CN108267484B - High-temperature and high-pressure transport property measuring device based on diamond anvil cell - Google Patents
High-temperature and high-pressure transport property measuring device based on diamond anvil cell Download PDFInfo
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- 238000012360 testing method Methods 0.000 claims abstract description 15
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
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Abstract
The invention discloses a diamond anvil cell based high-temperature and high-pressure transport property measuring device, and belongs to the technical field of physical quantity in-situ measuring devices under extreme conditions. The device comprises an upper die (1) of the press, a lower die (11) of the press, diamond anvil blocks (2), a metal gasket (6) clamped between the two diamond anvil blocks, the two diamond anvil blocks are respectively fixed on a supporting block (4) and a shaking table (5), a shaking table base (7) is arranged at the bottom of the shaking table, a shaking table cover (8) is arranged at the upper part of the shaking table, mica sheets (9) are arranged between the supporting block and the shaking table base as well as the press, a prepared ceramic die (3) is fixed in a step groove of the supporting block, and a ceramic die (13) is sleeved on the shaking table. The invention ensures that the sample (10) is in a high-temperature and high-pressure environment, realizes the test of the high-temperature and high-pressure transport property of the sample on the basis of convenient operation and overcoming the defects of damage to a press and pressure loss caused by high temperature, and provides favorable conditions for the in-situ measurement of multiple physical quantities under extreme conditions.
Description
Technical Field
The invention belongs to the technical field of in-situ measurement devices of physical quantities under extreme conditions, and particularly relates to a device for measuring high-temperature and high-voltage electric transportation and thermal transportation properties in a diamond anvil cell.
Background
A Diamond Anvil Cell (DAC) is the only scientific device capable of generating million-atmosphere static pressure at present and is the most important scientific instrument in the field of high-pressure science and technical research. The known upper limit of pressure exceeds 1TPa by utilizing a specially-made two-diamond anvil, if a high-temperature technology is combined, the physical and chemical properties of related substances in the earth can be completely researched by a laboratory simulation temperature and pressure environment, the method is an important way for explaining seismic wave data and understanding the internal structure and dynamic process of the earth, and the development of the DAC technology makes it possible to reveal the secret in the earth. Meanwhile, the pressure and the temperature can regulate and control the energy gap width, the lattice structure and the atom occupation of the material, and the research on the electric transport and the thermal transport properties of the material at high temperature and high pressure plays a vital role in analyzing the processes of the structure, chemical bonds, lattice vibration, molecular rotation and the like of the material. However, how to detect the change of the pressure and the temperature to the material transportation property in real time has a huge technical problem, the main reason is that the related experimental technology of the in-situ test under high temperature and high pressure is very complicated, and the technical breakthrough of the improvement of the diamond anvil cell device is mainly realized in order to fundamentally solve the problem.
The pressure generation and calibration technology under extreme conditions is mature up to now, but the temperature range of the experiment is limited due to the high-temperature oxidation of the diamond anvil, the high-temperature damage of the diamond anvil press and the like, so that the heating problem of the sample in the DAC is not well solved. The prior art generally has three methods for heating a sample in a DAC: (1) a strong laser pulse is utilized to penetrate through the diamond to directly heat the sample; (2) putting the press into an oven, and heating the press to further increase the temperature of the sample; (3) and winding an electric heating wire in the DAC, and heating the DAC by utilizing the electrified electric heating wire so as to improve the temperature of the sample. However, all three of the above methods have their own drawbacks that limit their use: in the first method, a sample is heated by using strong laser pulses, and a heat insulation and pressure transmission medium is introduced, so that partial measurement of electric transportation and heat transportation properties is limited. In addition, because the method adopts the black body radiation mode for temperature measurement, the requirement on experimental equipment is high, the temperature measurement error is large, the temperature measurement error of the temperature measurement method can reach about 50K above 1500K, and the temperature measurement error is large below 1500K. In the second and third methods, the temperature range of the experiment is limited because the press is damaged due to the deformation caused by the over-high temperature of the press, the pressing disc spring is softened at high temperature, the pressure is lost, and the diamond anvil exposed in the air is oxidized.
In order to solve the damage to the press and the pressure loss caused by the high-temperature environment, an inner-cooling diamond anvil cell press (patent number: 201510036364.X) of the applicant discloses a diamond anvil cell press with built-in water cooling, wherein in the high-temperature experiment process, a press body can be ensured to be at room temperature, the problems of high-temperature damage and pressure loss of the press are basically solved, however, the experiment temperature is still limited because the problem of oxidation of the diamond anvil cell cannot be solved. The inner-cooling diamond anvil cell press adopts a sleeve type design, and the arrangement and operation difficulty of an electrode and a thermocouple is higher; because the refrigerating effect of the press is obvious and most heat is consumed, the electric heating wire needs higher power, the service life of the electric heating wire is shortened, and the temperature rising space is still limited; in order to solve the problem of temperature limitation, a mica sheet is placed between the support block and the press, which in turn limits the accuracy of leveling and centering; the heating wire twines on tray upper surface or gasket, and the effective heat that transmits to on the sample is few, and more heat is dissipated with the form of air heat conduction, thermal convection, heat radiation.
