CN110183240B - Preparation method of skutterudite with high mechanical strength - Google Patents
Preparation method of skutterudite with high mechanical strength Download PDFInfo
- Publication number
- CN110183240B CN110183240B CN201910273992.8A CN201910273992A CN110183240B CN 110183240 B CN110183240 B CN 110183240B CN 201910273992 A CN201910273992 A CN 201910273992A CN 110183240 B CN110183240 B CN 110183240B
- Authority
- CN
- China
- Prior art keywords
- skutterudite
- powder
- finished
- temperature
- potassium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
-
- C04B35/803—
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/405—Iron group metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5276—Whiskers, spindles, needles or pins
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6565—Cooling rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention relates to a preparation method of skutterudite with high mechanical strength, which comprises the following steps: weighing high-purity cobalt powder and antimony powder according to a stoichiometric ratio, and weighing 1vol% of potassium hexatitanate crystal whisker; adding a dispersing agent into the potassium hexatitanate whiskers, carrying out ultrasonic treatment to preliminarily disperse the potassium hexatitanate whiskers to obtain a potassium titanate mixed solution, carrying out ball milling on the mixed solution of the raw materials cobalt powder and antimony powder and the potassium titanate after the ultrasonic treatment is finished, and drying after the ball milling is finished; and (3) performing hot-pressing synthesis on the dried powder by using a vacuum hot-pressing furnace, sintering the powder into blocks, and cooling the blocks along with the furnace after the heat preservation is finished to obtain the high-strength skutterudite. The beneficial effects of the invention include: by adopting the special process, the skutterudite particles have small particle size, uniform and compact distribution, the potassium titanate whiskers are uniformly distributed, and the strength of the skutterudite is obviously improved. The reaction condition is easy to realize, the process operation is simple, and the method is efficient and reliable; the strength of the skutterudite obtained by the method is improved by about 100 percent compared with that of the skutterudite obtained by the traditional process.
Description
Technical Field
The invention belongs to the technical field of thermoelectric materials, and particularly relates to a preparation method of skutterudite with high mechanical strength.
Background
The skutterudite has the characteristics of no pollution, no toxicity, relatively simple preparation process and the like, has great application prospect in the field of medium-high temperature thermoelectric application, and is a thermoelectric material with great potential. At present, great progress has been made in the study of thermoelectric properties of skutterudite, but relatively few studies have been made on mechanical properties thereof. The method for improving the mechanical property of the skutterudite is to compound a second phase in a skutterudite matrix, but the process is relatively complex, and the improvement range of the mechanical property is relatively small. Therefore, how to greatly improve the mechanical property of the skutterudite material is a problem to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a preparation method for synthesizing skutterudite with high mechanical strength in one step. The preparation method has strong operability and relatively simple process, and the obtained high-strength skutterudite has stable performance and high mechanical strength.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of skutterudite with high mechanical strength comprises the following steps:
1) weighing high-purity cobalt powder and antimony powder according to a stoichiometric ratio, and weighing 1vol% of potassium hexatitanate crystal whisker;
2) adding a dispersing agent into the potassium hexatitanate whiskers, carrying out ultrasonic treatment to preliminarily disperse the potassium hexatitanate whiskers to obtain a potassium titanate mixed solution, carrying out ball milling on the mixed solution of the raw materials cobalt powder and antimony powder and the potassium titanate after the ultrasonic treatment is finished, and drying after the ball milling is finished;
3) and (3) performing hot-pressing synthesis on the dried powder by using a vacuum hot-pressing furnace, sintering the powder into blocks, and cooling the blocks along with the furnace after the heat preservation is finished to obtain the high-strength skutterudite.
According to the scheme, the purity of the raw material high-purity cobalt powder is 99.9%, the purity of the raw material antimony powder is 99.999%, and the potassium hexatitanate whisker has a diameter of 0.2-1.5 mu m and a length of 10-100 mu m.
According to the scheme, the ultrasonic time in the step 2) is 0.5-1h, and the ball milling time is 0.5-1 h.
According to the scheme, the dispersing agent is ethanol, hexane or water.
