CN112062591B - ZrO (ZrO)2Low-temperature rapid sintering method of ceramic and metal, connecting piece and device - Google Patents
ZrO (ZrO)2Low-temperature rapid sintering method of ceramic and metal, connecting piece and device Download PDFInfo
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Abstract
The invention relates to a ZrO2The low-temperature rapid sintering connection method of the ceramic and the metal comprises the following specific steps: ZrO 2 is mixed with2Pressing the powder into a blank containing air holes, and then sequentially pressing a metal substrate, a metal foil and ZrO2Placing the blank between electrodes in a vacuum furnace, and heating to 600-1200 ℃; ZrO using upper and lower electrode pairs2First, applying a current with a density of 50 to 300mA/mm to a metal foil/metal substrate2The alternating current lasts for 3s to 30min, and the output current density is switched to 5 to 300mA/mm2The direct current lasts for 3s to 30min, and finally the furnace body is cooled to room temperature to obtain ZrO2The connecting piece of the ceramic and the metal substrate. The invention does not need to sinter the ceramic green bodies at high temperature before connection, has low working temperature, short period and strong universality, and has obvious technical advantages and higher application value.
Description
Technical Field
The invention relates to a sintering and connecting integrated method of a heterogeneous material, in particular to a ZrO method2A low-temperature rapid sintering method of ceramics and metals, a connecting piece and a device.
Background
ZrO2The ceramic has the physical characteristics of high temperature resistance, wear resistance, high hardness, high temperature ion conductivity and the like, and has important application value in the fields of thermal barrier coatings, stomatology, Solid Oxide Fuel Cells (SOFC) and the like. To solve the problem of poor workability, ZrO is generally ground2Ceramics are connected with various metal materials to expand the application of the ceramics in industry. Conventional ZrO2The preparation process of the metal joint mainly comprises two steps of sintering a ceramic green body at a high temperature and then connecting the ceramic green body and a metal base material at the high temperature. At present, for ZrO2The sintering of ceramics mostly adopts the traditional pressureless sintering method, and the method generally needs to put a green body in the sintering furnaceThe compact ZrO can be obtained only by sintering for several hours at a high temperature of more than 1600 DEG C2A ceramic. For ZrO2At present, brazing, diffusion welding and other methods are commonly adopted for connecting ceramics and metals. Among them, diffusion welding requires applying a large pressure to a sample at a sufficiently high temperature and holding for a long time, and requires a large facility. In the brazing technology, metals or alloys with lower melting points than that of the base metal, such as Ag and Cu, are added in the middle of the connecting piece as brazing filler metal, and the liquid brazing filler metal is used for filling a joint gap and mutually diffusing with the base metal to realize connection by utilizing the wettability of the liquid brazing filler metal on ceramics in a high-temperature environment. However, typical Ag-based and Cu-based solders are in ZrO2In order to improve the wettability of the solder metal in ZrO2In the above wettability, active elements such as Zr, Ti, V and Hf are usually added to the solder base. Not only does this increase the material and manufacturing costs, but also the active elements can form intermetallic compounds in the braze, leading to a greatly increased brittleness of the braze, which makes it difficult to process into foils or wires. On the other hand, the interface reaction between the active metal and the base metal at high temperature is not easily controlled, and thus the joint performance may be adversely affected. In summary, the existing ZrO2The manufacturing process of the metal joint is complex, sintering and connection are carried out independently, and both of them need to be heat treated at high temperature for a long time to be completed, which undoubtedly causes a great consumption of energy and cost.
In order to develop a novel and efficient ceramic Sintering process, Cologna et al first proposed a Flash Sintering technology (Flash Sintering of Nanograin Zirconia in 2010) assisted by an electric field<5s at 850 deg.C, Journal of the American Ceramic Society, vol. 93, No. 11, 2010, P3556-P3559). The technology mainly utilizes the high-temperature ion conduction characteristic of the ceramic, and the electric field initiates the sudden rise of current, so that the activity of particles is improved under the influence of Joule heat, the diffusion and migration rate of the surface layer of crystal grains is promoted, and the ceramic is rapidly densified. However, this work describes sintering of ceramics only and does not involve joining ceramics to other materials. The applicant has previously provided a ZrO2Method for connecting ceramic and metal (Chinese patent application No. CN201710436241.4, publication No. CN107129316A, title of invention: ZrO2Ceramic to metal connectionMethod) using a direct current electric field as an auxiliary, and utilizing an electric field-induced interfacial electrochemical reaction to realize ZrO2The highest shear strength of the joint can reach 144MPa when the ceramic is connected with the metal. However, this method still requires the use of ZrO which is previously densified by sintering by other methods2Ceramics are used as the base material, and are applicable only to metals that can form an intermetallic compound reaction phase with Zr.