Disclosure of Invention
The invention aims to solve the technical problems that a brand-new high-temperature and high-pressure diamond anvil cell press is designed, a ceramic die, a bilateral heating mode, a shaking table and the like are adopted, a sample is ensured to be in a high-temperature and high-pressure environment, and the measurement of the high-temperature and high-pressure transport property of the sample is realized on the basis of improving the convenience of experimental operation; the water cooling system maintains the room temperature of the press body, further prevents the high temperature damage of the press and the pressure loss caused by the high temperature, and the introduction of the vacuum system inhibits the oxidation of diamond, provides a wider experimental temperature range and is beneficial to the measurement of the high-temperature and high-pressure transport properties of the sample.
The measurement of the transport property of the anvil based on the diamond is divided into measurement of the electric transport property and measurement of the thermal transport property. The measurement of the electrical transport properties mainly comprises: dielectric properties, resistance, magnetic resistance, carrier concentration, Hall coefficient and the like are measured by an electrode arranged on the anvil face of the diamond anvil cell in combination with a system of resistivity, impedance spectrum, Hall and the like; the measurement of the heat transport properties mainly includes: thermal conductivity, seebeck coefficient, etc. were measured by thermocouple temperature measurement in conjunction with thermal transport analysis placed on a diamond anvil.
The specific technical scheme of the invention is described in the following by combining the figures 1 and 2 in the attached drawings of the specification.
The utility model provides a transport nature measuring device based on diamond anvil cell high temperature high pressure, its structure includes press upper die 1, press lower mould 11, two diamond anvil cells 2, press the metal gasket 6 of putting between two diamond anvil cell 2 hammering block faces, packing sample 10 in the gasket sample cavity, the temperature measurement point of two thermocouples 16 is fixed respectively at two diamond anvil cell 2 lateral edges, one end of test electrode 15 is placed and is used for connecting testing arrangement in another end of sample cavity, two diamond anvil cell 2 bottom surfaces are fixed respectively in the support block 4 below and shaking table 5 top, place mica sheet 9 between press upper die 1 and support block 4. The structure is also provided with a supporting block end ceramic mould 3 and a shaking table end ceramic mould 13, and heating wires are respectively wound in the supporting block end ceramic mould 3 and the shaking table end ceramic mould 13; the upper die 1 and the lower die 11 of the press adopt a four-column structure; the middle of the supporting block 4 is provided with a hole, and the inner wall of the supporting block 4 is provided with a circumferential stepped groove for placing the supporting block end ceramic die 3; the cradle 5 is in a shape that the ball segment and a cylinder on the bottom surface of the ball segment are integrated and a hole is formed in the middle, the radius of the cylinder is smaller than that of the bottom surface of the ball segment, and a cradle end ceramic die 13 is sleeved on a step formed by the outer surface of the cylinder and the bottom surface of the ball segment; the shaking table 5 is placed on a shaking table base 7, a hole is formed in the middle of the shaking table base 7, a spherical pit is formed in the upper surface of the shaking table base 7 and is matched with the spherical surface of the shaking table 5, a circular shaking table cover 8 is placed on the upper portion of the shaking table 5, and the shaking table 5 is clamped between the shaking table base 7 and the shaking table cover 8 and is fixed through a leveling screw 26; mica sheets 9 are placed between the shaking table base 7 and the lower die 11 of the press, and the mica sheets 9 are placed on the ceramic die 3 at the supporting block end.
The invention is a measuring device based on the high-temperature and high-pressure transport property of a diamond anvil cell, so that a high-temperature and high-pressure experimental environment needs to be manufactured. The mechanism of the high pressure environment is as follows: according to the large-mass supporting principle, a sample 10 filled in a sample cavity of the metal gasket 6 is extruded by two diamond anvils 2 by utilizing the characteristic of high diamond hardness, so that a high-pressure environment is generated; the mechanism of generation of the high temperature environment is: the temperature of the sample 10 is further improved by heating the DAC through the electrified electric heating wires, the iron-chromium-aluminum electric heating wires with high resistivity are selected, the electric heating wires are wound on the supporting block end ceramic die 3 and the shaking table end ceramic die 13, the supporting block end ceramic die 3 and the shaking table end ceramic die 13 are respectively fixed at the designated positions of the supporting block 4 and the shaking table 5, and a high-temperature environment and a temperature difference between the upper surface and the lower surface of the sample 10 are generated.
The high-temperature high-pressure diamond anvil cell press in the device adopts a four-column design (different from a sleeve type design in the background technology), provides a wide experiment operation space for experiments, and obviously reduces the experiment operation difficulty; the bottom surface of the spherical segment of the shaking table 5 is designed, so that convenience is provided for leveling and centering the diamond anvil cell 2, and the technical problem caused by the process flatness of the mica sheet 9 is solved; the introduction of shaking table base 7 provides the platform for arranging of mica sheet 9, and the placing of upper and lower both sides mica sheet 9 has effectively isolated the heat loss of heat conduction form.
