CN111155172A - Application of spiral crystal selector in preparation of thermocouple wire material, thermocouple wire and application of thermocouple wire - Google Patents
Application of spiral crystal selector in preparation of thermocouple wire material, thermocouple wire and application of thermocouple wire Download PDFInfo
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- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
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- C—CHEMISTRY; METALLURGY
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
- G01K7/02—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using thermoelectric elements, e.g. thermocouples
Abstract
The invention discloses application of a spiral crystal selector in preparation of a thermocouple wire material, a thermocouple wire and application thereof. Wherein, the step that the spiral crystal selector is used for preparing the thermocouple wire in the application comprises the following steps: adding seed crystals into the spiral crystal selector, placing the seed crystals on a crystal starter, and adjusting the heat preservation temperature of the crystal starter so as to melt the seed crystals; melting the raw material of the electric couple wire, injecting the obtained molten liquid into a spiral crystal selector to form a whole with the melting part of the seed crystal, and standing; vertically immersing a spiral crystal selector into cooling liquid so as to cool and crystallize the melting liquid from bottom to top to obtain a single crystal ingot-shaped material; carrying out stretch forming treatment on the single crystal ingot-shaped material so as to obtain a single crystal wire; and performing stress relief annealing on the single crystal wire so as to obtain the positive electrode and/or negative electrode thermocouple wire. The spiral crystal selector is used for preparing the temperature thermocouple wire material, so that the integral uniformity of the thermocouple wire can be obviously improved, the internal resistance is reduced, and the temperature measurement precision of the thermocouple is obviously improved.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to application of a spiral crystal selector in preparation of a thermocouple wire material, a thermocouple wire and application of the thermocouple wire.
Background
Temperature is a very important parameter in industrial production and scientific experiments, many physical phenomena and chemical properties are related to temperature, many production processes can be carried out only in a specific temperature range, and therefore, in modern life, accurate temperature is indispensable information content. With the continuous development of science and technology and the deep application of temperature sensors, people also put higher and higher requirements on the physical structure and the measurement accuracy of the temperature sensors. The thermoelectric temperature sensor is the most commonly used temperature detection device in daily life, industrial production and scientific research. The temperature is detected by measuring the change of the electrical parameter by utilizing the characteristic that the electrical parameter of a temperature-measuring sensitive element changes along with the temperature, and the temperature-measuring sensitive element can be mainly divided into a contact type thermocouple, a thermistor, a semiconductor integrated temperature sensor and a non-contact type pyroelectric sensor.
Among the various types of thermoelectric sensors, the conversion of temperature into electrical potential and resistance is the most common, which corresponds to a thermocouple sensor and a thermal resistance sensor, respectively. In contrast, the thermal resistance sensor has a simple structure, a small volume and high sensitivity, while the thermocouple sensor has a large temperature measurement range and a short response time, and generally needs a high temperature environment of about 1000 ℃ in industrial production, drilling and manufacturing and forming of special high-performance materials. However, the non-uniformity of the thermocouple wire material can cause self-measurement accuracy errors, because the anode and the cathode are in a temperature gradient field, and the non-uniformity can generate an additional thermoelectric force on the thermocouple wire, thereby interfering with the measurement accuracy. Therefore, there is a need to further improve the uniformity of thermocouple wire materials.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to propose the use of a spiral crystal selector in the preparation of a thermocouple wire material, and a thermocouple wire and its applications. The spiral crystal selector for preparing the single crystal alloy is used for preparing the temperature measuring thermocouple wire material, so that the integral uniformity of the thermocouple wire can be obviously improved, the internal resistance of the thermocouple wire can be further reduced, and the temperature measuring precision of the thermocouple can be obviously improved.
The invention is mainly based on the following problems:
the nonuniformity of thermocouple wire material can cause self-measurement accuracy errors. The thermocouple wire material cannot be a perfect single crystal structure, and a certain number of non-uniform non-single crystal structures and structural defects exist in the thermocouple wire material; meanwhile, some non-uniformity may be caused by unreleased internal stress, segregation of alloy components, volatilization or oxidation of metal elements on the local surface of the thermocouple wire, thermal diffusion at high temperature, contamination and corrosion of the surface of the thermocouple wire, and the presence of internal impurities. Since the positive and negative electrodes are in a temperature gradient field, this inhomogeneity can produce an additional thermoelectric potential on the thermocouple wire, which can interfere with the measurement accuracy.
To this end, according to a first aspect of the invention, the invention proposes the use of a spiral crystal selector for the preparation of single crystal alloys for the preparation of thermometric thermocouple wire materials. According to an embodiment of the present invention, in this application, the step of using the spiral crystal selector for preparing the thermocouple wire includes:
(1) adding seed crystals into the spiral crystal selector, placing the seed crystals on a crystal starter, and adjusting the heat preservation temperature of the crystal starter so as to partially melt the seed crystals;
(2) melting the raw material of the electric couple wire, injecting the obtained molten liquid into the spiral crystal selector to form a whole with the melting part of the seed crystal, and standing;
(3) vertically immersing the spiral crystal selector obtained in the step (2) into cooling liquid so as to cool and crystallize the melting liquid from bottom to top, thereby obtaining a single crystal ingot-shaped material;
(4) performing stretch forming treatment on the single crystal ingot-shaped material so as to obtain a single crystal wire;
(5) and performing stress relief annealing on the single crystal wire so as to obtain the positive electrode and/or negative electrode thermocouple wire.