Disclosure of Invention
The invention is based on the flash sintering technology and electric field assisted ZrO2The research of ceramic/metal connection technology aims at providing an electric field assisted ZrO2And sintering and connecting the metal. The invention can ensure that ZrO can be realized in one step on the premise of compact and stable sintering connection2Sintering of the green body and its attachment to the metal. The problems of long preparation process cycle, poor efficiency and low energy utilization rate of the existing metal/ceramic connecting piece can be effectively solved.
The technical scheme of the invention is realized as follows:
the invention provides an electric field assisted ZrO2The low-temperature rapid sintering connection method of the ceramic and the metal comprises the following steps: a metal substrate, a metal foil, and ZrO containing air holes2The green body is sequentially placed on a lower electrode in a vacuum furnace from bottom to top, the vacuum pumping is carried out, the furnace body is heated to a target temperature and then an upper pressure head is screwed down, uniaxial pressure is applied to a sample group by utilizing an upper electrode and a lower electrode, then an alternating current power switch is turned on, and ZrO is firstly subjected to ZrO2After the AC electric field is applied to the metal foil/metal substrate, the AC power switch is closed and the DC power switch is immediately opened, and then ZrO is added2Closing a direct current power switch after the metal foil/metal substrate continuously outputs a direct current electric field, and then cooling the furnace body to room temperature to obtain ZrO2The connecting piece of the ceramic and the metal substrate.
As a further improvement of the invention, the method specifically comprises the following steps: metal substrate, metal foil, and ZrO having pores, the surfaces of which are mechanically polished and ultrasonically cleaned2Sequentially placing the green bodies on a lower electrode in a vacuum furnace from bottom to top, and vacuumizing to 10 DEG-2~10-5Pa, heating the furnace body to a target temperature of 600 toScrewing off the upper pressure head after 1200 ℃, applying uniaxial pressure of 0.1-10 MPa to the sample group by using the upper electrode and the lower electrode, then opening an alternating current power switch, and firstly carrying out ZrO on the sample group2Applying an alternating current electric field to the metal foil/metal substrate, closing the alternating current power switch and immediately opening the direct current power switch after lasting for 3 s-30 min, and then applying ZrO to the direct current power switch2Closing a direct current power switch after continuously outputting a direct current electric field for 3 s-30 min through the metal foil/metal substrate, and then cooling the furnace body to room temperature at the speed of 1-20 ℃/min to obtain ZrO2The connecting piece of the ceramic and the metal substrate.
As a further improvement of the invention, the ZrO2The green body is doped with 3-15 mol% of Y2O3ZrO of MgO or CaO stabilizers2ZrO containing air holes and prepared by pressing powder under the pressure of more than or equal to 100MPa2A green body.
As a further improvement of the present invention, the metal foil is a pure metal or alloy capable of forming an intermetallic compound interface reaction phase with Zr at high temperature, preferably, the metal foil includes, but is not limited to, copper foil, 72Ag28Cu (wt.%) alloy, sn3.0ag0.5cu (wt.%) alloy.
As a further improvement of the present invention, the metal substrate is a pure metal or alloy that can form a solid solution or intermetallic compound interface reaction phase with the metal foil used at high temperature, preferably, the metal substrate includes, but is not limited to, 304 stainless steel substrate, nickel-base superalloy GH3128, pure metal Ni.
As a further improvement of the invention, the initial electric field intensity effective value of the alternating current electric field is 50-300V/cm, and the current density effective value is 50-300 mA/mm2The frequency is 10-5000 Hz.