The specific structure of the pallet end ceramic mold 3 and the table end ceramic mold 13 will be further described below.
The supporting block end ceramic mould 3 and the shaking table end ceramic mould 13 are made of high-temperature-resistant ceramic materials and are customized into two different configurations, namely a flat-bottom mould and a trapezoidal mould; by adjusting the power of the heating wires in the supporting block end ceramic mold 3 and the shaking table end ceramic mold 13, the temperature gradient required for measuring the heat transport property can be generated on the upper and lower surfaces of the sample 10.
The cross section of the flat bottom mould is in a rectangular annular shape, grooves 27 are carved on the upper surface and the lower surface of the flat bottom mould, the ends of the grooves 27 on the upper surface and the lower surface are communicated end to end through flat bottom mould holes 28, and electric heating wires are wound on the flat bottom mould through the flat bottom mould holes 28 and the grooves 27 and are embedded into the grooves 27; the trapezoidal mold is in a convex annular shape in cross section, the cross section of the trapezoidal mold is composed of an annular base part and an annular protruding part, an inner annular trapezoidal platform 29 and an outer annular trapezoidal platform 29 are formed on the upper surface of the base part and the side surface of the protruding part, a trapezoidal mold hole 30 is formed in the protruding part along the radius direction, electric heating wires sequentially penetrate through the trapezoidal mold hole 30 and are wound on the trapezoidal mold, and the wound electric heating wires are located in the edge of the base part.
The contact surface between the support block end ceramic mold 3 and the support block 4, the contact surface between the shaking table end ceramic mold 13 and the shaking table 5, and the contact surface between the support block end ceramic mold 3 and the mica sheet 9 are all fixed by using a high-temperature repairing agent.
The main reasons for the short service life of the heating wire are that the traditional heating wire winding mode can generate deformation at high temperature to cause local heating wire short circuit, and the heating wire falls off due to different thermal expansion coefficients of the support block 4 and the high-temperature repairing agent. The flat-bottom ceramic mold and the trapezoidal ceramic mold with two different geometric configurations can be used according to different experimental requirements, the flat-bottom ceramic mold is wound with relatively longer electric heating wires, and the sample 10 can reach higher temperature; the design of the step of the trapezoidal ceramic mold reduces the contact area of the heating wire and air, inhibits the heat convection and the heat radiation form, and reduces the heat dissipation caused by the heating of the heating wire to the press. The ceramic mould with each geometrical configuration is processed into different sizes according to the geometrical configurations of the supporting block 4 and the shaking table 5, so that the ceramic mould is ensured to be just fixed in the stepped groove on the inner wall of the supporting block 4 and on the platform of the shaking table 5, and the heating and temperature control on two sides can be carried out. Compared with the electric heating wire winding on the metal gasket 6 in the background technology, the two-side heating temperature control mode has the advantages that: heating the sample 10 on both sides can achieve higher temperatures; double-sided temperature control can produce an ideal temperature difference across the sample 10 to enable measurement of heat transport properties.
The diamond anvil cell-based high-temperature high-pressure transport property measuring device can be additionally provided with a water cooling system. The water cooling system is composed of a beryllium copper built-in water tank water cooling platform upper die 17 and a beryllium copper built-in water cooling platform lower die 18, the beryllium copper built-in water tank water cooling platform upper die and the beryllium copper built-in water cooling platform lower die are respectively arranged on the upper surface of the press upper die 1 and the lower surface of the press lower die 11, and the built-in water tank is connected with the circulating water cooler through a pneumatic quick coupling 19 and; the upper water cooling platform mould 17 and the lower water cooling platform mould 18 are both provided with central holes; by rotating the nuts on the water-cooling slide rails 20, the water-cooling platforms are applied with a force approaching each other, so that the water-cooling platform upper die 17 and the press upper die 1 are ensured to be in close contact with each other, and the water-cooling platform lower die 18 and the press lower die 11 are ensured to be in close contact with each other.
The beryllium-copper water-cooling table and the diamond anvil cell press are separately designed, so that the defects of large size and inconvenient operation of the press caused by built-in water cooling are overcome. A water-cooling platform upper die 17 is provided with a pressurizing screw groove and a guide column groove, a pressurizing screw and a guide column of a press are correspondingly embedded into the groove of the water-cooling platform upper die, and the press and the water-cooling platform are tightly jointed by applying a force close to each other to the water-cooling platform through rotating two nuts on a water-cooling slide rail 20; the central holes are designed on the upper water-cooling platform die 17 and the lower water-cooling platform die 18 for facilitating spectral measurement; the water cooling platform is connected with the circulating water cooling machine through the pneumatic quick connector 19 and a water pipe, and the temperature of the water cooling platform can be adjusted through the circulating water cooling machine.