According to the scheme, the hot-press synthesis system comprises the following steps: raising the temperature from room temperature to 550-700 ℃ at a speed of 5-10 ℃/min, and the pressure is 40-50 MPa; then raising the temperature to 600-750 ℃ at the temperature of 2-10 ℃/min, keeping the pressure at 0MPa, and keeping the temperature for 15-25 min; after the heat preservation is finished, the temperature is reduced to 600 ℃ at the speed of 10 ℃/min, the heat preservation is carried out for 2h, at the moment, the sample is pressurized again, and the pressure intensity is 35-50 MPa.
In the high temperature stage, because of no pressure limitation, the crystal grains grow freely, the size of the crystal grains is uniform, and the crystal boundary is obvious. And after the temperature is reduced, the pressure is maintained again, the residual stress in the obtained sample is small, the particle size of the skutterudite particles is small, the skutterudite particles are uniformly and compactly distributed, and the compactness of the sample is about 97 percent. On the other hand, potassium titanate with excellent mechanical properties is introduced into the matrix as a reinforcing agent material. The potassium titanate is distributed in the matrix relatively uniformly, and the potassium titanate whiskers embedded and inserted into the matrix at the grain boundary form bridging with the matrix, and in the fracture process of the composite material, the bridging is accompanied with the pulling-out of the whiskers, so that the plastic deformation of the matrix along the interface of the matrix and the whiskers is increased, and the expansion of cracks is effectively hindered or the expansion path is forced to be changed.
The beneficial effects of the invention include: 1) by adopting the special process, the skutterudite particles have small particle size, uniform and compact distribution, the potassium titanate whiskers are uniformly distributed, and the strength of the skutterudite is obviously improved. The reaction condition is easy to realize, the process operation is simple, and the method is efficient and reliable; 2) the strength of the skutterudite obtained by the method is improved by about 100% compared with that of the skutterudite obtained by the traditional process, and the skutterudite has stable performance and great popularization value.
Drawings
FIG. 1 is CoSb of example 13650-40 MPa of K-free2Ti6O13SEM image of control (magnification 20000 times);
FIG. 2 is CoSb of example 23-650-40 MPa SEM images (magnification 20000 times);
FIG. 3 is CoSb of example 33700 ℃ -40MPa SEM images (magnification 20000 times);
FIG. 4 shows the bending strength of skutterudite samples obtained by different processes;
FIG. 5 fracture toughness of skutterudite samples obtained by different processes.
Detailed Description
The skutterudite having high strength and the preparation method thereof according to the present invention will be described in detail. The features and properties of the present invention are further described in detail below with reference to examples:
example 1:
the embodiment provides skutterudite with high mechanical strength, which is prepared by the following method:
firstly, raw materials comprise high-purity cobalt powder (99.9%), antimony powder (99.999%) and potassium hexatitanate whiskers (the diameter is 0.2-1.5 mu m, the length is 10-100 mu m), and the cobalt powder and the antimony powder (10g) are weighed by an electronic balance according to the stoichiometric ratio of 1: 3. Placing the weighed cobalt powder and antimony powder into an agate ball milling tank, and carrying out ball milling for 1h at a ball-material ratio of 3:1 and a rotating speed of 250 rpm. And after the ball milling is finished, putting the sample into a drying box for drying. And (2) putting the dried powder into a graphite die, and performing hot-pressing synthesis and simultaneous sintering to form blocks by using a vacuum hot-pressing furnace (combined fertilizer crystal, model OTF-1200X), wherein the specific hot-pressing scheme is as follows: heating from room temperature to 600 deg.C at 10 deg.C/min under 40 MPa; then heating to 650 ℃ from the temperature at the speed of 2 ℃/min, keeping the pressure at 0MPa, and keeping the temperature for 20 min; and after the heat preservation is finished, cooling to 600 ℃ at a speed of 10 ℃/min, preserving the heat for 2h, re-pressurizing the sample at the moment, wherein the pressure is 40MPa, and cooling along with the furnace after the heat preservation is finished to obtain the skutterudite with high mechanical strength. The microscopic morphology was observed by field emission scanning electron microscopy, as shown in FIG. 1.