As a further improvement of the invention, the initial electric field intensity of the direct current electric field is 5-300V/cm, and the current density is 5-300 mA/mm2Wherein the metal substrate is connected with the negative electrode of the power supply, ZrO2The ceramic is connected with the positive pole of the power supply.
The invention further protects ZrO prepared by the method2The connecting piece of the ceramic and the metal substrate.
The invention further protects the electric field assisted ZrO2The low-temperature rapid sintering connecting device for the ceramic and the metal comprises a high-temperature vacuum furnace and a power supply system, wherein the high-temperature vacuum furnace consists of an upper pressure head 1, an upper electrode 2 and ZrO2Ceramic green compact 3, metal forming 4, metal substrate 5, bottom electrode 6, wire 7 and furnace body 12 are constituteed, electrical power generating system includes alternating current power supply 8 and DC power supply 9, alternating current power supply 8 connects alternating current power supply switch 10, DC power supply 9 connects DC power supply switch 11, and wherein upper pressure head 1 can freely go up and down and exert pressure to upper electrode 2.
As a further improvement of the present invention, the material of the upper electrode 2 and the lower electrode 6 is graphite, and the lead 7 is a high temperature resistant metal wire, preferably molybdenum or platinum.
The invention realizes ZrO2The mechanism of the low-temperature rapid sintering connection of the ceramic and the metal is as follows:
contains a certain amount (3 to 15 mol%) of Y2O3ZrO of MgO or CaO stabilizers2The ceramic exhibits ion-conducting characteristics after reaching a certain temperature (450 ℃). With the rise of the temperature, when the electrical conductivity of the ceramic reaches a certain value, the joule heat and mass transfer effect induced by the alternating current electric field in the ceramic blank can improve the activity of particles and the diffusion and migration rate of substances on the surfaces of the particles, so that the rapid densification at low temperature is realized. On the basis of which ZrO when further direct current is applied2Oxygen ion vacancies with positive charges inside can migrate to the negative electrode, the oxygen vacancies can be combined with Zr ions in crystal lattices to form metal Zr in a free state, and free electrons can be captured at the same time in ZrO2The interior is piled up to form fine vacancy defects. Therefore, when ZrO2When connected to the positive pole of the power supply, ZrO2A layer of Zr-Me intermetallic compound (Me represents the metal foil) is generated at the interface of the/Me to realize ZrO2Connection of the/Me interface. At the same time, ZrO2The joule heat released under the action of the current is also quickly conducted to the metal foil/metal substrate interface, the actual temperature is related to the applied current density, and can reach more than 1600 ℃ at most, and the connection with the metal can be easily realized.
If ZrO is carried out under pure direct current2Sintering and joining, then, joiningZrO of negative electrode part of power supply2Due to the higher electrical conductivity, not enough joule heat is generated to achieve full densification of the green body. Thus, the resulting joint may not achieve the desired bond because of the presence of more hole defects in the cathode portion. The alternating electric field is helpful to the ZrO2The uniform distribution of Joule heat is generated in the interior, and ZrO can be realized2Full densification of (2). In addition, by adopting the flexible metal as the intermediate transition layer, even under the condition that the temperature of the furnace is lower than the melting point temperature of the metal, the metal layer can be quickly melted due to the release of joule heat during electrification and has the function of filling gaps between interfaces, thereby providing sufficient interface contact for connection. Thus, ZrO obtained by the present invention2The strength of the metal joint is higher and the defects are less.
The invention has the following beneficial effects:
1. compared with the existing metal/ceramic joint preparation method of traditional sintering plus brazing or diffusion welding, the method provided by the invention does not need to perform high-temperature sintering on the ceramic green body in advance, and can directly realize ZrO in one step by applying a specific electric field2The sintering of the ceramic green body and the connection between the ceramic green body and the metal greatly shorten the preparation period of the metal/ceramic connecting piece and reduce the energy consumption.
2. Compared with the existing electric field auxiliary connection technology, the invention can flexibly select the corresponding intermediate layer metal foil according to the properties of the connected metal, thereby being suitable for wider connection systems. Moreover, the heat provided by the flash firing can quickly act on a ceramic-metal interface to melt the brazing filler metal, and then the secondary quick heating initiated by direct current can shorten the preparation process of the joint to dozens of seconds or even seconds, so that the method has high industrial application value.