The device comprises a vacuum device matched with a high-temperature and high-pressure diamond anvil cell press for use. Namely, a diamond anvil cell-based high-temperature high-pressure transport property measuring device is arranged in a vacuum system; the vacuum system structurally comprises an organic glass cover 25, a vacuum gauge 24 and a vacuum pump, wherein the organic glass cover 25 is placed on a vacuum base station 21; copper column electrodes 22 are integrated through the vacuum base station 21 and used for connecting the thermocouples 16 and the testing electrodes 15, the copper column electrodes 22 are respectively and correspondingly electrically connected with binding posts 23 outside the organic glass cover 25, and the binding posts 23 are used for connecting external equipment when measuring high-temperature and high-pressure transport properties.
In order to meet the requirement of diamond on anvil cell transport property measurement, 8 metal copper column electrodes 22 can be respectively integrated on the left and right sides in a vacuum device, and heating, temperature measurement and transmission and measurement of electric signals can be fully met; the water cooling platform is integrated in the vacuum device, so that the press body is ensured to be at room temperature in a vacuum environment; the vacuum is pumped by a mechanical pump, and the vacuum gauge 24 reads the air pressure environment in the vacuum device in real time; the organic glass cover 25 is convenient for observing the internal experimental environment of the vacuum device and provides possibility for optical measurement. The vacuum system can effectively inhibit the oxidation of the diamond anvil 2 and the DAC device, the temperature range of the experiment is improved, meanwhile, the vacuum environment isolates heat dissipation caused by air heat conduction and heat convection, the effective utilization of heat is improved, and the temperature measurement error caused by air heat conduction and heat convection is reduced.
The invention has the beneficial effects that the diamond anvil cell technology, the heating wire heating technology, the circulating water cooling technology and the vacuum technology are combined, high pressure is generated by utilizing a large-mass supporting principle, the DAC is heated by the electrified heating wire so as to improve the temperature of a sample, the circulating water cooling system ensures that a press maintains room temperature, and the vacuum system provides a vacuum environment for an experiment, so that the experimental device and the experimental method based on the measurement of the high-temperature and high-pressure transport properties of the diamond anvil cell are constructed. The experimental device can maintain the high-temperature and high-pressure environment for the sample under the condition of the room temperature of the press, thereby solving the problems that the press is damaged and the pressure is lost due to the high temperature of the press body, the design of the ceramic mould obviously prolongs the service life of the heating wire, the design of the stepped groove on the inner wall of the supporting block increases the effective utilization of the heat of the heating wire, the design of heating and temperature control at two sides can more efficiently provide high temperature for the sample, the introduction of a vacuum system inhibits the oxidation of the diamond anvil 2, and the experimental temperature range is widened. The device provided by the invention is simple to operate, high in experiment repetition rate and good in compatibility with other test systems, can effectively realize measurement of various transport properties under high temperature and high pressure, and provides favorable conditions for in-situ measurement of multiple physical quantities under the conditions of high temperature and high pressure. The invention is supported by national science fund (11674404, 11374121, 11404133, 11774126 and 11604133), Jilin province science and technology advancement plan (20140520105JH) and super-hard material national key laboratory open project (201612).
Drawings
FIG. 1 is a schematic longitudinal section of the high temperature and high pressure diamond anvil cell press of the present invention.
FIG. 2 is a layout diagram of test electrodes and thermocouples on a diamond anvil for transport property measurement.
Fig. 3 is a top view of the flat bottom mold of the present invention.
Fig. 4 is a sectional view taken along line a-a of fig. 3.
Fig. 5 is a top view of the inventive ladder mold.
Fig. 6 is a sectional view taken along line a-a of fig. 5.
FIG. 7 is a schematic longitudinal cross-sectional view of the press and water cooled platform of the present invention.
FIG. 8 is a top view of the water cooled upper die of the present invention.
FIG. 9 is a schematic longitudinal sectional view of the vacuum apparatus of the present invention.
Fig. 10 is a schematic top view of the vacuum apparatus of the present invention.
Detailed description of the preferred embodiments
In fig. 1 to 6, 1 is an upper die of a press, 2 is a diamond anvil, 3 is a ceramic die at a supporting block end, 4 is a supporting block, 5 is a table, 6 is a metal gasket, 7 is a table base, 8 is a table cover, 9 is a mica sheet, 10 is a sample, 11 is a lower die of the press, 12 is a fixing screw, 13 is a ceramic die at a table end, 14 is a centering screw, 26 is a leveling screw, 15 is a test electrode, 16 is a thermocouple, 27 is a groove, 28 is a flat bottom die hole, 29 is a circular step, and 30 is a trapezoidal die hole.