Example 2:
the present example provides skutterudite with high mechanical strength, which is different from example 1 in that:
firstly, raw materials comprise high-purity cobalt powder (99.9%), antimony powder (99.999%) and potassium hexatitanate whiskers (diameter is 0.2-1.5 mu m, length is 10-100 mu m), cobalt powder and antimony powder (10g) are weighed by an electronic balance according to a stoichiometric ratio of 1:3, and 1vol% of potassium titanate whiskers (0.0436g) are weighed. Putting the potassium titanate whiskers into a beaker, adding a proper amount of alcohol, carrying out ultrasonic treatment for 0.5h (model KQ-100E, frequency 40KHz), putting the mixed solution of the raw materials of cobalt powder, antimony powder and potassium titanate alcohol into an agate ball milling tank after the ultrasonic treatment is finished, and carrying out ball milling for 1h at a ball-to-material ratio of 3:1 and a rotation speed of 250 rpm. And after the ball milling is finished, putting the sample into a drying box for drying. And (2) putting the dried powder into a graphite die, and performing hot-pressing synthesis and simultaneous sintering to form blocks by using a vacuum hot-pressing furnace (combined fertilizer crystal, model OTF-1200X), wherein the specific hot-pressing scheme is as follows: heating from room temperature to 600 deg.C at 10 deg.C/min under 40 MPa; then heating to 650 ℃ from the temperature at the speed of 2 ℃/min, keeping the pressure at 0MPa, and keeping the temperature for 20 min; and after the heat preservation is finished, cooling to 600 ℃ at a speed of 10 ℃/min, preserving the heat for 2h, re-pressurizing the sample at the moment, wherein the pressure is 40MPa, and cooling along with the furnace after the heat preservation is finished to obtain the skutterudite with high mechanical strength. The microscopic morphology was observed by field emission scanning electron microscopy, as shown in FIG. 2.
Example 3:
the present example provides skutterudite with high mechanical strength, which is different from example 1 in that: firstly, raw materials comprise high-purity cobalt powder (99.9%), antimony powder (99.999%) and potassium hexatitanate whiskers (diameter is 0.2-1.5 mu m, length is 10-100 mu m), cobalt powder and antimony powder (10g) are weighed by an electronic balance according to a stoichiometric ratio of 1:3, and 1vol% of potassium titanate whiskers (0.0436g) are weighed. Putting the potassium titanate whiskers into a beaker, adding a proper amount of alcohol, carrying out ultrasonic treatment for 0.5h (model KQ-100E, frequency 40KHz), putting the raw material powder and the potassium titanate alcohol mixed solution into an agate ball milling tank after the ultrasonic treatment, carrying out ball milling for 1h, wherein the ball-to-material ratio is 3:1, and the rotating speed is 250 rpm. And after the ball milling is finished, putting the sample into a drying box for drying. And (2) putting the dried powder into a graphite die, and performing hot-pressing synthesis and simultaneous sintering to form blocks by using a vacuum hot-pressing furnace (combined fertilizer crystal, model OTF-1200X), wherein the specific hot-pressing scheme is as follows: heating from room temperature to 700 deg.C at 10 deg.C/min under 40 MPa; then heating to 750 ℃ from the temperature at the speed of 2 ℃/min, keeping the pressure at 0MPa, and keeping the temperature for 20 min; and after the heat preservation is finished, cooling to 600 ℃ at a speed of 10 ℃/min, preserving the heat for 2h, re-pressurizing the sample at the moment, wherein the pressure is 40MPa, and cooling along with the furnace after the heat preservation is finished to obtain the skutterudite with high mechanical strength. The microscopic morphology was observed by field emission scanning electron microscopy, as shown in FIG. 3.
FIG. 1, FIG. 2 and FIG. 3 are scanning electron micrographs of fractures of the sample, and it can be seen from the images that the sample has no obvious cracks and holes on the cross section and has good compactness. The skutterudite crystal is in a rock candy block shape, the grain size is between 2 and 3 mu m, and the grain boundary is obvious. Fig. 2 and 3 are scanning electron micrographs of hot press sintered samples at 650 c and 700 c, respectively, from which it can be seen that there is a slight increase in grain size with increasing temperature. Fig. 1 shows a sample without potassium titanate, and fig. 2 shows a sample with potassium titanate, and it can be seen from the figure that potassium titanate whiskers are distributed among crystal grains and are inserted in a matrix.
The variation of the bending strength of skutterudite with the process at different reaction temperatures is shown in FIG. 4. As can be seen in the figure, the bending strength of BC650-0 (potassium titanate not compounded) is improved by nearly 94% compared to the sample prepared by the conventional process (not compounded with the nanomaterial). After the potassium titanate is doped, the bending performance of the sample is obviously improved. The flexural strength of the solid phase/650 (raw material powder after solid phase reaction, grinding and grinding, adding potassium titanate and then hot pressing at 650 ℃) was improved by about 28% compared with that of BC650-0 (potassium titanate not compounded).