3. The invention can flexibly regulate and control the grain size, the relative density and the shearing strength of the joint of the ceramic body by regulating the parameters of the alternating current power supply and the direct current power supply, and has the characteristics of simple operation, high efficiency and strong controllability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic diagram of a test apparatus used in the present invention;
FIG. 2 is a graph of the variation of the electric field strength, the current density and the power density with time recorded in the first embodiment of the present invention;
FIG. 3 shows ZrO obtained in example one of the present invention2A micro-topography of the interior of the ceramic;
FIG. 4 shows ZrO obtained in the first embodiment of the present invention2A microstructure diagram of a longitudinal section of a/Cu/304 stainless steel joint;
FIG. 5 shows ZrO obtained in example two of the present invention2A microstructure diagram of a longitudinal section of a/Cu/304 stainless steel joint;
FIG. 6 shows ZrO obtained in example III of the present invention2A microstructure diagram of a longitudinal section of a/Cu/304 stainless steel joint;
wherein, 1 is an upper pressure head, 2 is an upper electrode, and 3 is ZrO2The ceramic green body, 4 is metal foil, 5 is metal substrate, 6 is bottom electrode, 7 is wire, 8 is AC power supply, 9 is DC power supply, 10 is AC power supply switch, 11 is DC power supply switch, 12 is furnace body.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The test device is shown in figure 1 and comprises a high-temperature vacuum furnace and a power supply system, wherein the high-temperature vacuum furnace consists of an upper pressure head 1, an upper electrode 2 and ZrO2The ceramic green body 3, the metal foil 4, the metal substrate 5, the lower electrode 6, the lead 7 and the furnace body 12, wherein the power supply system comprises an alternating current power supply 8 and a furnace bodyThe direct current power supply 9, alternating current power supply 8 connects alternating current power switch 10, direct current power supply, 9 connect direct current power switch 11, and wherein go up the pressure head 1 and can freely go up and down and exert pressure to last electrode 2.
Before the experiment, the prepared ZrO2The ceramic green sheet 3, the metal foil 4 and the mechanically polished metal substrate 5 are sequentially placed on a lower electrode 6 in a furnace, and an ac power supply 8 and a dc power supply 9 are connected in parallel to an external electrode of a furnace body 12 in the manner shown in fig. 1. The furnace body 12 is vacuumized to 10-2~10-5Pa, heating to a target temperature of 600-1200 ℃, screwing off the upper pressure head 1, applying uniaxial pressure of 0.1-10 MPa to the sample group by using the upper electrode 2 and the lower electrode 6, then opening the alternating current power switch 10, wherein the effective value of the applied initial field strength is 50-300V/cm, and the effective value of the current density is 5-300 mA/mm2And keeping the current for 3 s-30 min after the current rises to the preset current density in an alternating current electric field with the frequency of 10-5000 Hz. Then, the AC power switch 10 is turned off, the DC power switch 11 is turned on, the initial field intensity is applied to be 5-300V/cm, and the current density is 5-300 mA/mm2And keeping the direct current field for 3 s-30 min after the current rises to the preset current density. After the electrification is finished, the direct current power switch 11 is closed, and the ZrO is cooled to the room temperature at the speed of 1-20 ℃/min2Sintering of the ceramic green body 3 and its connection to the metal substrate 5. The change law of the electric field intensity, the current density and the power density with time in the whole electrifying process is shown in figure 2.
The invention is further illustrated with reference to the following figures and examples, but the invention is not limited to the following examples.