The upper die 1 and the lower die 11 of the press form a press with a four-column structure. Two diamond anvils 2 are arranged in the inner space of the upper die 1 and the lower die 11 of the press, and a metal gasket 6 is arranged between the two diamond anvils 2. A supporting block 4 is fixedly arranged between the upper die 1 of the press and the diamond anvil 2, and a shaking table base 7 and a shaking table 5 are arranged between the lower die 11 of the press and the diamond anvil 2. The upper surface of the shaking table base 7 is provided with a spherical pit which is matched with the spherical surface below the shaking table 5, the upper part of the shaking table 5 is provided with a circular shaking table cover 8, and the shaking table 5 is clamped between the shaking table base 7 and the shaking table cover 8. The leveling screws 26 can be 3 for leveling and fixing the cradle base 7 and the cradle cover 8 of the cradle 5. The press presses the sample 10 between the anvil faces through the pad 4 and table 5 and the diamond anvil 2. The ceramic mould 13 at the end of the shaking table and the ceramic mould 3 at the end of the supporting block are used for installing electric heating wires, and the samples 10 in the sample cavity are heated at the upper end and the lower end through the diamond anvil blocks 2. The contact surface between the support block end ceramic mold 3 and the support block 4, the contact surface between the shaking table end ceramic mold 13 and the shaking table 5, and the contact surface between the support block end ceramic mold 3 and the mica sheet 9 can be fixed by a high-temperature repairing agent. The number of the fixing screws 12 can be 3, and the fixing screws are used for fixing the lower die 11 of the press, the mica sheet 9 and the shaking table base 7; the centering screws 14 can be 4 in number and are arranged on the upper die 1 of the press machine and used for adjusting the center of the anvil surface of the diamond anvil 2 to be coincided with the center of the sample cavity pre-pressed by the metal gasket 6. The test electrode 15 is arranged at the anvil face of the diamond anvil 2 when the transport property measurement is required; the temperature measuring points of the two thermocouples 16 are respectively fixed at the side edges of the two diamond anvils 2.
Fig. 3 to 6 show the structure diagrams of the cradle end ceramic mold 13 and the pallet end ceramic mold 3. The ceramic mold described in the following paragraphs is a general name for the cradle end ceramic mold 13 and the pallet end ceramic mold 3. The ceramic mould is designed into two different configurations, namely a flat-bottom mould and a trapezoidal mould. The flat bottom mould is in a circular ring shape with a rectangular cross section, grooves 27 are carved on the upper surface and the lower surface of the flat bottom mould, the grooves 27 on the upper surface and the lower surface are communicated with each other end to end through a flat bottom mould hole 28, and the electric heating wire is wound on the flat bottom mould through the flat bottom mould hole 28 and the grooves 27 and is embedded into the grooves 27; the ladder-shaped mould is characterized in that large rings and small rings are concentrically overlapped into a whole to form a circular ring shape with a convex cross section, wherein the large rings are regarded as circular ring base parts of the ladder-shaped mould, and the small rings are regarded as circular ring protrusion parts of the ladder-shaped mould. The surface of the large ring connected with the small ring and the side surface of the small ring form a circular step 29, a trapezoidal mold hole 30 is arranged on the cross section of the small ring along the radius direction, the electric heating wires sequentially penetrate through the trapezoidal mold hole 30 and are wound on the trapezoidal mold, and the wound electric heating wires are all arranged in the edge of the side surface of the large ring.
The inner wall of the supporting block 4 is provided with a circle of stepped grooves, and the ceramic die 3 at the end of the supporting block is placed in the stepped grooves at the inner wall of the supporting block 4. The ceramic mould 13 at the end of the shaking table is sleeved on the outer side of the cylinder of the shaking table 5 and is positioned on the platform at the bottom surface of the ball gap. The ceramic die 3 at the supporting block end can be made into two different configurations, namely a flat bottom die and a trapezoidal die, according to the circumferential diameter of a stepped groove formed in the inner wall of the supporting block 4; similarly, the ceramic mold 13 at the end of the shaking table can be made into two different configurations, namely a flat bottom mold and a ladder-shaped mold, according to the diameter of the cylinder of the shaking table 5. The design of the stepped groove of the inner wall of the support block 4, the heat source is embedded into the stepped groove, the contact area of the heat source and the support block 4 is increased, the heat of the electric heating wire is more effectively utilized, and the heat dissipation of the electric heating wire in the form of air heat conduction, heat convection and heat radiation is inhibited.
In fig. 7 to 10, 17 is a water-cooling bench upper mold, 18 is a water-cooling bench lower mold, 19 is a pneumatic quick coupling, 20 is a water-cooling slide rail, 21 is a vacuum base, 22 is a copper column electrode, 23 is a binding post, 24 is a vacuum gauge, and 25 is an organic glass cover.
The water cooling bench upper die 17 and the water cooling bench lower die 18 are respectively arranged on the press upper die 1 and the lower surface of the press lower die 11, and the built-in water tank is connected with the circulating water cooler through a pneumatic quick coupling 19 and a water pipe. A vacuum system is formed by a vacuum base station 21, an organic glass cover 25, a vacuum gauge 24 and a vacuum pump; 16 copper column electrodes 22 are integrated through the vacuum base station 21 and used for connecting the thermocouple 16, the testing electrode 15 and the like, the 16 copper column electrodes 22 are respectively and electrically connected with 16 binding posts 23 outside the organic glass cover 25, and the binding posts 23 are used for connecting external equipment when the high-temperature high-pressure transport property is measured.
Example 2 the high temperature and high pressure diamond anvil press assembly process is described in connection with figures 1 and 2.
The first step is as follows: removing stains on the surface of the diamond anvil 2 by a conventional method, putting the diamond anvil 2 into a mixed solution of acetone and alcohol, performing ultrasonic treatment for 20 minutes to remove the stains on the surface, taking out the diamond anvil, and washing the diamond anvil with deionized water.
The second step is that: and (3) fixing the two cleaned diamond anvils 2 on the support block 4 and the shaking table 5 respectively by using a male press, enabling the center of the anvil surface of the diamond anvil 2 to coincide with the center holes of the support block 4 and the shaking table 5 by adjusting the positions of the diamond anvil 2, and rotating a pressure screw of the male press to enable the diamond anvil 2 to be tightly jointed with the support block 4 and the shaking table 5.
The third step: uniformly mixing the high-temperature repairing agent A and the high-temperature repairing agent B according to the mass ratio of 1:1, coating the mixture on the joint of the diamond anvil block 2, the support block 4 and the shaking table 5, standing at room temperature for 24 hours, dehydrating at 100 ℃ for 2-3 hours, and curing at 150 ℃ for 2-3 hours.
The fourth step: as shown in fig. 1, the processed mica sheets 9 are respectively placed at the designated positions of the upper die 1 and the lower die 11 of the press, the shaking table base 7 is placed in the lower die 11 of the press, the shaking table base and the lower die 11 of the press are fixed by using 3 fixing screws, the prepared support block 4 is fixed in the upper die 1 of the press by using a centering screw 14, the prepared shaking table 5 is placed on the shaking table base 7, the shaking table cover 8 is placed on the upper portion of the shaking table 5, and the shaking table 5, the shaking table cover 8 and the lower die 11 of the press are fixed by using a leveling screw 26.
The fifth step: the anvil surfaces of the two diamond anvils 2 are ensured to be parallel by adjusting the leveling screws 26, and the centers of the anvil surfaces of the two diamond anvils 2 are coincided by adjusting the centering screws 14.
And a sixth step: selecting 250 mu m thick T301 steel or metal rhenium as a gasket material, prepressing the gasket material to be about 50 mu m thick by using the diamond anvil 2, punching a hole at the center of an indentation circle of the anvil surface of the diamond anvil 2 by using a laser punching machine to serve as a sample cavity, wherein the diameter of the hole is smaller than the diameter of the indentation of the anvil surface of the diamond anvil 2.
The seventh step: as shown in FIG. 2, according to the experimental conditions, a test electrode 15 was disposed on the anvil surface of the diamond anvil 2, and two K-type thermocouples 16 having a wire diameter of 100 μm were fixed at the specified positions on the lateral edges of the two diamond anvils 2.
Eighth step: resetting the prepared metal gasket 6 to ensure that the center of the sample cavity is coincident with the center of the anvil surface, filling the sample cavity with the sample and the ruby, applying pressure, and marking by using the fluorescence peak of the ruby.
Example 3 a winding method of the heating wire and installation of the ceramic mold will be described with reference to fig. 1 and 3 to 6.
The first step is as follows: according to the experimental requirements, the supporting block end ceramic mold 3 and the shaking table end ceramic mold 13 are determined to be a flat bottom mold or a trapezoid mold.
The second step is that: selecting a flat bottom mold, winding the upper surface and the lower surface of the electric heating wire in a crossed manner, and ensuring that the electric heating wire is embedded into the groove of the mold in the winding process so as to prevent the electric heating wire from contacting with a support block or a shaking table to cause local short circuit in the experiment process of the exposed part of the electric heating wire; a trapezoid die is selected, the heating wire is sequentially wound in the inner radial direction and the outer radial direction, care is taken to ensure that the heating wire can be covered by the edge of the terrace in the winding process, and local short circuit caused by contact of the exposed part of the heating wire with a supporting block or a shaking table in the experimental process is also prevented.
The third step: the copper wire is tightly wound and jointed with the electric heating wire joint.
The fourth step: as shown in fig. 1, a prepared support block end ceramic mold 3 (which can be a flat-bottom ceramic mold or a trapezoidal ceramic mold) is placed in a stepped groove on the inner wall of a support block 4 and is fixed by a high-temperature repairing agent; a ceramic mould 13 at the end of the shaking table (which can be a flat-bottom ceramic mould or a trapezoidal ceramic mould) is placed on the platform of the shaking table 5 and is fixed by a high-temperature repairing agent; and then, covering the processed mica sheets 9 on the upper surface of the ceramic die 3 at the support block end by a high-temperature repairing agent, so as to reduce the heat dissipation of the ceramic die.
