thermoelectricity capability is particularly evident.
The present invention is achieved through the following technical solutions：
The invention provides a kind of Cu-Te it is nanocrystalline/Cu2SnSe3Type thermoelectric composite material, the Cu-Te are nanocrystalline compound
Volume ratio in material is 0.2-1.2%.
Further, mainly by Cu inside nanocrystalline second phases of the Cu-Te2-xTe、Cu2Te、Cu3-xTe2Phase composition.
Present invention also offers a kind of Cu-Te it is nanocrystalline/Cu2SnSe3The preparation method of type thermoelectric composite material, including with
Lower step：
（1）After weighing the uniform mixing of copper, tellurium block simple substance in proportion, it is put into rotation and gets rid of with quartz ampoule, copper roller is adjusted to suitable
Rotating speed and argon gas protection under carry out melt rotation get rid of, obtain containing ribbon sample nanocrystalline Cu-Te, after be ground into
Powder；
（2）Copper, tin, selenium powder simple substance is weighed in proportion to be uniformly put into graphite crucible after mixing, and by the graphite equipped with sample
Crucible is put into quartz ampoule, and it is carried out to be put into resistance furnace after vacuum sealing to carry out frit reaction, obtains Cu2SnSe3Ingot casting,
Afterwards by its hand-ground to powder；The copper, tin, the mol ratio of selenium powder are 2:1:3；
（3）By step（1）With（2）The powder of middle preparation, which is put into after weighing in proportion in ball mill, carries out planetary ball mill；
（4）Powder after ball milling is fitted into graphite jig, after be put into discharge plasma sintering stove and carry out vacuum-sintering,
Be made Cu-Te it is nanocrystalline/Cu2SnSe3Thermoelectric composite material.
Further, step（1）In, the copper billet, the mol ratio 1.6 ~ 1.8 of tellurium block:1.
Further step（1）In, the technological parameter that the melt rotation is got rid of is：Induced-current frequency is 28 ~ 35Hz, jet
Pressure is 0.02 ~ 0.06MPa, and the rotating speed of copper roller is 1500 ~ 3000r/min.
Further, step（2）In, the frit reaction is carried out using two-step method：First with 5 ~ 10 DEG C/min heating
Speed is warming up to 900 DEG C~1000 DEG C, is then incubated 10 ~ 12h, and insulation is cooled to 600 DEG C after terminating, is then incubated 24h, finally
Cool to room temperature with the furnace.
Further, step（3）In, the technological parameter of the planetary ball mill is：Ratio of grinding media to material is 15：1, rotating speed be 200 ~
300r/min, wherein star ball milling stop interval 20min, rear reversely ball milling 1h, stop 20min points of interval per positive ball milling 1h
Clock, circulate 2 ~ 3 times.
Further, step（4）In, the technological parameter of the discharge plasma sintering is：Choose the diameter of graphite jig
For 10mm or 12mm, vacuum is less than 4.5Pa, and sintering pressure is 50 ~ 60MPa, and heating rate is 100 DEG C/min, sintering temperature
For 450 ~ 500 DEG C, 10min is then incubated.
The beneficial effects of the invention are as follows：
（1）Cu-Te nano-crystalline thin ribbons prepared by the present invention are uniformly distributed, and grain size is in 500nm or so；
（2）Cu-Te prepared by the present invention is nanocrystalline/Cu2SnSe3Type thermoelectric composite material shows preferable thermoelectricity capability, greatly
Width improves Cu2SnSe3The ZT values of matrix；
（3）Technological operation is simple, parameter is controllable, suitable for fairly large production needed for present invention preparation.
Brief description of the drawings：
Fig. 1：Got rid of in embodiment 1 by melt rotation（1500r/min）The Cu-Te compound powder XRD spectrums of preparation.
Fig. 2：Embodiment 1 is got rid of by melt rotation（1500r/min）The Flied emission scanning electricity of the Cu-Te compound strips of preparation
Mirror（FESEM）Figure.
Fig. 3：The Cu-Te that is prepared in embodiment 1 after ball milling is nanocrystalline/Cu2SnSe3Thermoelectric composite material powder XRD spectrum.
Fig. 4：In embodiment 1 block Cu-Te it is nanocrystalline/Cu2SnSe3The Seebeck coefficient of thermoelectric composite material is with temperature
Change.
Fig. 5：In embodiment 1 block Cu-Te it is nanocrystalline/Cu2SnSe3The electrical conductivity of thermoelectric composite material with temperature change
Change.
Fig. 6：In embodiment 1 block Cu-Te it is nanocrystalline/Cu2SnSe3The thermal conductivity of thermoelectric composite material with temperature change
Change.
Fig. 7：In embodiment 1 block Cu-Te it is nanocrystalline/Cu2SnSe3The ZT value variation with temperature of thermoelectric composite material.
Fig. 8：In embodiment 2 block 0.8%Cu-Te it is nanocrystalline/Cu2SnSe3The Seebeck coefficient of thermoelectric composite material is with temperature
The change of degree.
Fig. 9：In embodiment 2 block 0.8%Cu-Te it is nanocrystalline/Cu2SnSe3The thermal conductivity of thermoelectric composite material is with temperature
Change.
Figure 10：In embodiment 2 block 0.8%Cu-Te it is nanocrystalline/Cu2SnSe3The ZT values of thermoelectric composite material are with temperature
Change.
Figure 11：Got rid of in embodiment 3 by melt rotation（2500r/min）The Cu-Te compound powder XRD spectrums of preparation.
Figure 12：Got rid of in embodiment 3 by melt rotation（1500r/min）The Flied emission of the Cu-Te compound strips of preparation is swept
Retouch Electronic Speculum（FESEM）Figure.
Figure 13：In embodiment 3 block 1.2%Cu-Te it is nanocrystalline/Cu2SnSe3The ZT values of thermoelectric composite material are with temperature
Change.
Embodiment
Illustrate the present invention below by way of instantiation.
Embodiment 1
1.1 by copper billet, tellurium block mol ratio 1.6:1 ratio weighs high-purity（>=99.9%）Copper, the common 12g of tellurium block simple substance,
Uniformly after mixing, it is put into rotation and gets rid of with quartz ampoule, copper roller is adjusted to 1500r/min rotating speeds and in argon gas protection (whiff pressure
For 0.02MPa), induced-current frequency be under 28Hz carry out melt rotation get rid of operation, obtain containing ribbon sample nanocrystalline Cu-Te
Product, afterwards by its hand-ground into powder；
1.2 according to mol ratio 2：1：3 weigh high-purity（>=99.9%）Copper, tin, the common 15g of selenium powder simple substance, uniformly mixing after
It is put into graphite crucible, and the graphite crucible equipped with sample is put into quartz ampoule, vacuum sealing is carried out to it（Vacuum is less than
0.01MPa）Processing；Quartz ampoule containing sample is put into resistance furnace and carries out melting, with 5 DEG C/min's during frit reaction
Then heating rate is incubated 12h from room temperature to 1000 DEG C, insulation is cooled to 600 DEG C after terminating, is then incubated 24h, obtains
Cu2SnSe3Ingot casting, after by its hand-ground to powder；
1.3 by the powder prepared in above-mentioned steps according to volume ratio be 0.4%：1(Cu-Te：Cu2SnSe3) ratio weigh 10g
Composite sample, after be put into ball mill and carry out homogenization ball milling（Ratio of grinding media to material is 15：1, rotating speed 300r/min）, wherein star
Ball milling stops interval 20min, rear reversely ball milling 1h, stops interval 20min minutes per positive ball milling 1h；
1.4 are fitted into the powder after ball milling in a diameter of 10mm graphite jigs, after be put into discharge plasma sintering stove
Row vacuum-sintering, it is less than 4.5Pa, sintering pressure 55MPa according to vacuum, heating rate is 100 DEG C/min, and sintering temperature is
480 DEG C, then be incubated 10min sintering condition be made Cu-Te it is nanocrystalline/Cu2SnSe3Thermoelectric composite material.
The XRD spectrum of dusty material nanocrystalline Cu-Te is shown in Fig. 1, the microscopic appearance of strip（FESEM）Fig. 2 is seen, by Fig. 1
Understood with Fig. 2, mainly by Cu2-xTe、Cu2Te、Cu3-xTe2The Cu-Te compounds of phase composition, its crystallite dimension are hundreds of and received
Rice.Powder XRD pattern in step 1.3 after ball milling is shown in Fig. 3, as shown in Figure 3 because the compound quantity for adding Cu-Te compares matrix water
It is flat very few, therefore fail to find the constituent phase of Cu-Te compounds.Finally prepd block Cu-Te is nanocrystalline/Cu2SnSe3Heat
The Sai Beike of composite, electrical conductivity, thermal conductivity, ZT value variation with temperature relations see Fig. 4,5,6,7 respectively, from figure
It can be seen that the Sai Beike of composite is slightly higher compared with non-complex matrix, thermal conductivity is significantly lower than non-complex matrix, ZT values also above
Non- compound tense is horizontal.