According to the application of the spiral crystal selector for preparing the single crystal alloy in preparing the temperature thermocouple wire material, the spiral crystal selector for preparing the single crystal alloy is used for preparing the temperature thermocouple wire material, and meanwhile, the preparation method can reduce the number of uneven mixed crystals, small-angle crystal boundaries, orientation deviation, recrystallization, shell reaction and microscopic lattice defect structures generated in the metal alloy forming process in the thermocouple wire forming process, and particularly can ensure that the single crystal orientation consistency is not lower than 90% and the mixed crystal probability is not higher than 10%. Therefore, the integral uniformity of the thermocouple wire can be obviously improved, the internal resistance of the thermocouple wire can be further reduced, and the temperature measurement precision of the thermocouple can be obviously improved.
In addition, the application of the spiral crystal selector for preparing single crystal alloy according to the above embodiment of the invention in preparing temperature thermocouple wire material can also have the following additional technical characteristics:
in some embodiments of the present invention, the raw material of the thermocouple wire is a raw material of a positive electrode and/or a raw material of a negative electrode, the raw material of the positive electrode is at least one selected from pure copper, pure nickel, pure chromium, pure iron, pure platinum, pure rhodium, pure tungsten and pure rhenium, and the raw material of the negative electrode is at least one selected from pure copper, pure nickel, pure silicon, pure platinum, pure tungsten and pure rhenium.
In some embodiments of the invention, in step (3), the spiral crystal selector is immersed in the cooling liquid at a draw rate of not more than 6 mm/min.
In some embodiments of the invention, in the step (5), the stress relief annealing is performed on the single crystal wire by using a rewinder at 400-550 ℃ and a winding speed of 30-70 rpm.
In some embodiments of the invention, the helix angle of the helical crystal selector helical section is 30-75 degrees, the pitch is 0.1-3 times of the product of the tangent value of the helix angle and the inner diameter of the helical section, and the number of helical turns of the helical section is not more than 2 turns.
In some embodiments of the invention, the ratio of the height of the crystal starter to the inner diameter of the crystal starter is 0.5-2, and the ratio of the inner diameter of the crystal starter to the inner diameter of the spiral section of the spiral crystal selector is 3-6.
According to a second aspect of the invention, a galvanic wire is proposed. According to the embodiment of the invention, the preparation method of the galvanic couple wire comprises the following steps:
(1) adding seed crystals into the spiral crystal selector, placing the seed crystals on a crystal starter, and adjusting the heat preservation temperature of the crystal starter so as to partially melt the seed crystals;
(2) melting the raw material of the electric couple wire, injecting the obtained molten liquid into the spiral crystal selector to form a whole with the melting part of the seed crystal, and standing;
(3) vertically immersing the spiral crystal selector obtained in the step (2) into cooling liquid so as to cool and crystallize the melting liquid from bottom to top, thereby obtaining a single crystal ingot-shaped material;
(4) performing stretch forming treatment on the single crystal ingot-shaped material so as to obtain a single crystal wire;
(5) and performing stress relief annealing on the single crystal wire so as to obtain the positive electrode and/or negative electrode thermocouple wire.
According to the thermocouple wire provided by the embodiment of the invention, the spiral crystal selector for preparing the single crystal alloy is used for preparing the temperature measuring thermocouple wire material, and the preparation method is adopted, so that the number of uneven mixed crystals, small-angle crystal boundaries, orientation deviation, recrystallization, shell reaction and microscopic lattice defect structures generated in the metal alloy forming process can be reduced in the thermocouple wire forming process, the single crystal orientation consistency can be not lower than 90%, and the mixed crystal probability is not higher than 10%. Compared with the existing thermocouple wire, the thermocouple wire has high integral uniformity and small internal resistance, and can remarkably improve the temperature measurement precision of the thermocouple.
In some embodiments of the present invention, the raw material of the thermocouple wire is a raw material of a positive electrode and/or a raw material of a negative electrode, the raw material of the positive electrode is at least one selected from pure copper, pure nickel, pure chromium, pure iron, pure platinum, pure rhodium, pure tungsten and pure rhenium, and the raw material of the negative electrode is at least one selected from pure copper, pure nickel, pure silicon, pure platinum, pure tungsten and pure rhenium.
In some embodiments of the invention, in step (3), the spiral crystal selector is immersed in the cooling liquid at a pulling rate of not more than 6mm/min,
in some embodiments of the invention, in the step (5), the stress relief annealing is performed on the single crystal wire by using a rewinder at 400-550 ℃ and a winding speed of 30-70 rpm.
In some embodiments of the invention, the helix angle of the helical crystal selector helical section is 30-75 degrees, the pitch is 0.1-3 times of the product of the tangent value of the helix angle and the inner diameter of the helical section, and the number of helical turns of the helical section is not more than 2 turns.
In some embodiments of the invention, the ratio of the height of the crystal starter to the inner diameter of the crystal starter is 0.5-2, and the ratio of the inner diameter of the crystal starter to the inner diameter of the spiral section of the spiral crystal selector is 3-6.
According to a third aspect of the present invention, a thermocouple sensor is provided. According to an embodiment of the present invention, the thermocouple sensor is the thermocouple wire described above. The thermocouple sensor has high temperature measuring precision which can reach 0.001 t in the whole range.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a flow chart of a method for manufacturing a thermocouple wire by using a spiral crystal selector according to an embodiment of the invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
According to a first aspect of the invention, the invention proposes the use of a spiral crystal selector for preparing single crystal alloys for preparing thermometric thermocouple wire materials. According to an embodiment of the present invention, referring to fig. 1, in this application, the step of using the spiral crystal selector for preparing the thermocouple wire comprises: (1) adding seed crystals into the spiral crystal selector, placing the seed crystals on a crystal starter, and adjusting the heat preservation temperature of the crystal starter so as to melt the seed crystals; (2) melting the raw material of the electric couple wire, injecting the obtained molten liquid into a spiral crystal selector to form a whole with the melting part of the seed crystal, and standing; (3) vertically immersing the spiral crystal selector obtained in the step (2) into cooling liquid so as to cool and crystallize the melting liquid from bottom to top, thereby obtaining a single crystal ingot-shaped material; (4) carrying out stretch forming treatment on the single crystal ingot-shaped material so as to obtain a single crystal wire; (5) and performing stress relief annealing on the single crystal wire so as to obtain the positive electrode and/or negative electrode thermocouple wire. In the application, the method for preparing the thermocouple wire is combined, so that the integral uniformity of the thermocouple wire can be obviously improved, the internal resistance of the thermocouple wire can be further reduced, and the temperature measurement precision of a thermocouple can be obviously improved.