Example 1
1. A mechanically polished 304 stainless steel substrate 5, a copper foil 4 having a thickness of 100 μm and a dopant of 3 mol% Y pressed at 500MPa2O3ZrO of stabilizer2The green bodies 3 are placed in the furnace in the manner of figure 1 in turn on a lower electrode 6;
2. the vacuum furnace is pumped to 1X 10-3After Pa, heating to 950 ℃ at the speed of 20 ℃/min and preserving heat for 15 min;
3. after connecting the circuit in the manner of fig. 1, the upper indenter 1 is unscrewed and the sample is alignedApplying 6MPa uniaxial pressure to the assembly, switching on the AC power switch 10, applying the initial field intensity of 100V/cm and the current density of 100mA/mm2An alternating electric field with a frequency of 100 Hz. When the current density rises to 100mA/mm2Timing is started later, and the AC power switch 10 is switched off after the time is kept for 30 s;
4. the DC power switch 11 is switched on, the initial field intensity is applied to be 50V/cm, the current density is 100mA/mm2In a direct current electric field of (3), wherein ZrO2The anode of the power supply is connected, and the 304 stainless steel is connected with the cathode of the power supply. When the current density rises to 100mA/mm2Timing is started later, and the direct-current power switch 11 is switched off after the time is kept for 30 s;
5. the furnace body 12 is cooled to room temperature at a rate of 5 ℃/min to obtain compact ZrO2A connection of ceramic 3 and 304 stainless steel 5.
The ZrO obtained was worked up using a universal tester (Instron 5689, Instron Corp., USA)2The shear strength test of the/Cu/304 stainless steel joint is carried out, and the obtained joint strength is 21 +/-1 MPa.
The time-dependent curves of the electric field strength, the current density and the power density recorded in example 1 of the present invention are shown in fig. 2. It can be seen that the alternating current and direct current electric fields are similar in change process and are kept at a constant voltage stage, at the moment, the electric field intensity is a preset value, and the current density continuously rises. When the current density rises to a preset value, the current density is kept constant, and meanwhile, the electric field intensity rapidly drops and is kept at a lower value. The whole process can be completed in several tens of seconds. ZrO (ZrO)2The micro-morphology of the interior of the ceramic is shown in fig. 3, and it can be observed that the ceramic body has achieved fully dense sintering. The microstructure of the joint cross section is shown in FIG. 4, ZrO2A layer of Cu-Zr intermetallic compound is generated on the/Cu interface, and ZrO is realized2Connection to Cu.
Example 2
This example differs from example 1 in that: the current density of the direct current power supply is 40mA/mm2Other parameters and steps are the same as in example 1. Measured ZrO2The shear strength of the/Cu/304 stainless steel joint is 5.3 +/-3 MPa. The microstructure of the cross section of the joint obtained is shown in FIG. 5, ZrO2At the/Cu interface form aThe layer is intercalated with a Cu-Zr intermetallic compound of a pure Cu phase, and at the same time, more Cu is remained on the lower side of the layer. We speculate that the reason for the lower strength is not in ZrO2the/Cu interface forms sufficient Cu-Zr intermetallic compounds.
Example 3
This example differs from example 1 in that: the current density of the direct current power supply is 120mA/mm2Other parameters and steps are the same as in example 1. Measured ZrO2The shear strength of the/Cu/304 stainless steel joint is 34 +/-2 MPa. The microstructure of the cross section of the joint obtained is shown in FIG. 6, ZrO2A thicker Cu-Zr intermetallic compound is formed at the/Cu interface, and only a small amount of Cu layer is arranged on the lower side of the Cu-Zr intermetallic compound. Thus, the shear strength of the resulting joint is high.
Example 4
This example differs from example 1 in that: the target furnace temperature was 800 ℃ and other parameters and procedures were the same as in example 1. Measured ZrO2The shear strength of the/Cu/304 stainless steel joint is 16 +/-3 MPa.
Example 5
This example differs from example 1 in that: the ZrO2Is ZrO doped with 8 mol% CaO stabilizer2Ceramic, other parameters and procedure were the same as in example 1. Measured ZrO2The shear strength of the/Cu/304 stainless steel joint is 18 +/-5 MPa.
Example 6
This example differs from example 1 in that: the metal foil was 72Ag28Cu (wt.%) alloy, and the other parameters and procedures were the same as in example 1. Measured ZrO2The shear strength of the/72 Ag28Cu/304 stainless steel joint is 42 +/-7 MPa.
Example 7
This example differs from example 1 in that: the metal substrate is a nickel-based superalloy GH3128, and other parameters and steps are the same as those of example 1. Measured ZrO2The shear strength of the/Cu/GH 3128 joint is 37 +/-9 MPa.