Embodiment 2
2.1 by copper billet, tellurium block mol ratio 1.7:1 ratio weighs high-purity（>=99.9%）Copper, the common 12g of tellurium block simple substance,
Uniformly after mixing, it is put into rotation and gets rid of with quartz ampoule, copper roller is adjusted to 2000r/min rotating speeds and in argon gas protection (whiff pressure
For 0.06MPa), induced-current frequency be under 30Hz carry out melt rotation get rid of operation, obtain containing ribbon nanocrystalline Cu-Te
Sample, afterwards by its hand-ground into powder；
2.2 according to mol ratio 2：1：3 weigh high-purity（>=99.9%）Copper, tin, the common 15g of selenium powder simple substance, uniformly mixing after
It is put into graphite crucible, and the graphite crucible equipped with sample is put into quartz ampoule, vacuum sealing is carried out to it（Vacuum is less than
0.01MPa）Processing；The good quartz ampoule containing sample of vacuum sealing is put into resistance furnace and carries out melting, frit reaction process
In with 5 DEG C/min heating rate from room temperature to 900 DEG C, be then incubated 12h, insulation is cooled to 600 DEG C after terminating, then
24h is incubated, obtains Cu2SnSe3Ingot casting, after by its hand-ground to powder；
2.3 by the powder prepared in above-mentioned steps according to volume ratio be 0.8%：1(Cu-Te：Cu2SnSe3) ratio weigh 10g
Composite sample, after be put into ball mill and carry out homogenization ball milling（Ratio of grinding media to material is 15：1, rotating speed 300r/min）, wherein star
Ball milling stops interval 20min, rear reversely ball milling 1h, stops interval 20min minutes per positive ball milling 1h；
2.4 are fitted into the powder after ball milling in a diameter of 10mm graphite jigs, after be put into discharge plasma sintering stove
Row vacuum-sintering, it is less than 4.5Pa, sintering pressure 60MPa according to vacuum, heating rate is 100 DEG C/min, and sintering temperature is
500 DEG C, then be incubated 10min sintering condition be made Cu-Te it is nanocrystalline/Cu2SnSe3Thermoelectric composite material.
The block Cu-Te of preparation is nanocrystalline/Cu2SnSe3The Sai Beike of thermoelectric composite material, thermal conductivity, ZT values are with temperature
Variation relation sees Fig. 8,9,10 respectively, and as can be seen from the figure the more non-complex matrixes of the Sai Beike of composite are high, thermal conductivity
Significantly lower than non-complex matrix, ZT values are horizontal also above non-compound tense.
Embodiment 3
3.1 by copper billet, tellurium block mol ratio 1.8:1 ratio weighs high-purity（>=99.9%）Copper, the common 12g of tellurium block simple substance,
Uniformly after mixing, it is put into rotation and gets rid of with quartz ampoule, copper roller is adjusted to 3000r/min rotating speeds and in argon gas protection (whiff pressure
For 0.04MPa), induced-current frequency be under 35Hz carry out melt rotation get rid of operation, obtain containing ribbon nanocrystalline Cu-Te
Sample, afterwards by its hand-ground into powder；
3.2 according to mol ratio 2：1：3 weigh high-purity（>=99.9%）Copper, tin, the common 15g of selenium powder simple substance, uniformly mixing after
It is put into graphite crucible, and the graphite crucible equipped with sample is put into quartz ampoule, vacuum sealing is carried out to it（Vacuum is less than
0.01MPa）Processing；The good quartz ampoule containing sample of vacuum sealing is put into resistance furnace and carries out melting, frit reaction process
In with 5 DEG C/min heating rate from room temperature to 1000 DEG C, be then incubated 10h, insulation is cooled to 600 DEG C after terminating, so
After be incubated 24h, obtain Cu2SnSe3Ingot casting, after by its hand-ground to powder；
3.3 by the powder prepared in above-mentioned steps according to volume ratio be 1.2%：1(Cu-Te：Cu2SnSe3) ratio weigh 10g
Composite sample, after be put into ball mill and carry out homogenization ball milling（Ratio of grinding media to material is 15：1, rotating speed 300r/min）, wherein star
Ball milling stops interval 20min, rear reversely ball milling 1h, stops interval 20min minutes per positive ball milling 1h；
3.4 are fitted into the powder after ball milling in a diameter of 10mm graphite jigs, after be put into discharge plasma sintering stove
Row vacuum-sintering, it is less than 4.5Pa, sintering pressure 55MPa according to vacuum, heating rate is 100 DEG C/min, and sintering temperature is
480 DEG C, then be incubated 10min sintering condition be made Cu-Te it is nanocrystalline/Cu2SnSe3Thermoelectric composite material.
The XRD spectrum of Cu-Te nanometer crystal powder powder materials is shown in Figure 11, the microscopic appearance of strip（FESEM）Figure 12 is seen, by Figure 11
Understand that the material obtained by step 1) is main Cu with Figure 122-xTe、Cu2Te、Cu3-xTe2The Cu-Te compounds of phase composition, its
Crystallite dimension is hundreds of nanometers.Finally prepd block Cu-Te is nanocrystalline/Cu2SnSe3The ZT values of thermoelectric composite material are with temperature
The variation relation of degree sees Figure 13 respectively, as can be seen from the figure level of the ZT values of composite apparently higher than non-compound tense.
Comparative example 1
Cu-Te manocrystalline powders and matrix Cu are prepared according to the step 1.1 of embodiment 1 and 1.22SnSe3Thermoelectric material, will be above-mentioned
The powder prepared in step is 0.1% according to volume ratio：1(Cu-Te：Cu2SnSe3) ratio weigh 10g composite sample, after put
Enter and homogenization ball milling is carried out in ball mill, then powder after ball milling is carried out plasma discharging burning by ball milling parameter with embodiment 1
Knot, sintering parameter with embodiment 1 be made Cu-Te it is nanocrystalline/Cu2SnSe3Thermoelectric composite material.But to 0.1%Cu-Te nanometers
Crystalline substance/Cu2SnSe3The thermoelectricity capability measurement of thermoelectric composite material is as shown in table 1, it can be seen that electrical conductivity under normal temperature, thermal conductivity and
Seebeck coefficient is not obviously improved, and its ZT value and matrix are more or less the same under high temperature 700K, illustrate that 0.1%Cu-Te is nanocrystalline
It is compound not to be obviously improved matrix Cu2SnSe3Thermoelectricity capability.
Comparative example 2
Cu-Te manocrystalline powders and matrix Cu are prepared according to the step 1.1 of embodiment 2 and 1.22SnSe3Thermoelectric material, will be above-mentioned
The powder prepared in step is 1.5% according to volume ratio：1(Cu-Te：Cu2SnSe3) ratio weigh 10g composite sample, after put
Enter and homogenization ball milling is carried out in ball mill, then powder after ball milling is carried out plasma discharging burning by ball milling parameter with embodiment 1
Knot, sintering parameter with embodiment 1 be made Cu-Te it is nanocrystalline/Cu2SnSe3Thermoelectric composite material.Nanocrystalline to 1.5%Cu-Te/
Cu2SnSe3The thermoelectricity capability measurement of thermoelectric composite material is as shown in table 1, it can be seen that Seebeck coefficient and electrical conductivity under normal temperature
It is improved, although certain nanostructured can effectively reduce the lattice thermal conductivity of thermoelectric material so as to reduce overall thermal conductance
Rate, but because the thermal conductivity raising that the thermal conductivity bulk effect of 1.5%Cu-Te nanocrystalline powders itself is brought has exceeded nanostructured
The reduction of caused thermal conductivity, therefore heat conductivity raises, its ZT value drops compared with matrix on the contrary under 700K under final high temperature
It is low, illustrate the nanocrystalline compound and not up to improvement matrix Cu of 1.5%Cu-Te2SnSe3Thermoelectricity capability effect.
Table 1
Comparative example 3
By copper billet, tellurium block mol ratio 1.9:1 ratio weighs high-purity（>=99.9%）Copper, the common 12g of tellurium block simple substance, uniformly
After mixing, it is put into rotation and gets rid of and carry out rotation with quartz ampoule and get rid of, parameter such as embodiment 3 is got rid of in rotation, and experiment is found due to copper billet, tellurium block mol ratio
The viscosity for changing Cu-Te melts, cause the mobility of melt poor, argon gas injection simultaneously it is unsuccessful, can not prepare
Band nanocrystalline Cu-Te.
Comparative example 4
By copper billet, tellurium block mol ratio 1.8:1 ratio weighs high-purity（>=99.9%）Copper, the common 12g of tellurium block simple substance, uniformly
After mixing, it is put into rotation and gets rid of with quartz ampoule, copper roller is adjusted to 1000r/min rotating speeds and (whiff pressure is in argon gas protection
0.01MPa), induced-current frequency is to carry out melt rotation under 25Hz to get rid of operation, is found in experimentation due to induced-current frequency
Change cause Cu-Te can not reach molten condition, alloy block is only that peony state is presented, and can not be blown
Rotation, which is got rid of, prepares the nanocrystalline bands of Cu-Te.
Claims (8)
1. a kind of Cu-Te is nanocrystalline/Cu2SnSe3Type thermoelectric composite material, it is characterised in that the Cu-Te is nanocrystalline compound
Volume ratio in material is 0.2-1.2%.
2. Cu-Te according to claim 1 is nanocrystalline/Cu2SnSe3Type thermoelectric composite material, it is characterised in that the Cu-
Mainly by Cu inside nanocrystalline second phases of Te2-xTe、Cu2Te、Cu3-xTe2Phase composition.
3. a kind of Cu-Te as claimed in claim 1 or 2 is nanocrystalline/Cu2SnSe3The preparation method of type thermoelectric composite material, its
It is characterised by, comprises the following steps：
（1）After weighing the uniform mixing of copper, tellurium block simple substance in proportion, it is put into rotation and gets rid of with quartz ampoule, copper roller is adjusted to suitable
Rotating speed and argon gas protection under carry out melt rotation get rid of, obtain containing ribbon sample nanocrystalline Cu-Te, after be ground into
Powder；
（2）Copper, tin, selenium powder simple substance is weighed in proportion to be uniformly put into graphite crucible after mixing, and by the graphite equipped with sample
Crucible is put into quartz ampoule, and it is carried out to be put into resistance furnace after vacuum sealing to carry out frit reaction, obtains Cu2SnSe3Ingot casting,
Afterwards by its hand-ground to powder；
（3）By step（1）With（2）The powder of middle preparation, which is put into after weighing in proportion in ball mill, carries out planetary ball mill；
（4）Powder after ball milling is fitted into graphite jig, after be put into discharge plasma sintering stove and carry out vacuum-sintering,
Be made Cu-Te it is nanocrystalline/Cu2SnSe3Thermoelectric composite material.
4. preparation method according to claim 3, it is characterised in that step（1）In, the copper billet, the mol ratio of tellurium block
1.6~1.8:1。
5. the preparation method according to claim 3 or 4, it is characterised in that：Step（1）In, the melt revolves the technique got rid of
Parameter is：Induced-current frequency is 28 ~ 35Hz, and whiff pressure is 0.02 ~ 0.06MPa, and the rotating speed of copper roller is 1500 ~ 3000r/
min。
6. preparation method according to claim 3, it is characterised in that：Step（2）In, the frit reaction uses two-step method
Carry out：900 DEG C~1000 DEG C are warming up to 5 ~ 10 DEG C/min heating rate first, 10 ~ 12h is then incubated, after insulation terminates
600 DEG C are cooled to, 24h is then incubated, finally cools to room temperature with the furnace.
7. preparation method according to claim 3, it is characterised in that step（3）In, the technological parameter of the planetary ball mill
For：Ratio of grinding media to material is 15：1, rotating speed is 200 ~ 300r/min, and wherein star ball milling stops interval 20min per positive ball milling 1h, after
Reverse ball milling 1h, stops interval 20min minutes, circulates 2 ~ 3 times.
8. according to the preparation method described in claim any one of 3-7, it is characterised in that step（4）In, the plasma discharging
The technological parameter of sintering is：Choose a diameter of 10mm or 12mm of graphite jig, vacuum is less than 4.5Pa, sintering pressure for 50 ~
60MPa, heating rate are 100 DEG C/min, and sintering temperature is 450 ~ 500 DEG C, is then incubated 10min.
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