The use of the spiral crystal selector for preparing single crystal alloy in preparing temperature thermocouple wire material is mainly described in two parts in detail below.
Preparation of single crystal ingot-like material
According to the embodiment of the invention, seed crystals are added into the spiral crystal selector and placed on the crystal starter, and the heat preservation temperature of the crystal starter is adjusted so as to melt the seed crystals partially; melting the raw material of the electric couple wire, injecting the obtained molten liquid into a spiral crystal selector to form a whole with the melting part of the seed crystal, and standing; then vertically immersing the spiral crystal selector into the cooling liquid so as to cool and crystallize the melting liquid from bottom to top, thereby obtaining the single crystal ingot-shaped material. Therefore, the number of uneven mixed crystals, small-angle crystal boundaries, orientation deviation, recrystallization, shell reaction and microscopic lattice defect structures generated in the forming process of the thermocouple metal alloy can be obviously reduced, the orientation consistency of single crystals is not lower than 90%, the mixed crystal probability is not more than 10%, the integral uniformity of the thermocouple wire can be obviously improved, and the temperature measurement precision of the thermocouple can be improved. It should be noted that, in the present invention, there is no particular limitation on the method for preparing the seed crystal, and those skilled in the art can select the seed crystal according to actual needs.
According to a specific embodiment of the present invention, the raw material of the thermocouple wire may be a positive electrode raw material and/or a negative electrode raw material of the thermocouple wire, wherein the types of the positive electrode raw material and the negative electrode raw material are not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the positive electrode raw material may be at least one selected from pure copper, pure nickel, pure chromium, pure iron, pure platinum, pure rhodium, pure tungsten and pure rhenium, and the negative electrode raw material may be at least one selected from pure copper, pure nickel, pure silicon, pure platinum, pure tungsten and pure rhenium.
According to another embodiment of the present invention, the particle sizes of the cathode material and the anode material may be 20 to 80 μm, respectively, so as to significantly improve the efficiency and effect of the melting process and reduce the structural defects that may be generated during the metal alloy forming process.
According to another embodiment of the invention, the pulling rate of the spiral crystal selector immersed in the cooling liquid can be not more than 6mm/min, for example, 4.5-6 mm/min, 1mm/min, 2mm/min, 3mm/min, 4mm/min, 5mm/min or 6mm/min, etc., and the inventor finds that if the pulling rate is too high, the mixed crystal control is not facilitated, but the spacing of the transverse secondary arms of the dendrites is controlled; on the contrary, if the drawing speed is too low, the control of the spacing between the dendritic crystal transverse secondary arms is not facilitated, but the generation of mixed crystals is favorably inhibited.
According to another embodiment of the invention, seed crystals can be loaded into a crystal starter in a spiral crystal selector, the temperature of the crystal starter is adjusted to partially melt the seed crystals to form a solid-liquid pasty area, and the temperature is kept for 30 min; smelting a cathode raw material/an anode raw material of a couple wire in a crucible to obtain molten alloy; pouring molten high-temperature alloy melt into the spiral crystal selector to form a whole with the seed crystal melting part after the heat preservation of the crystal starter is finished, and standing for 10 min; and then slowly and vertically putting the spiral crystal selector into cooling liquid at the speed of 100 mu m/s, and gradually cooling and crystallizing the molten cathode raw material from bottom to top to obtain the single crystal ingot-shaped material of the cathode raw material. The preparation method of the seed crystal in the present invention is not particularly limited, and those skilled in the art can select the seed crystal according to actual needs.
According to another embodiment of the present invention, the spiral angle of the spiral section of the spiral crystal selector may be 30 to 75 degrees, for example, 35 degrees, 40 degrees, 45 degrees, 50 degrees, 55 degrees, 60 degrees, 65 degrees, or 70 degrees; the pitch can be 0.1-3 times of the product of the tangent value of the helix angle and the inner diameter of the helix section, such as 0.2, 0.6, 1.2, 1.8, 2.4 or 3 times; the number of spiral turns of the spiral section can be not more than 2, wherein the number of spiral turns of the spiral section can be non-integer turns, such as 0.5 turn, 0.8 turn, 1.2 turn, 1.5 turn, 1.8 turn and the like.
According to another embodiment of the present invention, the ratio of the height of the crystal starter to the inner diameter of the crystal starter may be 0.5 to 2, for example, 0.5, 0.8, 1.1, 1.4, 1.6, 1.7 or 2; the ratio of the inner diameter of the crystal starter to the inner diameter of the spiral section of the spiral crystal selector can be 3-6, for example, 3.4, 3.8, 4.2, 4.6, 5, 5.4 or 5.8. According to the invention, by adjusting the ratio of the height of the crystal starter to the inner diameter of the crystal starter to be in the range, the number of crystal grains can be further reduced, the uniformity of single crystal orientation can be improved, and the crystal structure and the appearance of the single crystal ingot-shaped material have better uniformity. In addition, the inventor also finds that if the diameter of the crystal starter is too large, the diameter of the seed crystal is easily too large, so that not only is the melt solidified too fast to enable the seed crystal to play a role of a crystallization core, but also the preparation difficulty of the single crystal alloy is increased; if the diameter of the crystal starter is too small, the effect of inhibiting mixed crystals in the spiral section of the spiral crystal selector is easily weakened. By controlling the structural parameters, the invention can further reduce the number of uneven mixed crystals, small-angle crystal boundaries, orientation deviation, recrystallization, shell reaction and microscopic lattice defect structures generated in the forming process of the thermocouple metal alloy, ensure that the single crystal orientation consistency is not lower than 90 percent and the mixed crystal probability is not more than 10 percent, thereby obviously improving the integral uniformity of the thermocouple wire.
Stretch forming and stress relief annealing
According to an embodiment of the present invention, a single crystal ingot-shaped material is subjected to a stretch forming process to obtain a single crystal wire; and performing stress relief annealing on the single crystal wire so as to obtain the positive electrode and/or negative electrode thermocouple wire. According to the invention, through stress relief annealing of the single crystal wire, crystal grains can be further refined, the crystalline phase structure of the thermocouple wire is improved, the structure defect is eliminated, the mechanical property is improved, the plasticity of the single wire is recovered, the internal stress of the thermocouple wire can be released, and the surface is cleaned to a certain extent, so that the overall uniformity of the thermocouple wire can be further improved, and the temperature measurement precision of the thermocouple can be further improved.
According to one embodiment of the invention, a rewinder can be used for performing stress relief annealing on the single crystal wire at 400-550 ℃ and at a winding speed of 30-70 rpm, so that the crystal phase structure of the thermocouple wire can be further improved, the structure defects can be eliminated, the mechanical property of the thermocouple wire can be improved, the plasticity of the single wire can be recovered, and the internal stress of the thermocouple wire can be released, so that the overall uniformity of the thermocouple wire can be further improved.
According to another embodiment of the invention, electric brush annealing equipment, such as contact electric brush transmission large current annealing equipment, can be selected to perform stress relief annealing on the single crystal wire.
In summary, the spiral crystal selector for preparing single crystal alloy in the above embodiment of the present invention is used for preparing temperature thermocouple wire material, and the spiral crystal selector for preparing single crystal alloy is used for preparing temperature thermocouple wire material, and the above preparation method can reduce the number of uneven mixed crystal, small-angle grain boundary, orientation deviation, recrystallization, shell reaction and microscopic lattice defect structure generated in the metal alloy forming process in the thermocouple wire forming process, and specifically can make the single crystal orientation uniformity not lower than 90%, and the mixed crystal probability not higher than 10%. Therefore, the integral uniformity of the thermocouple wire can be obviously improved, the internal resistance of the thermocouple wire can be further reduced, and the temperature measurement precision of the thermocouple can be obviously improved.
According to a second aspect of the invention, a galvanic wire is proposed. According to the embodiment of the invention, as shown in fig. 1, the preparation method of the galvanic wire comprises the following steps: (1) adding seed crystals into the spiral crystal selector, placing the seed crystals on a crystal starter, and adjusting the heat preservation temperature of the crystal starter so as to melt the seed crystals; (2) melting the raw material of the electric couple wire, injecting the obtained molten liquid into a spiral crystal selector to form a whole with the melting part of the seed crystal, and standing; (3) vertically immersing the spiral crystal selector obtained in the step (2) into cooling liquid so as to cool and crystallize the melting liquid from bottom to top, thereby obtaining a single crystal ingot-shaped material; (4) carrying out stretch forming treatment on the single crystal ingot-shaped material so as to obtain a single crystal wire; (5) and performing stress relief annealing on the single crystal wire so as to obtain the positive electrode and/or negative electrode thermocouple wire. Compared with the existing thermocouple wire, the thermocouple wire has high integral uniformity and small internal resistance, and can remarkably improve the temperature measurement precision of the thermocouple, so that the full-range temperature measurement precision of the thermocouple sensor can reach 0.001| t |. The above-described electric coupling wire is described in detail mainly from two parts below.
Preparation of single crystal ingot-like material
According to the embodiment of the invention, seed crystals are added into the spiral crystal selector and placed on the crystal starter, and the heat preservation temperature of the crystal starter is adjusted so as to melt the seed crystals partially; melting the raw material of the electric couple wire, injecting the obtained molten liquid into a spiral crystal selector to form a whole with the melting part of the seed crystal, and standing; then vertically immersing the spiral crystal selector into the cooling liquid so as to cool and crystallize the melting liquid from bottom to top, thereby obtaining the single crystal ingot-shaped material. Therefore, the number of uneven mixed crystals, small-angle crystal boundaries, orientation deviation, recrystallization, shell reaction and microscopic lattice defect structures generated in the forming process of the thermocouple metal alloy can be obviously reduced, the orientation consistency of single crystals is not lower than 90%, the mixed crystal probability is not more than 10%, the integral uniformity of the thermocouple wire can be obviously improved, and the temperature measurement precision of the thermocouple can be improved. It should be noted that, in the present invention, there is no particular limitation on the method for preparing the seed crystal, and those skilled in the art can select the seed crystal according to actual needs.
According to a specific embodiment of the present invention, the raw material of the thermocouple wire may be a positive electrode raw material and/or a negative electrode raw material of the thermocouple wire, wherein the types of the positive electrode raw material and the negative electrode raw material are not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the positive electrode raw material may be at least one selected from pure copper, pure nickel, pure chromium, pure iron, pure platinum, pure rhodium, pure tungsten and pure rhenium, and the negative electrode raw material may be at least one selected from pure copper, pure nickel, pure silicon, pure platinum, pure tungsten and pure rhenium.
According to another embodiment of the present invention, the particle sizes of the cathode material and the anode material may be 20 to 80 μm, respectively, so as to significantly improve the efficiency and effect of the melting process and reduce the structural defects that may be generated during the metal alloy forming process.
According to another embodiment of the invention, the pulling rate of the spiral crystal selector immersed in the cooling liquid can be not more than 6mm/min, for example, 4.5-6 mm/min, 1mm/min, 2mm/min, 3mm/min, 4mm/min, 5mm/min or 6mm/min, etc., and the inventor finds that if the pulling rate is too high, the mixed crystal control is not facilitated, but the spacing of the transverse secondary arms of the dendrites is controlled; on the contrary, if the drawing speed is too low, the control of the spacing between the dendritic crystal transverse secondary arms is not facilitated, but the generation of mixed crystals is favorably inhibited.
According to another embodiment of the invention, seed crystals can be loaded into a crystal starter in a spiral crystal selector, the temperature of the crystal starter is adjusted to partially melt the seed crystals to form a solid-liquid pasty area, and the temperature is kept for 30 min; smelting a cathode raw material/an anode raw material of a couple wire in a crucible to obtain molten alloy; pouring molten high-temperature alloy melt into the spiral crystal selector to form a whole with the seed crystal melting part after the heat preservation of the crystal starter is finished, and standing for 10 min; and then slowly and vertically putting the spiral crystal selector into cooling liquid at the speed of 100 mu m/s, and gradually cooling and crystallizing the molten cathode raw material from bottom to top to obtain the single crystal ingot-shaped material of the cathode raw material. The preparation method of the seed crystal in the present invention is not particularly limited, and those skilled in the art can select the seed crystal according to actual needs.
According to another embodiment of the present invention, the spiral angle of the spiral section of the spiral crystal selector may be 30 to 75 degrees, for example, 35 degrees, 40 degrees, 45 degrees, 50 degrees, 55 degrees, 60 degrees, 65 degrees, or 70 degrees; the pitch can be 0.1-3 times of the product of the tangent value of the helix angle and the inner diameter of the helix section, such as 0.2, 0.6, 1.2, 1.8, 2.4 or 3 times; the number of spiral turns of the spiral section can be not more than 2, wherein the number of spiral turns of the spiral section can be non-integer turns, such as 0.5 turn, 0.8 turn, 1.2 turn, 1.5 turn, 1.8 turn and the like, so that not only can the deviation of single crystal orientation be obviously reduced, but also the number of crystal grains can be further reduced, the uniformity of single crystal orientation of the single crystal ingot material can be obviously improved, and the crystal structure and the appearance of the single crystal ingot material can have better uniformity.
According to another embodiment of the present invention, the ratio of the height of the crystal starter to the inner diameter of the crystal starter may be 0.5 to 2, for example, 0.5, 0.8, 1.1, 1.4, 1.6, 1.7 or 2; the ratio of the inner diameter of the crystal starter to the inner diameter of the spiral section of the spiral crystal selector can be 3-6, for example, 3.4, 3.8, 4.2, 4.6, 5, 5.4 or 5.8. According to the invention, by adjusting the ratio of the height of the crystal starter to the inner diameter of the crystal starter to be in the range, the number of crystal grains can be further reduced, the uniformity of single crystal orientation can be improved, and the crystal structure and the appearance of the single crystal ingot-shaped material have better uniformity. In addition, the inventor also finds that if the diameter of the crystal starter is too large, the diameter of the seed crystal is easily too large, so that not only is the melt solidified too fast to enable the seed crystal to play a role of a crystallization core, but also the preparation difficulty of the single crystal alloy is increased; if the diameter of the crystal starter is too small, the effect of inhibiting mixed crystals in the spiral section of the spiral crystal selector is easily weakened. By controlling the structural parameters, the invention can further reduce the number of uneven mixed crystals, small-angle crystal boundaries, orientation deviation, recrystallization, shell reaction and microscopic lattice defect structures generated in the forming process of the thermocouple metal alloy, ensure that the single crystal orientation consistency is not lower than 90 percent and the mixed crystal probability is not more than 10 percent, thereby obviously improving the integral uniformity of the thermocouple wire.
Stretch forming and stress relief annealing
According to an embodiment of the present invention, a single crystal ingot-shaped material is subjected to a stretch forming process to obtain a single crystal wire; and performing stress relief annealing on the single crystal wire so as to obtain the positive electrode and/or negative electrode thermocouple wire. According to the invention, through stress relief annealing of the single crystal wire, crystal grains can be further refined, the crystalline phase structure of the thermocouple wire is improved, the structure defect is eliminated, the mechanical property is improved, the plasticity of the single wire is recovered, the internal stress of the thermocouple wire can be released, and the surface is cleaned to a certain extent, so that the overall uniformity of the thermocouple wire can be further improved, and the temperature measurement precision of the thermocouple can be further improved.
According to one embodiment of the invention, a rewinder can be used for performing stress relief annealing on the single crystal wire at 400-550 ℃ and at a winding speed of 30-70 rpm, so that the crystal phase structure of the thermocouple wire can be further improved, the structure defects can be eliminated, the mechanical property of the thermocouple wire can be improved, the plasticity of the single wire can be recovered, and the internal stress of the thermocouple wire can be released, so that the overall uniformity of the thermocouple wire can be further improved.
According to another embodiment of the invention, electric brush annealing equipment, such as contact electric brush transmission large current annealing equipment, can be selected to perform stress relief annealing on the single crystal wire.
In summary, according to the thermocouple wire of the embodiment of the present invention, the spiral crystal selector for preparing the single crystal alloy is used for preparing the temperature measuring thermocouple wire material, and the preparation method is adopted, so that the number of uneven mixed crystals, small-angle grain boundaries, orientation deviation, recrystallization, shell reaction and micro lattice defect structures generated in the metal alloy forming process can be reduced in the thermocouple wire forming process, the single crystal orientation consistency can be not lower than 90%, and the mixed crystal probability is not higher than 10%. Compared with the existing thermocouple wire, the thermocouple wire has high integral uniformity and small internal resistance, and can remarkably improve the temperature measurement precision of the thermocouple.
According to a third aspect of the present invention, a thermocouple sensor is provided. According to an embodiment of the present invention, the thermocouple sensor is the thermocouple wire described above. The inventor finds that the thermocouple sensor with the thermocouple wire has high temperature measurement accuracy, and the full-range temperature measurement accuracy can reach 0.001 t, wherein t represents the real-time temperature. It should be noted that the features and effects described above for the thermocouple wire are also applicable to the thermocouple sensor, and are not described in detail here.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
A preparation method of an ultralong T-shaped single crystal couple wire comprises the following steps:
1) preparing a positive and negative electrode single crystal ingot material:
2.75Kg of pure copper powder and 2.25Kg of pure nickel powder are evenly mixed to be used as a negative electrode material; 5Kg of pure copper powder was used as the positive electrode material.
Respectively preparing seed crystals of the anode material and the cathode material, and respectively loading the seed crystals on a crystal starter in the spiral crystal selector. Adjusting the temperature of the crystal starter to melt the seed crystal part to form a solid-liquid pasty area, and keeping the temperature for 30 min.
Smelting the cathode raw material in a crucible at 1300 ℃ to obtain molten alloy solution; pouring molten high-temperature alloy melt into the spiral crystal selector after the heat preservation of the crystal starter is finished to form a whole with the melting part of the negative electrode material seed crystal, and standing for 10 min; and then slowly and vertically putting the spiral crystal selector into cooling liquid at the speed of 100 mu m/s, and gradually cooling and crystallizing the molten cathode raw material from bottom to top to obtain the single crystal ingot-shaped material of the cathode raw material.
Smelting the anode raw material in a crucible at 1100 ℃ to obtain molten alloy melt; pouring molten high-temperature alloy melt into the spiral crystal selector after the heat preservation of the crystal starter is finished to form a whole with the melting part of the positive material seed crystal, and standing for 10 min; and then slowly and vertically putting the spiral crystal selector into cooling liquid at the speed of 100 mu m/s, and gradually cooling and crystallizing the molten anode raw material from bottom to top to obtain the single crystal ingot-shaped material of the anode raw material.
2) And (3) stretching and forming: forging and rolling the high-single-crystallinity positive and negative electrode ingot-shaped materials subjected to spiral crystal selection, repeatedly drawing the materials, and drawing the materials into wire materials with required sizes.
3) Stress relief annealing: and (3) performing filament annealing on the thermocouple positive wire material on a rewinding machine by using electric brush annealing equipment, wherein the temperature is 400 ℃, the winding speed is 30 r/min, and the negative wire material is performed filament annealing on the rewinding machine, the temperature is 400 ℃, and the winding speed is 30 r/min.
Example 2
A preparation method of an ultralong J-shaped single crystal couple wire comprises the following steps:
1) preparing a positive and negative electrode single crystal ingot material:
2.75Kg of pure copper powder and 2.25Kg of pure nickel powder are evenly mixed to be used as a negative electrode material; 5Kg of pure iron powder was used as the positive electrode material.
Respectively preparing seed crystals of the anode material and the cathode material, and respectively loading the seed crystals on a crystal starter in the spiral crystal selector. Adjusting the temperature of the crystal starter to melt the seed crystal part to form a solid-liquid pasty area, and keeping the temperature for 30 min.
Smelting the cathode raw material in a crucible at 1300 ℃ to obtain molten alloy solution; pouring molten high-temperature alloy melt into the spiral crystal selector after the heat preservation of the crystal starter is finished to form a whole with the melting part of the negative electrode material seed crystal, and standing for 10 min; and then slowly and vertically putting the spiral crystal selector into cooling liquid at the speed of 100 mu m/s, and gradually cooling and crystallizing the molten cathode raw material from bottom to top to obtain the single crystal ingot-shaped material of the cathode raw material.
Smelting the anode raw material in a crucible at 1600 ℃ to obtain molten alloy; pouring molten high-temperature alloy melt into the spiral crystal selector after the heat preservation of the crystal starter is finished to form a whole with the melting part of the positive material seed crystal, and standing for 10 min; and then slowly and vertically putting the spiral crystal selector into cooling liquid at the speed of 100 mu m/s, and gradually cooling and crystallizing the molten anode raw material from bottom to top to obtain the single crystal ingot-shaped material of the anode raw material.
2) And (3) stretching and forming: forging and rolling the high-single-crystallinity positive and negative electrode ingot-shaped materials subjected to spiral crystal selection, repeatedly drawing the materials, and drawing the materials into wire materials with required sizes.
3) Stress relief annealing: and (3) performing filament annealing on the thermocouple positive wire material on a rewinder by using electric brush annealing equipment at the temperature of 450 ℃ and the winding speed of 50 revolutions per minute, and performing filament annealing on the thermocouple negative wire material on the rewinder at the temperature of 400 ℃ and the winding speed of 30 revolutions per minute.
Example 3
A preparation method of an ultralong K-type single crystal couple wire comprises the following steps:
1) preparing a positive and negative electrode single crystal ingot material:
4.85Kg of pure nickel powder and 0.15Kg of pure silicon powder are evenly mixed to be used as a negative electrode material; 4.5Kg of pure nickel powder and 0.5Kg of pure chromium powder are used as the anode material.
Respectively preparing seed crystals of the anode material and the cathode material, and respectively loading the seed crystals on a crystal starter in the spiral crystal selector. Adjusting the temperature of the crystal starter to melt the seed crystal part to form a solid-liquid pasty area, and keeping the temperature for 30 min.
Smelting the cathode raw material in a crucible at 1500 ℃ to obtain molten alloy; pouring molten high-temperature alloy melt into the spiral crystal selector after the heat preservation of the crystal starter is finished to form a whole with the melting part of the negative electrode material seed crystal, and standing for 10 min; and then slowly and vertically putting the spiral crystal selector into cooling liquid at the speed of 100 mu m/s, and gradually cooling and crystallizing the molten cathode raw material from bottom to top to obtain the single crystal ingot-shaped material of the cathode raw material.
Smelting the anode raw material in a crucible at 1400 ℃ to obtain molten alloy melt; pouring molten high-temperature alloy melt into the spiral crystal selector after the heat preservation of the crystal starter is finished to form a whole with the melting part of the positive material seed crystal, and standing for 10 min; and then slowly and vertically putting the spiral crystal selector into cooling liquid at the speed of 100 mu m/s, and gradually cooling and crystallizing the molten anode raw material from bottom to top to obtain the single crystal ingot-shaped material of the anode raw material.
2) And (3) stretching and forming: forging and rolling the high-single-crystallinity positive and negative electrode ingot-shaped materials subjected to spiral crystal selection, repeatedly drawing the materials, and drawing the materials into wire materials with required sizes.
3) Stress relief annealing: and (3) performing filament annealing on the thermocouple positive wire material on a rewinding machine by using electric brush annealing equipment, wherein the temperature is 400 ℃, the winding speed is 40 r/min, and the negative wire material is performed filament annealing on the rewinding machine, the temperature is 400 ℃, and the winding speed is 40 r/min.
Example 4
A preparation method of an ultralong S-shaped single crystal couple wire comprises the following steps:
1) preparing a positive and negative electrode single crystal ingot material:
5g of platinum powder is used as a negative electrode material; 4.5g of platinum powder and 0.5g of rhodium powder were uniformly mixed to obtain a positive electrode material.
Respectively preparing seed crystals of the anode material and the cathode material, and respectively loading the seed crystals on a crystal starter in the spiral crystal selector. Adjusting the temperature of the crystal starter to melt the seed crystal part to form a solid-liquid pasty area, and keeping the temperature for 30 min.
Smelting the cathode raw material in a crucible at 1800 ℃ to obtain molten alloy; pouring molten high-temperature alloy melt into the spiral crystal selector after the heat preservation of the crystal starter is finished to form a whole with the melting part of the negative electrode material seed crystal, and standing for 10 min; and then slowly and vertically putting the spiral crystal selector into cooling liquid at the speed of 100 mu m/s, and gradually cooling and crystallizing the molten cathode raw material from bottom to top to obtain the single crystal ingot-shaped material of the cathode raw material.
Smelting the anode raw material in a crucible at 1900 ℃ to obtain molten alloy; pouring molten high-temperature alloy melt into the spiral crystal selector after the heat preservation of the crystal starter is finished to form a whole with the melting part of the positive material seed crystal, and standing for 10 min; and then slowly and vertically putting the spiral crystal selector into cooling liquid at the speed of 100 mu m/s, and gradually cooling and crystallizing the molten anode raw material from bottom to top to obtain the single crystal ingot-shaped material of the anode raw material.
2) And (3) stretching and forming: forging and rolling the high-single-crystallinity positive and negative electrode ingot-shaped materials subjected to spiral crystal selection, repeatedly drawing the materials, and drawing the materials into wire materials with required sizes.
3) Stress relief annealing: and (3) performing filament annealing on the thermocouple positive wire material on a rewinder by using electric brush annealing equipment at the temperature of 450 ℃ and the winding speed of 50 revolutions per minute, and performing filament annealing on the thermocouple negative wire material on the rewinder at the temperature of 450 ℃ and the winding speed of 50 revolutions per minute.
The evaluation method comprises the following steps:
the single crystal orientation and the impurity crystal probability of the thermocouple wires prepared in the embodiments 1 to 4 are tested, and the thermocouple wires prepared in the embodiments 1 to 4 are used for replacing the same thermocouple wire in an armored thermocouple to perform a temperature measurement test.
Results and conclusions:
(1) the single crystal orientation consistency of the thermocouple wires prepared in the embodiments 1 to 4 is not lower than 90%, and the probability of mixed crystal is not higher than 10%.
(2) Replacing the thermocouple wire prepared in the embodiment 1 with the same thermocouple wire in an armored thermocouple to perform temperature measurement test, and improving the full-range temperature measurement precision to 0.0015| t |; the thermocouple wire prepared in the embodiment 2 replaces the same thermocouple wire in an armored thermocouple to carry out temperature measurement test, and the whole-range temperature measurement precision is improved to 0.001| t |; replacing the thermocouple wire prepared in the embodiment 3 with the same thermocouple wire in an armored thermocouple to perform temperature measurement test, and improving the full-range temperature measurement precision to 0.0015| t |; the thermocouple wire prepared in the embodiment 4 replaces the same thermocouple wire in an armored thermocouple to carry out temperature measurement test, and the full-range temperature measurement precision is improved to 0.001| t |.
In conclusion, when the thermocouple wire prepared by using the spiral crystal selector is used in the thermocouple, the temperature measurement precision of the thermocouple can be obviously improved, and the full-range temperature measurement precision is improved to 0.001 to 0.002 t.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The application of a spiral crystal selector for preparing single crystal alloy in preparing a temperature thermocouple wire material is characterized in that the spiral crystal selector is used for preparing a thermocouple wire and comprises the following steps:
(1) adding seed crystals into the spiral crystal selector, placing the seed crystals on a crystal starter, and adjusting the heat preservation temperature of the crystal starter so as to partially melt the seed crystals;
(2) melting the raw material of the electric couple wire, injecting the obtained molten liquid into the spiral crystal selector to form a whole with the melting part of the seed crystal, and standing;
(3) vertically immersing the spiral crystal selector obtained in the step (2) into cooling liquid so as to cool and crystallize the melting liquid from bottom to top, thereby obtaining a single crystal ingot-shaped material;
(4) performing stretch forming treatment on the single crystal ingot-shaped material so as to obtain a single crystal wire;
(5) and performing stress relief annealing on the single crystal wire so as to obtain the positive electrode and/or negative electrode thermocouple wire.
2. The use according to claim 1, wherein the raw material of the electric couple wire is a raw material of a positive electrode and/or a raw material of a negative electrode of the electric couple wire, the raw material of the positive electrode is at least one selected from pure copper, pure nickel, pure chromium, pure iron, pure platinum, pure rhodium, pure tungsten and pure rhenium, and the raw material of the negative electrode is at least one selected from pure copper, pure nickel, pure silicon, pure platinum, pure tungsten and pure rhenium.
3. The use according to claim 1, wherein in step (3), the screw crystal selector is immersed in the cooling liquid at a pulling rate of not more than 6mm/min,
optionally, in the step (5), the stress relief annealing is performed on the single crystal wire by using a rewinder at 400-550 ℃ and a winding speed of 30-70 rpm.
4. The use according to claim 1, wherein the helical angle of the helical selector helical section is 30-75 degrees, the pitch is 0.1-3 times of the product of the tangent value of the helical angle and the inner diameter of the helical section, the number of helical turns of the helical section is not more than 2 turns,
optionally, the ratio of the height of the crystal starter to the inner diameter of the crystal starter is 0.5-2, and the ratio of the inner diameter of the crystal starter to the inner diameter of the spiral section of the spiral crystal selector is 3-6.
5. A galvanic couple wire is characterized in that the preparation method comprises the following steps:
(1) adding seed crystals into the spiral crystal selector, placing the seed crystals on a crystal starter, and adjusting the heat preservation temperature of the crystal starter so as to partially melt the seed crystals;
(2) melting the raw material of the electric couple wire, injecting the obtained molten liquid into the spiral crystal selector to form a whole with the melting part of the seed crystal, and standing;
(3) vertically immersing the spiral crystal selector obtained in the step (2) into cooling liquid so as to cool and crystallize the melting liquid from bottom to top, thereby obtaining a single crystal ingot-shaped material;
(4) performing stretch forming treatment on the single crystal ingot-shaped material so as to obtain a single crystal wire;
(5) and performing stress relief annealing on the single crystal wire so as to obtain the positive electrode and/or negative electrode thermocouple wire.
6. The electric couple wire of claim 5, wherein the electric couple wire raw material is a positive electrode raw material and/or a negative electrode raw material of the electric couple wire, the positive electrode raw material is at least one selected from pure copper, pure nickel, pure chromium, pure iron, pure platinum, pure rhodium, pure tungsten and pure rhenium, and the negative electrode raw material is at least one selected from pure copper, pure nickel, pure silicon, pure platinum, pure tungsten and pure rhenium.
7. The electric couple wire of claim 5, wherein in step (3), the helical crystal selector is immersed in the cooling liquid at a draw rate of not more than 6mm/min,
optionally, in the step (5), the stress relief annealing is performed on the single crystal wire by using a rewinder at 400-550 ℃ and a winding speed of 30-70 rpm.
8. The electric couple wire of claim 5, wherein the helix angle of the helical selector helical section is 30-75 degrees, the pitch is 0.1-3 times the product of the tangent value of the helix angle and the internal diameter of the helical section, and the number of helical turns of the helical section is not more than 2.
9. The electric couple wire according to claim 5 or 8, wherein the ratio of the height of the crystal starter to the inner diameter of the crystal starter is 0.5-2, and the ratio of the inner diameter of the crystal starter to the inner diameter of the spiral section of the spiral crystal selector is 3-6.
10. A thermocouple sensor, characterised in that it comprises a thermocouple wire according to any of claims 5 to 9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1428115A (en) * | 1965-02-13 | 1966-02-11 | Degussa | Process for the preparation of thermocouple wires of noble metals, in particular of platinum wires, as well as products conforming to those obtained by the present process or similar process |
| JPS61235512A (en) * | 1985-04-12 | 1986-10-20 | Furukawa Electric Co Ltd:The | Annealing method for grain oriented structure material |
| CN102312280A (en) * | 2010-07-05 | 2012-01-11 | 赵钧永 | Method and device for casting crystal material by using crystal selector |
| CN103143690A (en) * | 2013-04-02 | 2013-06-12 | 安泰科技股份有限公司 | Continuous casting device and method for directly preparing metal rod or wire |
| US20170101700A1 (en) * | 2014-04-04 | 2017-04-13 | Furuya Metal Co., Ltd. | Platinum thermocouple wire |
-
2020
- 2020-01-14 CN CN202010036890.7A patent/CN111155172A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1428115A (en) * | 1965-02-13 | 1966-02-11 | Degussa | Process for the preparation of thermocouple wires of noble metals, in particular of platinum wires, as well as products conforming to those obtained by the present process or similar process |
| JPS61235512A (en) * | 1985-04-12 | 1986-10-20 | Furukawa Electric Co Ltd:The | Annealing method for grain oriented structure material |
| CN102312280A (en) * | 2010-07-05 | 2012-01-11 | 赵钧永 | Method and device for casting crystal material by using crystal selector |
| CN103143690A (en) * | 2013-04-02 | 2013-06-12 | 安泰科技股份有限公司 | Continuous casting device and method for directly preparing metal rod or wire |
| US20170101700A1 (en) * | 2014-04-04 | 2017-04-13 | Furuya Metal Co., Ltd. | Platinum thermocouple wire |
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