CN115286385B - Adjustable thermal expansion coefficient material Ta 1-x Ti x Mo x V 1-x O 5 And method for preparing the same - Google Patents
Adjustable thermal expansion coefficient material Ta 1-x Ti x Mo x V 1-x O 5 And method for preparing the same Download PDFInfo
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Abstract
The invention belongs to the field of inorganic non-metallic materials, and discloses a heat-adjustable materialMaterial of coefficient of expansion Ta x1‑ Ti x Mo x V x1‑ O 5 And a method for preparing the same. The preparation steps are as follows: (1) Selecting V 2 O 5 、TiO 2 、MoO 3 And Ta 2 O 5 Using Ta as a raw material 2 O 5 、TiO 2 、MoO 3 And V 2 O 5 According to the target product Ta x1‑ Ti x Mo x V x1‑ O 5 The molar ratio of Ta to Ti to Mo to V = (1-x）∶x∶x∶（1‑x) Grinding and mixing uniformly, and pressing the obtained mixed powder into a sheet shape; (2) Taking the pressed sheet obtained in the step (1) as a center, and placing a circle of V around the pressed sheet 2 O 5 Sintering the powder at the temperature of 620-670 ℃ for 12-24 h, and cooling to obtain a target product Ta 1‑ x Ti x Mo x V x1‑ O 5 . The invention selects metal elements with different ionic radii to be TaVO for the first time 5 Double-element substitution is carried out to realize effective regulation and control of the thermal expansion coefficient, so that the material with zero expansion coefficient or near-zero expansion coefficient is prepared.
Description
Technical Field
The invention belongs to the field of inorganic non-metallic materials, and particularly relates to a material Ta with an adjustable thermal expansion coefficient 1- x Ti x Mo x V x1- O 5 And a method for preparing the same.
Background
In recent years, with the higher and higher requirements for the performance of materials, the research on materials with good expansion performance is more and more intensive, and a plurality of negative thermal expansion, low thermal expansion and near-zero expansion materials appear. The negative thermal expansion phenomenon is opposite to the thermal expansion phenomenon commonly existing in the nature, the thermal expansion phenomenon commonly existing in the nature is thermal expansion and cold contraction, but the performance can bring adverse effects to precision instruments, photoelectric communication, electronic devices and the like. It is therefore of great importance to find new negative thermal expansion, low thermal expansion and near zero expansion materials.
The low thermal expansion and near-zero expansion material has a smaller expansion coefficient than that of the common material, so that the material can show stronger thermal shock resistance and has great application potential. Early reports on low thermal expansion materials such as Invar alloy, siO 2 -TiO 2 Glass and the like have been widely used in various fields requiring high thermal stability. Even though such reports are earlier than the research on the negative thermal expansion material, the research on the negative thermal expansion material is later conducted to promote the research progress of the low thermal expansion material.
In order to fundamentally solve a series of problems caused by the thermal expansion phenomenon, the thermal expansion coefficient of the material must be accurately regulated and controlled, and a low-thermal expansion material or even a near-zero expansion material is designed. In order to design a low thermal expansion and near zero expansion material, atoms of a negative thermal expansion material are partially replaced, so that the low thermal expansion and near zero expansion material is obtained. To A 2 B 3 O 12 In the research of negative thermal expansion materials, regulating and controlling the thermal expansion performance of the materials is a hot spot of research. And for A 2 B 3 O 12 This method is also relatively easy to implement for negative thermal expansion materials. A. The 2 B 3 O 12 The negative thermal expansion material can be substituted by A-site ions, such as Cr 2 Mo 3 O 12 Is Er at the A position 3+ 、Y 3+ Partial substitution, the coefficient of thermal expansion of the synthesized sample becomes more negative with the increase of the substitution amount; sc (Sc) 2 Mo 3 O 12 Is substituted by Cr 3+ Partially substituted, the synthesized sample has near-zero expansion performance; fe 2 Mo 3 O 12 Is Er at the A position 3 + 、Cr 3+ 、Al 3+ Partially substituted, the synthesized samples had low thermal expansion properties. In addition, A 2 B 3 O 12 The position B of the negative thermal expansion material can also be substituted by ions, and the position B can be substituted by W 6+ Ion substitution can also have a great influence on the thermal expansion performance of the synthesized sample; in addition, the A position and the B position can also be simultaneouslyAnd (4) carrying out double-ion substitution.
For AM 2 O 8 In series of negative thermal expansion materials, the A position may be partially replaced by an ionic moiety, e.g. ZrW 2 O 8 Position A of (1) by Hf 4+ Ion substitution; the A position may also be Sn 4+ Or Ti 4+ And (4) ion substitution. The B position can also be easily substituted by ions, e.g. the B position can be replaced by Mo 6+ 、V 5+ 、P 5+ Ion substitution; the A position and the B position can be simultaneously replaced by a plurality of ions, and the replacement of different positions also has certain influence on the thermal expansion coefficient of the synthesized sample. The negative thermal expansion material of vanadate has wide application and is a hot point for controlling the thermal expansion performance of vanadate, for example, a V atom of zirconium vanadate can be replaced by a P atom, a Mo atom and a W atom, a Zr atom can be replaced by a Hf atom, a Y atom and a Nb atom, and a Zr atom and a V atom can be simultaneously replaced by two atoms. At AMO 5 In family, A is a pentavalent metal, which may be Nb 5+ 、Ta 5+ 、V 5+ M may be P 5+ 、V 5+ And As 5+ NTE properties are mainly expressed in NbPO 5 、TaVO 5 、NbVO 5 Orthogonal phase and TaPO of 5 The tetragonal phase of (1). For AMO 5 There are few reports on the regulation of negative thermal expansion behavior, and Nb has been reported 5+ Chemical substitution of elements for Ta 5+ Element, as 5+ Element substitution V 5+ Elemental, but not to TaVO 5 The thermal expansion performance of the material is well regulated and controlled. In summary, in the regulation of negative thermal expansion oxide materials, vanadate and AM are used 2 O 8 And A 2 B 3 O 12 And the negative thermal expansion material containing more oxygen elements is easy to regulate and control and is easy to prepare. But for AMO 5 The negative thermal expansion material containing less oxygen elements is difficult to prepare by an ion substitution method, and the thermal expansion performance of the material is difficult to regulate.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the material Ta with the adjustable thermal expansion coefficient x1- Ti x Mo x V x1- O 5 And a method for preparing the same.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a material with adjustable thermal expansion coefficient and its molecular formula is Ta 1-x Ti x Mo x V 1-x O 5 Wherein 0.00 <x≤0.75。
The preparation method of the adjustable thermal expansion coefficient material comprises the following preparation steps:
(1) Selecting V 2 O 5 、TiO 2 、MoO 3 And Ta 2 O 5 Using Ta as a raw material 2 O 5 、TiO 2 、MoO 3 And V 2 O 5 According to the target product Ta x1- Ti x Mo x V x1- O 5 The molar ratio of Ta to Ti to Mo to V = (1-x）∶x∶x∶（1-x) Grinding and mixing uniformly, and pressing the obtained mixed powder into a sheet shape;
(2) Taking the pressed sheet obtained in the step (1) as a center, and placing a circle of V around the pressed sheet 2 O 5 Sintering the powder at the temperature of 620-670 ℃ for 12-24 h, and cooling to obtain a target product Ta x1- Ti x Mo x V x1- O 5 。
Preferably, in step (2), V 2 O 5 The distance between the powder and the center of the tablet is 1-2 cm 2 O 5 The total mass of the powder is 1-2 times of that of the tablet.
Preferably, in step (1), wet grinding is adopted, and ethanol is added during grinding of the raw materials in an amount to wet V 2 O 5 、TiO 2 、MoO 3 And Ta 2 O 5 The standard is.
Compared with the prior art, the invention has the following beneficial effects: the invention selects metal elements with different ionic radii to be TaVO for the first time 5 Double-element doping is carried out to realize the regulation and control of the thermal expansion coefficient, so that the material with zero expansion coefficient or near-zero expansion coefficient is preparedFeeding; the adjustable thermal expansion coefficient material has good stability, wide application, simple preparation process and low cost, is suitable for industrial production, and is expected to be applied to the high-tech fields of biomedical materials, aerospace equipment, precision instruments and the like.
Drawings
FIG. 1: ta prepared in examples 1 to 4 x1- Ti x Mo x V x1- O 5 (x=0.00, 0.25, 0.50, 0.75) XRD pattern corresponding to product.
FIG. 2: ta prepared in examples 1 to 4 x1- Ti x Mo x V x1- O 5 (x=0.00, 0.25, 0.50, 0.75) product corresponding Raman spectrum.
FIG. 3: ta prepared in examples 1 to 4 x1- Ti x Mo x V x1- O 5 (x=0.00, 0.25, 0.50, 0.75) relative length versus temperature profile for the product.
FIG. 4: ta prepared in comparative example 1-2 0.75 Ti 0.25 VO 5 、TaMo 0.1 V 0.9 O 5 And (3) XRD pattern corresponding to the product.
FIG. 5: taMo prepared in comparative examples 3 to 4 0.25 V 0.75 O 5 、Ta 0.75 P 0.25 VO 5 And (3) XRD pattern corresponding to the product.
FIG. 6: ta prepared in comparative example 1-2 0.75 Ti 0.25 VO 5 、TaMo 0.1 V 0.9 O 5 The relative length of the product is plotted against temperature.
FIG. 7: ta prepared in examples 2 and 3 0.75 Ti 0.25 Mo 0.25 V 0.75 O 5 、Ta 0.5 Ti 0.5 Mo 0.5 V 0.5 O 5 TG curve of product.
Detailed Description
In order to make the invention clearer and clearer, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Preparation of TaVO by solid phase method 5 Ceramic powder: selecting analytically pure V 2 O 5 And Ta 2 O 5 Using Ta as a raw material 2 O 5 And V 2 O 5 Mixing according to the molar ratio of Ta to V =1 to 1, adding absolute ethyl alcohol to wet, grinding in an agate mortar for 2 hours, and pressing the obtained powder into a cylinder with the diameter of 8mm and the height of 5 mm; using the cylinder as the center, handle V 2 O 5 Powder is sprinkled around the cylinder, V 2 O 5 The distance of the powder from the center of the cylinder is 1 cm 2 O 5 The total mass of the powder is 1 time of that of the cylinder, the temperature is raised to 800 ℃ in a muffle furnace at the heating rate of 5 ℃/min, the temperature is maintained and calcined for 24 hours, and the temperature is naturally reduced to the room temperature in the air to obtain the TaVO with the negative thermal expansion performance 5 。
Example 2
Preparation of Ta by solid phase method 0.75 Ti 0.25 Mo 0.25 V 0.75 O 5 Ceramic powder:
selecting analytically pure V 2 O 5 、TiO 2 、MoO 3 And Ta 2 O 5 Using Ta as a raw material 2 O 5 、TiO 2 、MoO 3 And V 2 O 5 Mixing according to the mol ratio of Ta to Ti to Mo to V =0.75 to 0.25 to 0.75, adding absolute ethyl alcohol to wet, grinding for 2 hours in an agate mortar, and pressing the obtained powder into a cylinder with the diameter of 8mm and the height of 5 mm; using the cylinder as the center, handle V 2 O 5 Powder sprinkled around the cylinder, V 2 O 5 The distance of the powder from the center of the cylinder is 1 cm 2 O 5 The total mass of the powder is 1 time of that of the cylinder, the powder is subjected to heat preservation and calcination for 12 hours in a muffle furnace at the temperature rise rate of 670 ℃ of 5 ℃/min, and the temperature is naturally reduced to the room temperature in the air to obtain the Ta with the negative expansion performance 0.75 Ti 0.25 Mo 0.25 V 0.75 O 5 。
Example 3
Preparation of Ta by solid phase method 0.5 Ti 0.5 Mo 0.5 V 0.5 O 5 Ceramic powder: selecting analytically pure V 2 O 5 、TiO 2 、MoO 3 And Ta 2 O 5 Using Ta as a raw material 2 O 5 、TiO 2 、MoO 3 And V 2 O 5 Mixing according to the mol ratio of Ta to Ti to Mo to V = 0.5: 0.5, adding absolute ethyl alcohol to wet, grinding for 2 hours in an agate mortar, and pressing the obtained powder into a cylinder with the diameter of 8mm and the height of 5 mm; using the cylinder as the center, handle V 2 O 5 Powder sprinkled around the cylinder, V 2 O 5 The distance of the powder from the center of the cylinder is 1 cm 2 O 5 The total mass of the powder is 1 time of that of the cylinder, the powder is subjected to heat preservation and calcination for 12 hours in a muffle furnace at the temperature rise rate of 650 ℃ at the speed of 5 ℃/min, and the temperature is naturally reduced to the room temperature in the air to obtain Ta with the near-zero expansion performance 0.5 Ti 0.5 Mo 0.5 V 0.5 O 5 。
Example 4
Preparation of Ta by solid phase method 0.25 Ti 0.75 Mo 0.75 V 0.25 O 5 Ceramic powder: selecting analytically pure V 2 O 5 、TiO 2 、MoO 3 And Ta 2 O 5 Using Ta as a raw material 2 O 5 、TiO 2 、MoO 3 And V 2 O 5 Mixing Ta, ti, mo and V = 0.25: 0.75: 0.25 according to a molar ratio, adding absolute ethyl alcohol to wet, grinding for 2 hours in an agate mortar, and pressing the obtained powder into a cylinder with the diameter of 8mm and the height of 5 mm; using the cylinder as the center, handle V 2 O 5 Powder is sprinkled around the cylinder, V 2 O 5 The distance of the powder from the center of the cylinder is 1 cm 2 O 5 The total mass of the powder is 1 time of that of the cylinder, the powder is subjected to heat preservation and calcination for 12 hours in a muffle furnace at the heating rate of 620 ℃ at the speed of 5 ℃/min, and the temperature is naturally reduced to the room temperature in the air to obtain the Ta with positive expansion performance 0.25 Ti 0.75 Mo 0.75 V 0.25 O 5 。
Comparative example 1
Preparation of Ta by solid phase method 0.75 Ti 0.25 VO 5 Ceramic powder: selecting analytically pure V 2 O 5 、TiO 2 And Ta 2 O 5 Using Ta as a raw material 2 O 5 、TiO 2 And V 2 O 5 Mixing according to the molar ratio of Ta to Ti to V =0.75 to 0.25 to 1, adding absolute ethyl alcohol to wet, grinding for 2 hours in an agate mortar, and pressing the obtained powder into a cylinder with the diameter of 8mm and the height of 5 mm; centering on the cylinder, handle V 2 O 5 Powder is sprinkled around the cylinder, V 2 O 5 The distance of the powder from the center of the cylinder is 1 cm 2 O 5 The total mass of the powder is 1 time of that of the cylinder, the powder is heated up in a muffle furnace at the heating rate of 5 ℃/min of 800 ℃, the powder is subjected to heat preservation and calcination for 24 hours, and the temperature is naturally reduced to the room temperature in the air to obtain the Ta with the negative expansion performance 0.75 Ti 0.25 VO 5 。
Comparative example 2
Preparation of TaMo by solid phase method 0.1 V 0.9 O 5 Ceramic powder: selecting analytically pure V 2 O 5 、MoO 3 And Ta 2 O 5 Using Ta as a raw material 2 O 5 、MoO 3 And V 2 O 5 Mixing according to the molar ratio of Ta to Mo to V = 1: 0.1: 0.9, adding absolute ethyl alcohol to wet, grinding for 2 hours in an agate mortar, and pressing the obtained powder into a cylinder with the diameter of 8mm and the height of 5 mm; using the cylinder as the center, handle V 2 O 5 Powder is sprinkled around the cylinder, V 2 O 5 The distance of the powder from the center of the cylinder is 1 cm 2 O 5 The total mass of the powder is 1 time of that of the cylinder, the powder is heated up to 750 ℃ at the heating rate of 5 ℃/min in a muffle furnace, the powder is subjected to heat preservation and calcination for 10 hours, and the temperature is naturally reduced to the room temperature in the air, so that TaMo with negative expansion performance is obtained 0.1 V 0.9 O 5 。
Comparative example 3
Solid phase method for preparing TaMo 0.25 V 0.75 O 5 Ceramic powder: selecting analytically pure V 2 O 5 、MoO 3 And Ta 2 O 5 Using Ta as a raw material 2 O 5 、MoO 3 And V 2 O 5 Mixing according to the molar ratio of Ta to Mo to V = 1: 0.25: 0.75, adding absolute ethyl alcohol to wet, grinding for 2 hours in an agate mortar, and pressing the obtained powder into a cylinder with the diameter of 8mm and the height of 5 mm; using the cylinder as the center, handle V 2 O 5 Powder is sprinkled around the cylinder, V 2 O 5 The distance of the powder from the center of the cylinder is 1 cm 2 O 5 The total mass of the powder is 1 time of that of the cylinder, the powder is calcined in a muffle furnace at the heating rate of 5 ℃/min of 700 ℃ for 12 h under heat preservation, and the temperature is naturally reduced to the room temperature in the air to obtain TaMo 0.25 V 0.75 O 5 。
Comparative example 4
Preparation of Ta by solid phase method 0.75 P 0.25 VO 5 Ceramic powder: selecting analytically pure V 2 O 5 、NH 4 H 2 PO 4 And Ta 2 O 5 Using Ta as a raw material 2 O 5 、NH 4 H 2 PO 4 And V 2 O 5 Mixing according to the mol ratio of Ta to P to V =0.75 to 0.25 to 1, adding absolute ethyl alcohol to wet, grinding in an agate mortar for 2 hours, heating the obtained powder in a muffle furnace at the heating rate of 750 ℃ at 5 ℃/min, keeping the temperature and calcining for 12 hours, and naturally cooling to room temperature in the air. Then adding the obtained powder into absolute ethyl alcohol, wetting the powder, grinding the powder in an agate mortar for 2 hours, and pressing the powder into a cylinder with the diameter of 8mm and the height of 5 mm; using the cylinder as the center, handle V 2 O 5 Powder is sprinkled around the cylinder, V 2 O 5 The distance of the powder from the center of the cylinder is 1 cm 2 O 5 The total mass of the powder is 1 time of that of the cylinder, the powder is subjected to heat preservation and calcination for 12 hours in a muffle furnace at the temperature rise rate of 750 ℃ at the speed of 5 ℃/min, and the temperature is naturally reduced to the room temperature in the air to obtain Ta 0.75 P 0.25 VO 5 。
Product characterization and thermal expansion testing
Ta prepared in examples 1 to 4 x1- Ti x Mo x V x1- O 5 (x0.00, 0.25, 0.50, 0.75) product as shown in figure 1, when doping ratioxWhen =0.5, moO appears 3 While the main phase is also TaVO 5 Phase (c). When doping ratioxMoO =0.75 3 Is stronger, but TaVO 5 The phases of (c) can be observed. The XRD results of fig. 1 show that: the obtained product changes the peak intensity ratio of XRD along with the change of the doping ratio, and marks that the crystal structure gradually changes along with the increase of the doping ratio.
Ta prepared in examples 1 to 4 x1- Ti x Mo x V x1- O 5 (x=0.00, 0.25, 0.50, 0.75) product corresponding Raman map see fig. 2. The Raman map results of fig. 2 show: the obtained product gradually changes along with the change of the doping ratio, and marks the change of the crystal structure.
Ta prepared in examples 1 to 4 x1- Ti x Mo x V x1- O 5 (x=0.00, 0.25, 0.50, 0.75) relative length of product (i.e.. DELTA.L/L) 0 Where Δ L is the length after expansion-the length before expansion, i.e., the original length, L 0 For the original length of the product, the same applies hereinafter) is shown in fig. 3. It can be seen that: the thermal expansion coefficients of products with different doping ratios are different, and Ta is realized x1- Ti x Mo x V x1- O 5 (x =0.00, 0.25, 0.50, 0.75) modulation of the coefficient of thermal expansion of the product. Calculating TaVO 5 Coefficient of thermal expansion of-3.7X 10 -6 K -1 （280-750K），Ta 0.75 Ti 0.25 Mo 0.25 V 0.75 O 5 Coefficient of thermal expansion of-2.2X 10 -6 K -1 （310-750K），Ta 0.5 Ti 0.5 Mo 0.5 V 0.5 O 5 Coefficient of thermal expansion of-0.1X 10 -6 K -1 （310-750K），Ta 0.25 Ti 0.75 Mo 0.75 V 0.25 O 5 Coefficient of thermal expansion of + 2.6X 10 -6 K -1 (310-750K). The results show that: ta of the invention 1- x Ti x Mo x V x1- O 5 (x=0.00、025, 0.50, 0.75) by different Ti+The Mo double-element doping proportion realizes the regulation and control of the thermal expansion coefficient of the product.
Ta prepared in comparative example 1-2 0.75 Ti 0.25 VO 5 、TaMo 0.1 V 0.9 O 5 The corresponding XRD pattern phase analysis of the product is shown in figure 4. The obtained product Ta 0.75 Ti 0.25 VO 5 And TaMo 0.1 V 0.9 O 5 All show impurity peaks in XRD, and Ta 0.75 Ti 0.25 VO 5 The impurity present in (A) is TiO 2 。
TaMo prepared in comparative examples 3 to 4 0.25 V 0.75 O 5 、Ta 0.75 P 0.25 VO 5 The corresponding XRD pattern phase analysis of the product is shown in figure 5. The obtained TaMo 0.25 V 0.75 O 5 、Ta 0.75 P 0.25 VO 5 XRD and TaVO of the product 5 The XRD of (a) was inconsistent, indicating that the doping was not successful.
Ta prepared in comparative example 1-2 0.75 Ti 0.25 VO 5 、TaMo 0.1 V 0.9 O 5 The relative length versus temperature curve for the product is shown in figure 6. It can be seen that: the thermal expansion coefficients of different single element doped products are different. Calculating Ta 0.75 Ti 0.25 VO 5 A coefficient of thermal expansion of-4.9X 10 -6 K -1 （290-670K），TaMo 0.1 V 0.9 O 5 Coefficient of thermal expansion of-3.7X 10 -6 K -1 (290-670K). The results show that: single element doping and does not target TaVO 5 Too much influence is caused by the thermal expansion properties of (b).
Stability test
Ta prepared as in examples 2 and 3 0.75 Ti 0.25 Mo 0.25 V 0.75 O 5 、Ta 0.5 Ti 0.5 Mo 0.5 V 0.5 O 5 For the product example, in-situ weight loss test was performed, and the TG curve is shown in fig. 7. As can be seen from fig. 7: the curve corresponding to the sample has small change, which indicates that the sample has no water absorption in the air and has good stability.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (4)
1. An adjustable coefficient of thermal expansion material, comprising: the molecular formula is Ta x1- Ti x Mo x V x1- O 5 Wherein 0.00 <x≤0.75。
2. The method for preparing the adjustable thermal expansion coefficient material according to claim 1, wherein the preparation steps are as follows:
(1) Selecting V 2 O 5 、TiO 2 、MoO 3 And Ta 2 O 5 Using Ta as a raw material 2 O 5 、TiO 2 、MoO 3 And V 2 O 5 According to the target product Ta 1- x Ti x Mo x V x1- O 5 The molar ratio of Ta to Ti to Mo to V = (1-x）∶x∶x∶（1-x) Grinding and mixing uniformly, and pressing the obtained mixed powder into a sheet shape;
(2) Taking the pressed sheet obtained in the step (1) as a center, and placing a circle of V around the pressed sheet 2 O 5 Sintering the powder at the temperature of 620-670 ℃ for 12-24 h, and cooling to obtain a target product Ta x1- Ti x Mo x V x1- O 5 。
3. The method of claim 2, wherein the adjustable cte material is selected from the group consisting of: in step (2), V 2 O 5 The distance between the powder and the center of the tablet is 1-2 cm 2 O 5 The total mass of the powder is tablet1-2 times of the total weight of the composition.
4. The method of claim 2, wherein the adjustable cte material is selected from the group consisting of: in the step (1), wet grinding is adopted, ethanol is added when raw materials are ground, and the adding amount is used for wetting V 2 O 5 、TiO 2 、MoO 3 And Ta 2 O 5 The standard is.
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| IN138239B (en) * | 1973-01-10 | 1976-01-10 | Shin Nihon Kagaku Kogyo Kk | |
| FR2555161B1 (en) * | 1983-11-23 | 1986-12-19 | Centre Nat Rech Scient | NOVEL OXYFLUORINATED PEROVSKITE COMPOSITIONS BASED ON LOW TEMPERATURE SINTER LEAD AND USEFUL AS DIELECTRIC CERAMICS FOR MULTILAYER CONDENSERS |
| US6132676A (en) * | 1997-06-30 | 2000-10-17 | Massachusetts Institute Of Technology | Minimal thermal expansion, high thermal conductivity metal-ceramic matrix composite |
| CN101746827B (en) * | 2009-12-23 | 2012-06-06 | 北京科技大学 | Negative thermal expansion material TaVO5 and preparation method thereof |
| CN101786663A (en) * | 2009-12-23 | 2010-07-28 | 北京科技大学 | Method for preparing NbVO5 powder with coprecipitation method |
| US11037738B2 (en) * | 2018-02-13 | 2021-06-15 | Nanotek Instruments Group, Llc | Hybrid supercapacitor containing a niobium composite metal oxide as an anode active material |
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| CN110713210A (en) * | 2019-10-29 | 2020-01-21 | 马刘东 | Conductive negative expansion material and preparation method thereof |
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