Example 8
This example differs from example 1 in that: the metal foil is Sn3.0Ag0.5Cu (w)t.%) alloy, the metal substrate was pure metal Ni, and other parameters and steps were the same as in example 1. Measured ZrO2The anti-shearing strength of the/Sn3.0Ag0.5Cu/Ni joint is 31 +/-4 MPa.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. Electric field assisted ZrO2The low-temperature rapid sintering connection method of the ceramic and the metal is characterized by comprising the following steps: metal substrate, metal foil, and ZrO having pores, the surfaces of which are mechanically polished and ultrasonically cleaned2Sequentially placing the green bodies on a lower electrode in a vacuum furnace from bottom to top, and vacuumizing to 10 DEG-2 ~ 10-5Pa, heating the furnace body to a target temperature of 600-1200 ℃, screwing off the upper pressure head, applying a uniaxial pressure of 0.1-10 MPa to the sample group by using the upper electrode and the lower electrode, then turning on an alternating current power switch, and firstly carrying out ZrO on the sample group2Applying an alternating current electric field to the metal foil/metal substrate, closing the alternating current power switch and immediately opening the direct current power switch after lasting for 3 s-30 min, and then applying ZrO to the direct current power switch2Closing a direct current power switch after continuously outputting a direct current electric field for 3 s-30 min through the metal foil/metal substrate, and then cooling the furnace body to room temperature at the speed of 1-20 ℃/min to obtain ZrO2A connecting piece of ceramic and metal substrate;
the metal foil is pure metal or alloy which can form an intermetallic compound interface reaction phase with Zr at high temperature; the metal substrate is pure metal or alloy which can form a solid solution or intermetallic compound interface reaction phase with the metal foil at high temperature;
the initial electric field intensity effective value of the alternating current electric field is 50-300V/cm, and the current density effective value is 50-300 mA/mm2The frequency is 10-5000 Hz; the initial electric field intensity of the direct current electric field is 5-300V/cm, and the current density is 5-300 mA/mm2Wherein the metal substrate is connected with the negative electrode of the power supply, ZrO2The ceramic is connected with the positive electrode of the power supply;
the above-mentionedZrO2The green body is doped with 3-15 mol% of Y2O3ZrO of MgO or CaO stabilizers2ZrO containing air holes and prepared by pressing powder under the pressure of more than or equal to 100MPa2A green body.
2. An electric field assisted ZrO according to claim 12The low-temperature rapid sintering connection method of the ceramic and the metal is characterized in that the metal foil is copper foil, 72Ag28Cu (wt.%) alloy or Sn3.0Ag0.5Cu (wt.%).
3. An electric field assisted ZrO according to claim 12The low-temperature rapid sintering connection method of the ceramic and the metal is characterized in that the metal substrate is a 304 stainless steel substrate, a nickel-based high-temperature alloy GH3128 or pure metal Ni.
4. ZrO prepared by the process according to any of claims 1 to 32The connecting piece of the ceramic and the metal substrate.
5. Electric field assisted ZrO2The low-temperature rapid sintering connecting device for the ceramic and the metal is characterized by comprising a high-temperature vacuum furnace and a power supply system, wherein the high-temperature vacuum furnace consists of an upper pressure head (1), an upper electrode (2) and ZrO2The ceramic green body (3), the metal foil (4), the metal substrate (5), the lower electrode (6), the lead (7) and the furnace body (12) form, the power supply system comprises an alternating current power supply (8) and a direct current power supply (9), the alternating current power supply (8) is connected with an alternating current power supply switch (10), the direct current power supply (9) is connected with a direct current power supply switch (11), and the upper pressure head (1) can freely lift and apply pressure to the upper electrode (2); the metal foil is pure metal or alloy which can form an intermetallic compound interface reaction phase with Zr at high temperature; the metal substrate is pure metal or alloy which can form a solid solution or intermetallic compound interface reaction phase with the metal foil at high temperature.
6. The device according to claim 5, characterized in that the upper electrode (2) and the lower electrode (6) are made of graphite and the wire (7) is a high temperature resistant wire.
7. The device of claim 6, wherein the refractory metal wire is molybdenum or platinum.
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