Example 4 the assembly process of the water-cooled stage and the vacuum apparatus is described with reference to FIGS. 5 to 8.
The first step is as follows: and placing the assembled high-temperature and high-pressure diamond anvil cell press between the water-cooling table upper die 17 and the water-cooling table lower die 18, and embedding a press pressurizing screw and a guide column into a groove of the water-cooling table upper die.
The second step is that: by rotating the two nuts on the water-cooled slide rail 20, a force close to each other is applied to the water-cooled platform, and the press is ensured to be tightly jointed with the water-cooled platform.
The third step: a pneumatic quick connector 19 on the water cooling platform is connected with a water pipe in the vacuum device, and a water pipe outside the vacuum device is connected with the circulating water cooling machine.
The fourth step: the wires from the heating wire, the thermocouple 16 and the test electrode 15 are connected to the copper cylinder electrode 22 in the vacuum apparatus in turn. Copper column electrodes 22 outside the vacuum device are sequentially connected to corresponding binding posts 23, and a direct-current voltage-stabilized power supply, a multifunctional data acquisition system, an impedance spectroscopy system, a Hall system or other transport property measurement systems are connected with the binding posts 23, so that the diamond anvil counter device inside the vacuum system is measured.
The fifth step: the organic glass cover 25 is placed on the vacuum base 21, the vacuum system is vacuumized by the mechanical pump, and the vacuum degree inside the vacuum device is read in real time by the vacuum gauge 24.
And a sixth step: the diamond anvil cell-based high-temperature and high-pressure transport property measurement system after connection can measure high-temperature and high-pressure in-situ electric transport or thermal transport properties of the sample 10 in a vacuum environment, and meanwhile, the press body is ensured to be at room temperature.
Claims (6)
1. A high-temperature and high-pressure transport property measuring device based on diamond anvil blocks structurally comprises an upper press die (1), a lower press die (11), two diamond anvil blocks (2), a metal gasket (6) clamped between anvil faces of the two diamond anvil blocks (2), a sample (10) filled in a sample cavity of the metal gasket, temperature measuring points of two thermocouples (16) are respectively fixed on lateral edges of the two diamond anvil blocks (2), one end of a testing electrode (15) is placed in the other end of the sample cavity and used for being connected with a testing device, the bottom faces of the two diamond anvil blocks (2) are respectively fixed below a supporting block (4) and above a shaking table (5), and a mica sheet (9) is placed between the upper press die (1) and the supporting block (4); the structure is characterized by also comprising a supporting block end ceramic die (3) and a shaking table end ceramic die (13), wherein heating wires are respectively wound in the supporting block end ceramic die (3) and the shaking table end ceramic die (13); the upper die (1) and the lower die (11) of the press adopt a four-column structure; the middle of the supporting block (4) is provided with a hole, and the inner wall of the supporting block is provided with a circumferential stepped groove for placing the supporting block end ceramic die (3); the cradle (5) is in a shape that the ball segment and a cylinder on the bottom surface of the ball segment are integrated and a hole is formed in the middle, the radius of the cylinder is smaller than that of the bottom surface of the ball segment, and a cradle end ceramic die (13) is sleeved on a step formed by the outer surface of the cylinder and the bottom surface of the ball segment; the shaking table (5) is placed on a shaking table base (7), a hole is formed in the middle of the shaking table base (7), a spherical pit is formed in the upper surface of the shaking table base (7) and is matched with the spherical surface of the shaking table (5) in an installation mode, a circular shaking table cover (8) is placed on the upper portion of the shaking table (5), and the shaking table (5) is clamped between the shaking table base (7) and the shaking table cover (8) and fixed through a leveling screw (26); mica sheets (9) are placed between the shaking table base (7) and the lower die (11) of the press, and the mica sheets (9) are placed on the ceramic die (3) at the supporting block end.
2. The device for measuring the high-temperature and high-pressure transport property of the anvil cell based on the diamond according to claim 1, wherein the support block end ceramic mold (3) and the table end ceramic mold (13) are made of high-temperature-resistant ceramic materials and are customized into two different configurations, namely a flat bottom mold and a trapezoid mold; the temperature gradient required by measuring the heat transport property can be generated on the upper surface and the lower surface of the sample (10) by adjusting the power of the electric heating wires in the supporting block end ceramic mould (3) and the shaking table end ceramic mould (13).
3. The diamond-anvil-based high-temperature high-pressure transport property measurement device according to claim 2, wherein the flat bottom mold has a rectangular ring shape in cross section, grooves (27) are cut on the upper and lower surfaces of the flat bottom mold, the ends of the grooves (27) on the upper and lower surfaces are connected end to end through a flat bottom mold hole (28), and the heating wire is wound on the flat bottom mold through the flat bottom mold hole (28) and the grooves (27) and is embedded in the grooves (27); the cross section of the ladder-shaped mould is in a convex annular shape, the cross section of the ladder-shaped mould is composed of an annular base part and an annular protruding part, an inner circular ladder platform (29) and an outer circular ladder platform are formed on the upper surface of the annular base part and the side surface of the annular protruding part, a ladder-shaped mould hole (30) is formed in the annular protruding part along the radius direction, electric heating wires sequentially penetrate through the ladder-shaped mould hole (30) and are wound on the ladder-shaped mould, and the wound electric heating wires are all located in the edge of the annular base part.
4. The device for measuring the high-temperature and high-pressure transport property based on the diamond anvil cell according to the claim 1, 2 or 3, wherein the contact surface between the supporting block end ceramic mold (3) and the supporting block (4), the contact surface between the shaking table end ceramic mold (13) and the shaking table (5) and the contact surface between the supporting block end ceramic mold (3) and the mica sheet (9) are fixed by using a high-temperature repairing agent.
5. The device for measuring the high-temperature and high-pressure transport property of the diamond-based anvil cell according to claim 1, wherein a water cooling system is additionally arranged on the device for measuring the high-temperature and high-pressure transport property of the diamond-based anvil cell; the water cooling system is composed of a beryllium copper water cooling platform upper die (17) and a beryllium copper water cooling platform lower die (18) which are respectively arranged on the upper surface of the press upper die (1) and the lower surface of the press lower die (11), and the built-in water tank is connected with the circulating water cooler through a pneumatic quick coupling (19) and a water pipe; the upper water cooling platform die (17) and the lower water cooling platform die (18) are both provided with central holes; by rotating nuts on the water-cooling slide rails (20), the water-cooling platform is applied with a force approaching each other, so that the upper water-cooling platform die (17) and the upper press die (1) are ensured to be in close contact with each other, and the lower water-cooling platform die (18) and the lower press die (11) are ensured to be in close contact with each other.
6. The diamond anvil cell based high temperature and high pressure transport property measuring device according to claim 1 or 5, wherein the diamond anvil cell based high temperature and high pressure transport property measuring device is installed in a vacuum system; the vacuum system structurally comprises an organic glass cover (25) placed on a vacuum base station (21), a vacuum gauge (24) and a vacuum pump; copper column electrodes (22) are integrated through the vacuum base station (21) and used for being connected with the thermocouples (16) and the testing electrodes (15), the copper column electrodes (22) are respectively and correspondingly electrically connected with binding posts (23) outside the organic glass cover (25), and the binding posts (23) are used for being connected with external equipment during high-temperature and high-pressure transport property measurement.
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| CN110095505A (en) * | 2019-03-13 | 2019-08-06 | 东北电力大学 | A kind of method of Transition-metal dichalcogenide energy gap regulation |
| CN111157571A (en) * | 2020-01-07 | 2020-05-15 | 吉林大学 | Method for measuring thermal conductivity of high-temperature and high-pressure sample based on diamond anvil cell |
| CN111929131A (en) * | 2020-08-05 | 2020-11-13 | 吉林大学 | Regulating La2Ti2O7Method of electrical properties |
| CN111982736B (en) * | 2020-08-31 | 2021-11-23 | 吉林大学 | High-temperature in-situ pressure calibration diamond anvil cell press and pressure calibration method |
| CN112782211B (en) * | 2020-12-28 | 2023-11-21 | 东北电力大学 | Water phase change detection method |
| CN113777404B (en) * | 2021-09-10 | 2022-06-07 | 吉林大学 | Device and method for accurately measuring electric heat transport properties at high temperature and high pressure in situ |
| CN117517044A (en) * | 2023-10-10 | 2024-02-06 | 北京爱森伯特科技有限公司 | External heating device for high-voltage test |
| CN117227240B (en) * | 2023-11-15 | 2024-01-16 | 吉林大学 | Controllable quick pressurizing technology for large-cavity press |
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| FR2661989B1 (en) * | 1990-05-10 | 1994-03-18 | Commissariat A Energie Atomique | DIAMOND ANVIL CELL AND DEVICE FOR OBSERVING AND ANALYZING VERY HIGH PRESSURE SAMPLES. |
| US5147446A (en) * | 1991-08-06 | 1992-09-15 | The United States Of America As Represented By The Secretary Of The Commerce | Method for fabrication of dense compacts from nano-sized particles using high pressures and cryogenic temperatures |
| JPH09171142A (en) * | 1995-12-19 | 1997-06-30 | Natl Inst For Res In Inorg Mater | Diamond anvil cell |
| CN101566543B (en) * | 2009-05-26 | 2013-03-20 | 吉林大学 | High temperature and high voltage experimental device for heating gasket |
| CN104596835B (en) * | 2015-01-25 | 2017-05-10 | 吉林大学 | Inner-condensing diamond anvil cell pressing machine |
| CN106442168B (en) * | 2016-09-26 | 2018-12-11 | 吉林大学 | Small rotary formula diamond anvil cell press device |
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