The variation of the skutterudite fracture toughness with process at different reaction temperatures is shown in FIG. 5. As can be seen in the figure, the fracture toughness of BC650-0 (potassium titanate not compounded) is improved by nearly 103% compared to the samples prepared by the conventional process (not compounded with the nanomaterial). After the potassium titanate is doped, the fracture toughness of the sample is obviously improved. Compared with BC650-0, the fracture toughness of BC700 (composite potassium titanate) is improved by about 11%.
Claims (4)
1. A preparation method of skutterudite with high mechanical strength comprises the following steps:
1) weighing high-purity cobalt powder and antimony powder according to a stoichiometric ratio, and weighing 1vol% of potassium hexatitanate crystal whisker;
2) adding a dispersing agent into the potassium hexatitanate whiskers, carrying out ultrasonic treatment to preliminarily disperse the potassium hexatitanate whiskers to obtain a potassium titanate mixed solution, carrying out ball milling on the mixed solution of the raw materials cobalt powder and antimony powder and the potassium titanate after the ultrasonic treatment is finished, and drying after the ball milling is finished;
3) hot-pressing the dried powder by using a vacuum hot-pressing furnace, sintering the powder into blocks, and cooling the blocks along with the furnace after the heat preservation is finished to obtain the high-strength skutterudite;
the hot-pressing synthesis system comprises the following steps: raising the temperature from room temperature to 550-700 ℃ at a speed of 5-10 ℃/min, and the pressure is 40-50 MPa; then raising the temperature to 600-750 ℃ at the temperature of 2-10 ℃/min, keeping the pressure at 0MPa, and keeping the temperature for 15-25 min; after the heat preservation is finished, the temperature is reduced to 600 ℃ at the speed of 10 ℃/min, the heat preservation is carried out for 2h, at the moment, the sample is pressurized again, and the pressure intensity is 35-50 MPa.
2. The method for preparing skutterudite with high mechanical strength according to claim 1, wherein the purity of the raw material high-purity cobalt powder is 99.9%, the purity of the raw material antimony powder is 99.999%, and the potassium hexatitanate whisker has a diameter of 0.2-1.5 μm and a length of 10-100 μm.
3. The method for preparing skutterudite having high mechanical strength according to claim 1, wherein the ultrasonic time in the step 2) is 0.5 to 1 hour, and the ball milling time is 0.5 to 1 hour.
4. The method of preparing skutterudite having high mechanical strength according to claim 1, wherein the dispersant is ethanol, hexane or water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910273992.8A CN110183240B (en) | 2019-04-04 | 2019-04-04 | Preparation method of skutterudite with high mechanical strength |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910273992.8A CN110183240B (en) | 2019-04-04 | 2019-04-04 | Preparation method of skutterudite with high mechanical strength |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110183240A CN110183240A (en) | 2019-08-30 |
| CN110183240B true CN110183240B (en) | 2021-11-02 |
Family
ID=67714049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910273992.8A Active CN110183240B (en) | 2019-04-04 | 2019-04-04 | Preparation method of skutterudite with high mechanical strength |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110183240B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112978684B (en) * | 2021-02-05 | 2023-07-04 | 武汉理工大学 | Intra-crystalline porous high-performance skutterudite thermoelectric material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5929351A (en) * | 1997-04-23 | 1999-07-27 | Matsushita Electric Industrial Co., Ltd. | Co-Sb based thermoelectric material and a method of producing the same |
| CN1594623A (en) * | 2004-06-29 | 2005-03-16 | 武汉理工大学 | Preparation method for nano skutterudite compound pyro electric material |
| CN1876283A (en) * | 2006-05-30 | 2006-12-13 | 武汉理工大学 | Titanium cobalt antimony base thermoelectric semiconductor material preparation method |
| CN1974889A (en) * | 2006-11-23 | 2007-06-06 | 四川大学 | Potassium hexatitanate whisker and its prepn process |
| CN102931335A (en) * | 2012-10-24 | 2013-02-13 | 东华大学 | Graphene compounded with stibine cobalt base skutterudite thermoelectric material and preparation method of material |
| CN103981468A (en) * | 2014-05-26 | 2014-08-13 | 中国科学院上海硅酸盐研究所 | Skutterudite-based thermoelectricity composite material with high mechanical property and preparation method thereof |
-
2019
- 2019-04-04 CN CN201910273992.8A patent/CN110183240B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5929351A (en) * | 1997-04-23 | 1999-07-27 | Matsushita Electric Industrial Co., Ltd. | Co-Sb based thermoelectric material and a method of producing the same |
| CN1594623A (en) * | 2004-06-29 | 2005-03-16 | 武汉理工大学 | Preparation method for nano skutterudite compound pyro electric material |
| CN1876283A (en) * | 2006-05-30 | 2006-12-13 | 武汉理工大学 | Titanium cobalt antimony base thermoelectric semiconductor material preparation method |
| CN1974889A (en) * | 2006-11-23 | 2007-06-06 | 四川大学 | Potassium hexatitanate whisker and its prepn process |
| CN102931335A (en) * | 2012-10-24 | 2013-02-13 | 东华大学 | Graphene compounded with stibine cobalt base skutterudite thermoelectric material and preparation method of material |
| CN103981468A (en) * | 2014-05-26 | 2014-08-13 | 中国科学院上海硅酸盐研究所 | Skutterudite-based thermoelectricity composite material with high mechanical property and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110183240A (en) | 2019-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109553419B (en) | Pneumatic solid-phase sintered boron carbide complex-phase ceramic and preparation method thereof | |
| CN109439940B (en) | Method for preparing particle reinforced aluminum matrix composite material by hot-pressing sintering under atmospheric atmosphere | |
| CN109836155A (en) | A kind of double rare earth tantalate solid solution refractory ceramics of densification ferroelasticity and preparation method thereof | |
| CN101434488B (en) | Silicon nitride-based composite ceramic with phosphates as sintering aid and preparation thereof | |
| CN110396632A (en) | A kind of Ti (C, N) based ceramic metal and preparation method thereof with homogeneous ring core structure | |
| CN112645726B (en) | Silicon carbide whisker ceramic with typical long particle morphology and rich in stacking faults and twin crystals and preparation method thereof | |
| CN107513651B (en) | A kind of preparation method of titanium particle reinforced magnesium base composite material | |
| CN111825458A (en) | High-density boron carbide ceramic material and pressureless sintering preparation method thereof | |
| CN103820691B (en) | A kind of normal pressure-sintered preparation method of FeAl/TiC matrix material | |
| CN110183240B (en) | Preparation method of skutterudite with high mechanical strength | |
| CN111116202A (en) | Method for sintering boron carbide-titanium boride material through discharge plasma reaction | |
| CN111116206A (en) | Preparation method of compact MoAlB ceramic material, product thereof and preparation method of high-purity MoAlB ceramic powder | |
| CN101734920B (en) | Titanium nitride porous ceramics and preparation method thereof | |
| CN114835473B (en) | Alumina ceramic and preparation method thereof | |
| CN108975918A (en) | A kind of high tenacity high-temperature structural material MoSi2-Mo5Si3The preparation of composite ceramics | |
| CN109851329A (en) | A kind of fine grain Al2O3/ SiC composite ceramic tool material and preparation process | |
| CN111548169B (en) | High-temperature high-pressure preparation method of high-strength transparent silicon nitride ceramic | |
| CN110343932B (en) | WVTaZrSc refractory high-entropy alloy with high strength and preparation method thereof | |
| JP2005089252A (en) | Metallic ceramic sintered compact titanium silicon carbide and method of manufacturing the same | |
| CN113416078A (en) | Non-stoichiometric titanium boride and high-entropy boride ceramic prepared from same | |
| CN109180209B (en) | Method for preparing silicon carbide nanowire reinforced graphite-silicon carbide composite material by adopting in-situ self-generation method | |
| CN113105216A (en) | Injection-molded zirconium-aluminum composite ceramic and preparation method thereof | |
| CN111606712A (en) | Method for preparing boron carbide ceramic by low-temperature pulse pressurization | |
| CN116730723B (en) | Al (aluminum) alloy 3 BC ceramic material and preparation method and application thereof | |
| CN113604722B (en) | Preparation method for in-situ synthesis of Fe-FeAl2O4 composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |