[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO2021261049A1 - Composé, procédé de production associé et matériau composite - Google Patents

Composé, procédé de production associé et matériau composite Download PDF

Info

Publication number
WO2021261049A1
WO2021261049A1 PCT/JP2021/014478 JP2021014478W WO2021261049A1 WO 2021261049 A1 WO2021261049 A1 WO 2021261049A1 JP 2021014478 W JP2021014478 W JP 2021014478W WO 2021261049 A1 WO2021261049 A1 WO 2021261049A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
mixture
volume
thermal expansion
compound according
Prior art date
Application number
PCT/JP2021/014478
Other languages
English (en)
Japanese (ja)
Inventor
佳弘 米田
芳夫 馬渡
宏二 秋次
敏宏 磯部
Original Assignee
三井金属鉱業株式会社
国立大学法人東京工業大学
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 三井金属鉱業株式会社, 国立大学法人東京工業大学 filed Critical 三井金属鉱業株式会社
Priority to KR1020237002158A priority Critical patent/KR20230027217A/ko
Priority to CN202180037455.9A priority patent/CN115667150A/zh
Priority to JP2021549561A priority patent/JP7029576B1/ja
Publication of WO2021261049A1 publication Critical patent/WO2021261049A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a novel compound showing a negative coefficient of thermal expansion whose volume decreases as the temperature rises, a method for producing the same, and a composite material using the novel compound.
  • thermal expansion control techniques a technique for controlling the overall coefficient of thermal expansion by combining a material having a negative coefficient of thermal expansion (also referred to as “negative thermal expansion material”) is attracting attention.
  • Examples of the negative thermal expansion material include ⁇ -eucriptite, zirconium tungate (ZrW 2 O 8 ), zirconium tungate phosphate (Zr 2 WO 4 (PO 4 ) 2 ), Zn x Cd 1-x (CN). 2.
  • Manganese nitride, bismuth, nickel, iron oxide, etc. are known.
  • Patent Document 1 discloses Bi 1-x Sb x NiO 3 (where x is 0.02 ⁇ x ⁇ 0.20) as a new negative thermal expansion material.
  • Patent Document 2 as a new negative thermal expansion material, Zr 2-a M a S x P 2 O 12 + ⁇ (M is, Ti, Ce, Sn, Mn , Hf, Ir, Pb, Pd, Cr, It is at least one selected, a is 0 ⁇ a ⁇ 2, x is 0.4 ⁇ x ⁇ 1, and ⁇ is a value determined to satisfy the charge neutrality condition).
  • M is, Ti, Ce, Sn, Mn , Hf, Ir, Pb, Pd, Cr, It is at least one selected, a is 0 ⁇ a ⁇ 2, x is 0.4 ⁇ x ⁇ 1, and ⁇ is a value determined to satisfy the charge neutrality condition).
  • the negative thermal expansion material disclosed in Patent Document 2 exhibits a negative coefficient of thermal expansion in the range of room temperature to 500 ° C., and the larger the sulfur content (x), the more negative it is, especially at 100 to 180 ° C. It is attracting attention as a useful material because it is a material that exhibits the thermal expansion coefficient of and can also realize low density. On the other hand, in a specific application, there is a demand for a material that exhibits a negative coefficient of thermal expansion, particularly in the temperature range of room temperature to 100 ° C., room temperature to 200 ° C., or room temperature to 300 ° C.
  • the coefficient of thermal expansion of a resin material when the coefficient of thermal expansion is adjusted by adding a negative thermal expansion material to the resin material as a positive thermal expansion material, the melting point or the glass transition temperature of the resin material is low.
  • a negative thermal expansion material that exhibits a negative coefficient of thermal expansion in the temperature range of room temperature to 100 ° C., room temperature to 200 ° C., or room temperature to 300 ° C.
  • the present invention is intended to provide a new compound having a composition different from the conventional one and exhibiting a negative coefficient of thermal expansion and having a high insulation resistance. More preferably, it does not provide new compounds that have high insulation resistance and that exhibit a particularly good negative coefficient of thermal expansion, especially in the temperature range from room temperature to 100 ° C, room temperature to 200 ° C, or room temperature to 300 ° C. Is to be.
  • the present invention provides a composition formula Zr 2.00-b M b S Y P Z O 12.00 + ⁇ (wherein, M is, Ti, Ce, Sn, Mn , Hf, Ir, Pb , Pd, Cr, W, Mo, and 0 ⁇ b ⁇ 2.00, 0 ⁇ Y ⁇ 0.30, Z ⁇ 2.00, ⁇ so as to satisfy the charge neutrality condition.
  • M is, Ti, Ce, Sn, Mn , Hf, Ir, Pb , Pd, Cr, W, Mo, and 0 ⁇ b ⁇ 2.00, 0 ⁇ Y ⁇ 0.30, Z ⁇ 2.00, ⁇ so as to satisfy the charge neutrality condition.
  • the present compound 1 represented by (determined value).
  • the present invention also provides, in the composition formula Zr 2.00-b M b S Y P Z O 12.00 + ⁇ (wherein, M is, Ti, Ce, Sn, Mn , Hf, Ir, Pb, Pd, Cr, It is at least one selected from W and Mo, and 0 ⁇ b ⁇ 2.00, 0.30 ⁇ Y ⁇ 1.00, Z> 2.00, and ⁇ are values determined so as to satisfy the charge neutrality condition).
  • a compound represented by (referred to as "the present compound 2”) is proposed.
  • Both the compounds 1 and 2 proposed by the present invention show a negative coefficient of thermal expansion. Therefore, it is possible to control the coefficient of thermal expansion of the composite material which is a mixture by mixing with a material exhibiting a positive coefficient of thermal expansion (referred to as "positive coefficient of thermal expansion material"). Further, since both of the present compounds 1 and 2 have excellent insulation resistance, they can be effectively used in the technical field where insulation resistance is required.
  • the present compound 1 proposed by the present invention exhibits a remarkably excellent negative coefficient of thermal expansion, especially in the temperature range from room temperature to 100 ° C. Therefore, it can be suitably used for controlling the coefficient of thermal expansion in the temperature range from room temperature to 100 ° C. For example, it is possible to control the coefficient of thermal expansion in the temperature range from room temperature to 100 ° C. of the composite material obtained by mixing with the positive thermal expansion material.
  • the present compound 2 proposed by the present invention exhibits a remarkably excellent negative coefficient of thermal expansion, especially in the temperature range of room temperature to 200 ° C. and room temperature to 300 ° C. Therefore, it can be suitably used for controlling the coefficient of thermal expansion in the temperature range of room temperature to 200 ° C. and room temperature to 300 ° C. For example, it is possible to control the coefficient of thermal expansion in the temperature range of room temperature to 200 ° C. and room temperature to 300 ° C. of the composite material obtained by mixing with the positive thermal expansion material.
  • M is preferably one or a combination of two or more selected from Ti, Ce, Sn, Mn, Hf, Ir, Pb, Pd, Cr, W and Mo.
  • "b” indicating the amount (atomic ratio) of the M element is preferably 0 or more and less than 2.00, particularly 0 or more or less than 1.50, and among them, 0 or more or It is more preferably 1.00 or less, and more preferably 0 or more or 0.80 or less.
  • Y indicating the amount (atomic ratio) of S (sulfur) is preferably larger than 0 and less than 0.30, and more than 0.10 or less than 0.30. Among them, it is more preferably 0.15 or more or less than 0.30, and more preferably 0.20 or more or less than 0.30.
  • Z indicating the amount (atomic ratio) of P (phosphorus) is preferably 2.00 or more, and more preferably more than 2.40. On the other hand, it is preferably 3.50 or less, more preferably 3.00 or less, and even more preferably 2.80 or less.
  • ⁇ in the composition formula of the present compound 1 is a value determined so as to satisfy the charge neutrality condition, and is usually -2.50 or more and 1.00 or less. Among them, -2.00 or more or 0.50 or less, among them, -1.50 or more or 0.00 or less, among them, -1.50 or more or -0.50 or less, among them, -1.33 or more or -0. It may be less than .80.
  • the "charge neutral condition” does not have to be completely neutral, and oxygen deficiency and oxygen excess composition within the allowable range of the compound are allowed.
  • the amount of each element excluding oxygen that is, the amount of Zr, M, S and P can be completely dissolved and measured by ICP-OES.
  • the composition ratio estimated as electrically neutral from the chemical ratio of the elements other than oxygen is used.
  • crystal phase present in compound 1 examples include ⁇ -Zr 2 SP 2 O 12 phase (ICDD card number: 04-017-0937 or / and ICDD card number: 00-038-0489), and this crystal can be mentioned.
  • the main phase that is, in the X-ray diffraction pattern obtained by analyzing compound 1 by an X-ray diffraction method (XRD, Cu radiation source), it is preferable that the peak intensity derived from this crystal is the highest. That is, other crystal phases may be contained in a part thereof.
  • M is preferably one or a combination of two or more selected from Ti, Ce, Sn, Mn, Hf, Ir, Pb, Pd, Cr, W and Mo.
  • "b” indicating the amount (atomic ratio) of the M element is preferably 0 or more and less than 2.00, particularly 0 or more or less than 1.50, and among them, 0 or more or It is more preferably 1.00 or less, and more preferably 0 or more or 0.80 or less.
  • Y indicating the amount (atomic ratio) of S (sulfur) is preferably 0.30 or more and 1.00 or less, and above all, 0.30 or more or 0.80 or less. Among them, it is more preferably 0.30 or more or 0.50 or less.
  • Z indicating the amount (atomic ratio) of P (phosphorus) needs to be larger than 2.00. On the other hand, it is preferably 3.50 or less, more preferably 3.00 or less, and even more preferably 2.80 or less.
  • ⁇ in the composition formula of the present compound 2 is a value determined so as to satisfy the charge neutrality condition, and is usually -2.50 or more and 1.00 or less. Among them, -2.00 or more or 0.50 or less, among them, -1.50 or more or 0.00 or less, among them, -1.50 or more or -0.50 or less, among them, -1.33 or more or -0. It may be less than .80.
  • the "charge neutral condition” does not have to be completely neutral, and oxygen deficiency and oxygen excess composition within the allowable range of the compound are allowed.
  • the amount of each element excluding oxygen that is, the amount of Zr, M, S and P can be completely dissolved and measured by ICP-OES.
  • a composition ratio estimated as electrically neutral from the chemical ratios of elements other than oxygen shall be used.
  • crystal phase present in compound 2 examples include ⁇ -Zr 2 SP 2 O 12 phase (ICDD card number: 04-017-0937 or / and ICDD card number: 00-038-0489), and this crystal can be mentioned.
  • the main phase that is, in the X-ray diffraction pattern obtained by analyzing compound 2 by an X-ray diffraction method (XRD, Cu radiation source), it is preferable that the peak intensity derived from this crystal is the highest. That is, other crystal phases may be contained in a part thereof.
  • Both of the present compounds 1 and 2 may be surface-treated. Since all of the compounds 1 and 2 are surface-treated with a predetermined surface-treated compound, the insulating property and the chemical resistance are improved, which contributes to the improvement of the wettability with respect to the resin.
  • Examples of the surface treatment compound include silane coupling agents as surface treatment agents, aluminumate coupling agents, titanate coupling agents, zirconium coupling agents, organic compounds such as organic carboxylic acids and organic amines, and dioxide. Any of the inorganic compounds such as silicon, aluminum oxide, zinc oxide and titanium oxide can be used.
  • the insulating property of the components constituting the compound of the present invention is improved, the component elution is prevented, and the wettability when mixed with a resin is improved. Shows a significant effect.
  • silane coupling agent as the surface treatment agent, various silane coupling agents such as epoxy-based, amino-based, vinyl-based, methacrylic-based, acrylic-based, mercapto-based, and alkyl-based can be used.
  • Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane.
  • carboxylic acid as a surface treatment agent examples include caproic acid (hexanoic acid), caproic acid (octanoic acid), caproic acid (decanoic acid), lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), and palmitic acid (hexadecanoic acid). Acid), stearic acid (octadecanoic acid), oleic acid, linolic acid, linolenic acid and the like can be mentioned.
  • amine as a surface treatment agent examples include aliphatic amines.
  • an aliphatic amine having 6 or more and 18 or less carbon atoms, particularly 10 or more and 18 or less carbon atoms can be preferably used.
  • Specific examples thereof include hexylamine, octylamine, decylamine, laurylamine, oleylamine and stearylamine.
  • the volume cumulative particle size D50 at the cumulative volume of 50% by volume by the laser diffraction / scattering type particle size distribution measurement method is 0.05 ⁇ m or more and 100 ⁇ m or less. If the D50 of the compounds 1 and 2 is 0.05 ⁇ m or more, the dispersibility in a substrate such as a resin is good, and if it is 100 ⁇ m or less, the smoothness of the molded product is good. preferable. From this point of view, the D50 of the present compounds 1 and 2 is more preferably 0.1 ⁇ m or more, particularly preferably 0.5 ⁇ m or more, and more preferably 1 ⁇ m or more. On the other hand, it is more preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, and further preferably 30 ⁇ m or less.
  • the BET specific surface area of each of the compounds 1 and 2 is 1 m 2 / g or more and 50 m 2 / g or less.
  • the smoothness of the molded product is good , for example, and when it is 50 m 2 / g or less, it is dispersed in a substrate such as a resin. It is preferable because it has good properties.
  • the BET specific surface area of the compounds 1 and 2 is more preferably 2 m 2 / g or more, particularly 5 m 2 / g or more, particularly 10 m 2 / g or more, and further 15 m 2 / g or more. It is even more preferable to have it. On the other hand, it is more preferably 45 m 2 / g or less.
  • the volume resistivity of the compounds 1 and 2 can be 2000 ⁇ ⁇ cm or more.
  • the volume resistivity is preferably high in applications where insulation is required. From this point of view, the volume resistivity of the present compounds 1 and 2 is more preferably 10,000 ⁇ ⁇ cm or more, particularly preferably 100,000 ⁇ ⁇ cm or more, and more preferably 1,000,000 ⁇ ⁇ cm or more.
  • the compounds 1 and 2 show a negative coefficient of thermal expansion. For example, it exhibits a negative coefficient of thermal expansion in a temperature range of 30 ° C to 100 ° C, a temperature range of 30 ° C to 200 ° C, a temperature range of 30 ° C to 300 ° C, and the like.
  • the present compound 1 exhibits a remarkably excellent negative coefficient of thermal expansion, especially in the temperature range of 30 ° C to 100 ° C. Specifically, when heated to 30 ° C. to 100 ° C., the volume at 100 ° C. can shrink by 0.15% to 2.0% with respect to the volume at 30 ° C. Of these, 0.15% to 1.0%, of which 0.15% to 0.70%, and even more preferably 0.15% to 0.45%, are more preferable.
  • the lower limit of each of the above ranges is 0.15%, but the lower limit is preferably 0.20%, more preferably 0.25%.
  • the present compound 2 exhibits a remarkably excellent negative coefficient of thermal expansion, particularly in the temperature range of 30 ° C. to 200 ° C. and the temperature range of 30 ° C. to 300 ° C.
  • the volume at 200 ° C. can shrink by 1.0% to 3.0% with respect to the volume at 30 ° C.
  • 1.0% to 2.0% of which 1.1% to 2.0%, and even more preferably 1.1% to 1.5%, are more preferable.
  • the lower limit of each range is 1.0%, but the lower limit is preferably 1.05%, more preferably 1.1%.
  • a Zr raw material, a phosphorus raw material, sulfuric acid, water, and, if necessary, an M raw material having the above composition formula are included.
  • the mixture is hydrothermally treated to obtain a mixture after hydrothermal treatment, the mixture after hydrothermal separation is solid-liquid separated and washed to obtain a mixture after washing, the mixture after washing is dried to obtain a mixture after drying, and the mixture after drying is obtained.
  • a method for producing a compound which comprises firing at a temperature of 300 to 1000 ° C.
  • this manufacturing method will be sequentially described.
  • Examples of the Zr raw material include zirconium oxychloride or its hydrate, zirconium chloride or its hydrate, zirconium oxyacetate or its hydrate, zirconium acetate or its hydrate, zirconium sulfate or its hydrate, oxynitrite.
  • zirconium or its hydrate, Zirconium nitrate or its hydrate, Zirconium carbonate or its hydrate, Zirconium ammonium carbonate or its hydrate, Zirconium sodium carbonate or its hydrate, Zirconium potassium or its hydrate, Etc. can be used. However, it is not limited to these.
  • Phosphoric acid H 3 PO 4
  • diammonium hydrogen phosphate (NH 4 ) 2 HPO 4 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), ammonium phosphate (NH 4 (NH 4)) PO 4 ) 3
  • pyrophosphoric acid polyphosphoric acid
  • polyphosphoric acid can be used. However, it is not limited to these.
  • the M raw material examples include compounds containing the element M, for example, a sulfate of the element M or a solution thereof, a chloride salt or a solution thereof, a nitrate, an acetate, an oxide, a polyacid or a salt thereof, and the like.
  • a titanium (IV) sulfate solution Ti (SO 4 ) 2
  • a titanium (IV) chloride solution TiCl 4
  • M Ce, cerium sulfate can be mentioned.
  • Ce (SO 4 ) 2 cerium chloride (CeCl 3 ) can be mentioned, and when M is Sn, first tin chloride, second tin chloride, tin sulfate, tin oxide (SnO 2 ) can be mentioned. If M is Mn, manganese dioxide (MnO 2 ) can be mentioned, and if M is W, tungsten trioxide (WO 3 ), ammonium paratungstate ((NH 4 ) 10 ) can be mentioned.
  • S (sulfur) raw material for example, ammonium sulfate, sulfur powder, etc. can be blended.
  • the Zr raw material, phosphoric acid, M raw material, sulfuric acid, and water, if necessary, are mixed, and the aqueous solution (mixture) obtained by stirring is hydrothermally treated to obtain a mixture after hydrothermal treatment. good.
  • the phosphorus raw material (P raw material) and the Zr raw material may be the same as the compound for which the P / Zr molar ratio is intended, or the phosphorus raw material may be increased.
  • an aqueous solution for example, an aqueous solution (mixture) is placed in a sealable container, heated to 100 to 230 ° C., and allowed to stand for 3 hours to 3 days under pressure. Just do it.
  • the mixture after hydrothermal treatment may be solid-liquid separated and washed to obtain a mixture after washing. That is, after the solid-liquid separation, water may be further added to separate the solid-liquid, or the washing may be performed by a method such as water flow washing. At this time, it is preferable to repeat washing as necessary. By this washing, the excess S component can be washed.
  • the post-washing mixture may be dried to obtain a post-drying mixture.
  • the washed mixture may be heated and dried so that the product temperature is 60 to 150 ° C.
  • the drying method may be appropriately adopted. It has been confirmed that when a box-type dryer such as an AS ONE ETTAS constant temperature dryer is used, the set temperature of the dryer and the product temperature are almost the same.
  • the mixture may be calcined to produce the present compound.
  • the post-drying mixture may be fired so that the product temperature is maintained at 300 to 1000 ° C., particularly 400 ° C. or higher or 1000 ° C. or lower, and particularly 400 ° C. or higher or 800 ° C. or lower for 1 to 24 hours. good.
  • a box-type electric furnace such as the KBF1150 ° C series electric furnace manufactured by Koyo Thermo System
  • the set temperature of the firing device that is, the temperature inside the furnace and the product temperature are almost the same.
  • the surface treatment may be carried out after crushing or crushing as necessary after the firing.
  • the surface treatment may be performed by using the above-mentioned surface treatment compound.
  • the compounds 1 and 2 and the surface treatment compound may be dry-mixed or wet-mixed. Wet mixing can be carried out using water, a mixed solvent in which water and a water-soluble organic solvent are mixed within the range of solubility in water, an organic solvent, or the like.
  • the production methods of the present compounds 1 and 2 are not limited to the above production methods.
  • the present compounds 1 and 2 are mixed with a material having a positive coefficient of thermal expansion (positive thermal expansion material) as a negative thermal expansion material, in other words, the negative thermal expansion material is dispersed in the positive thermal expansion material. Therefore, it is possible to form a composite material having a controlled coefficient of thermal expansion.
  • a material having a positive coefficient of thermal expansion positive thermal expansion material
  • the negative thermal expansion material is dispersed in the positive thermal expansion material. Therefore, it is possible to form a composite material having a controlled coefficient of thermal expansion.
  • Examples of the positive thermal expansion material include resin materials, metal materials, and ceramic materials.
  • Example 1 ZrCl 2 O ⁇ 8H 2 O and phosphoric acid (H 3 PO 4 ) were dissolved in distilled water to 0.8 mol / L and then mixed, and then 20 ml and 6 ml of each of these aqueous solutions were mixed. 98% H 2 SO 4 was mixed and stirred with a stirrer for 90 minutes. Next, the stirred aqueous solution (mixture) was poured into a closed container made of Teflon (registered trademark) and set in a pressure-resistant stainless steel outer cylinder. Then, the container set in this outer cylinder was placed in a hot air circulation oven and heated, and the state was maintained at 130 ° C. for 12 hours for hydrothermal treatment.
  • Teflon registered trademark
  • Example 2 ZrCl 2 O ⁇ 8H 2 O and phosphoric acid (H 3 PO 4 ) were dissolved in distilled water to 0.8 mol / L and then mixed, and then 20 ml and 4. 5 ml of 98% H 2 SO 4 was mixed and stirred with a stirrer for 90 minutes. Next, the stirred aqueous solution (mixture) was poured into a closed container made of Teflon (registered trademark) and set in a pressure-resistant stainless steel outer cylinder. Then, the container set in this outer cylinder was placed in a hot air circulation oven and heated, and the state was maintained at 130 ° C. for 12 hours for hydrothermal treatment.
  • Teflon registered trademark
  • Teflon registered trademark
  • aqueous solution 20ml was prepared ZrCl 2 O ⁇ 8H 2 O in 0.8 mol / L, an aqueous solution was prepared ammonium dihydrogen phosphate the (NH 4 H 2 PO 4) to 1.1 mol / L 20ml were mixed, followed Then, 6 ml of 98% H 2 SO was mixed with this aqueous solution, and the mixture was stirred with a stirrer for 90 minutes. Next, the stirred aqueous solution (mixture) was poured into a closed container made of Teflon (registered trademark) and set in a pressure-resistant stainless steel outer cylinder.
  • Teflon registered trademark
  • the container set in this outer cylinder was placed in a hot air circulation oven and heated, and the state was maintained at 130 ° C. for 12 hours for hydrothermal treatment.
  • hydrothermal treatment solid-liquid separation, removal of supernatant liquid, and further washing by adding water and repeating solid-liquid separation are performed, then poured into an evaporating dish and the solid content is heated with a hot air dryer at 110 ° C. It was dried. The dried powder was placed in an electric furnace and calcined at 500 ° C. (product temperature) for 4 hours to obtain a compound (sample).
  • aqueous solution 20ml was prepared ZrCl 2 O ⁇ 8H 2 O in 0.8 mol / L, an aqueous solution was prepared ammonium dihydrogen phosphate the (NH 4 H 2 PO 4) to 0.9 mol / L 20ml were mixed, followed Then, 6 ml of 98% H 2 SO 4 was mixed with this aqueous solution, and the mixture was stirred with a stirrer for 90 minutes. Next, the stirred aqueous solution (mixture) was poured into a closed container made of Teflon (registered trademark) and set in a pressure-resistant stainless steel outer cylinder.
  • Teflon registered trademark
  • the container set in this outer cylinder was placed in a hot air circulation oven and heated, and the state was maintained at 130 ° C. for 12 hours for hydrothermal treatment.
  • hydrothermal treatment solid-liquid separation, removal of supernatant liquid, and further washing by adding water and repeating solid-liquid separation are performed, then poured into an evaporating dish and the solid content is heated with a hot air dryer at 110 ° C. It was dried. The dried powder was placed in an electric furnace and calcined at 500 ° C. (product temperature) for 4 hours to obtain a compound (sample).
  • Example 5 To 5 g of the compound (sample) obtained by the same procedure as in Example 1, 0.21 g of the silane coupling agent 3-isocyanatepropyltriethoxysilane was added as a surface treatment compound, and a mixer (Osaka Chemical Force Mill FM-) was added. After mixing in 1) for 2 minutes, heat treatment was performed under the conditions of 140 ° C. for 1 hour to obtain a compound (sample).
  • Example 6 To 5 g of the compound (sample) obtained by the same procedure as in Example 3, 0.20 g of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent was added as a surface treatment compound, and the mixture was mixed with a mixer for 2 minutes. Then, heat treatment was performed at 140 ° C. for 1 hour to obtain a compound (sample).
  • Example 7 To 5 g of the compound (sample) obtained from the same procedure as in Example 3, 0.19 g of hexyltrimethoxysilane as a silane coupling agent was added as a surface treatment compound, mixed with a mixer 4 for 2 minutes, and then 140. A compound (sample) was obtained by heat treatment under the condition of ° C. for 1 hour.
  • aqueous solution 20ml was prepared ZrCl 2 O ⁇ 8H 2 O in 0.72 mol / L, were mixed with the addition of a 30% solution of titanium sulphate 1.28 g, of ammonium dihydrogenphosphate thereto (NH 4 H 2 PO 4) 20 ml of an aqueous solution prepared at 0.9 mol / L was mixed, and then 6 ml of 98% H 2 SO 4 was mixed with this aqueous solution, and the mixture was stirred with a stirrer for 90 minutes. Next, the stirred aqueous solution (mixture) was poured into a closed container made of Teflon (registered trademark) and set in a pressure-resistant stainless steel outer cylinder.
  • Teflon registered trademark
  • the container set in this outer cylinder was placed in a hot air circulation oven and heated, and the state was maintained at 130 ° C. for 12 hours for hydrothermal treatment.
  • hydrothermal treatment solid-liquid separation, removal of supernatant liquid, and further washing by adding water and repeating solid-liquid separation are performed, then poured into an evaporating dish and the solid content is heated with a hot air dryer at 110 ° C. It was dried. The dried powder was placed in an electric furnace and calcined at 500 ° C. (product temperature) for 4 hours to obtain a compound (sample).
  • aqueous solution 20ml was prepared ZrCl 2 O ⁇ 8H 2 O in 0.64 mol / L, were mixed with the addition of a 30% solution of titanium sulphate 2.56 g, of ammonium dihydrogenphosphate thereto (NH 4 H 2 PO 4) 20 ml of an aqueous solution prepared at 0.9 mol / L was mixed, and then 6 ml of 98% H 2 SO 4 was mixed with this aqueous solution, and the mixture was stirred with a stirrer for 90 minutes. Next, the stirred aqueous solution (mixture) was poured into a closed container made of Teflon (registered trademark) and set in a pressure-resistant stainless steel outer cylinder.
  • Teflon registered trademark
  • the container set in this outer cylinder was placed in a hot air circulation oven and heated, and the state was maintained at 130 ° C. for 12 hours for hydrothermal treatment.
  • hydrothermal treatment solid-liquid separation, removal of supernatant liquid, and further washing by adding water and repeating solid-liquid separation are performed, then poured into an evaporating dish and the solid content is heated with a hot air dryer at 110 ° C. It was dried. The dried powder was placed in an electric furnace and calcined at 500 ° C. (product temperature) for 4 hours to obtain a compound (sample).
  • Example 10 The ZrCl 2 O ⁇ 8H 2 solution O was prepared in 0.72mol / L 20ml, CeCl 3 ⁇ 7H 2 O were added and mixed 0.61g of ammonium dihydrogen phosphate thereto (NH 4 H 2 PO 4 ) was mixed with 20 ml of an aqueous solution prepared at 0.9 mol / L, and then 6 ml of 98% H 2 SO 4 was mixed with this aqueous solution, and the mixture was stirred with a stirrer for 90 minutes. Next, the stirred aqueous solution (mixture) was poured into a closed container made of Teflon (registered trademark) and set in a pressure-resistant stainless steel outer cylinder.
  • Teflon registered trademark
  • the container set in this outer cylinder was placed in a hot air circulation oven and heated, and the state was maintained at 130 ° C. for 12 hours for hydrothermal treatment.
  • hydrothermal treatment solid-liquid separation, removal of supernatant liquid, and further washing by adding water and repeating solid-liquid separation are performed, then poured into an evaporating dish and the solid content is heated with a hot air dryer at 110 ° C. It was dried. The dried powder was placed in an electric furnace and calcined at 500 ° C. (product temperature) for 4 hours to obtain a compound (sample).
  • aqueous solution 20ml was prepared ZrCl 2 O ⁇ 8H 2 O in 0.64 mol / L, the CeCl 3 ⁇ 7H2O were added and mixed 1.22 g, ammonium dihydrogen phosphate thereto the (NH 4 H 2 PO 4) 20 ml of an aqueous solution prepared to 0.9 mol / L was mixed, and then 6 ml of 98% H 2 SO 4 was mixed with this aqueous solution, and the mixture was stirred with a stirrer for 90 minutes. Next, the stirred aqueous solution (mixture) was poured into a closed container made of Teflon (registered trademark) and set in a pressure-resistant stainless steel outer cylinder.
  • Teflon registered trademark
  • the container set in this outer cylinder was placed in a hot air circulation oven and heated, and the state was maintained at 130 ° C. for 12 hours for hydrothermal treatment.
  • hydrothermal treatment solid-liquid separation, removal of supernatant liquid, and further washing by adding water and repeating solid-liquid separation are performed, then poured into an evaporating dish and the solid content is heated with a hot air dryer at 110 ° C. It was dried. The dried powder was placed in an electric furnace and calcined at 500 ° C. (product temperature) for 4 hours to obtain a compound (sample).
  • Example 12 It was added ammonium tungstate para pentahydrate 1.57g ammonium dihydrogen phosphate the (NH 4 H 2 PO 4) in an aqueous solution 20ml was prepared in 0.9 mol / L, this, ZrCl 2 O ⁇ 8H 2 O was added to and mixed with 20 ml of an aqueous solution prepared at 0.72 mol / L, and then 6 ml of 98% H 2 SO 4 was mixed with this aqueous solution and stirred with a stirrer for 90 minutes. Next, the stirred aqueous solution (mixture) was poured into a closed container made of Teflon (registered trademark) and set in a pressure-resistant stainless steel outer cylinder.
  • Teflon registered trademark
  • the container set in this outer cylinder was placed in a hot air circulation oven and heated, and the state was maintained at 130 ° C. for 12 hours for hydrothermal treatment.
  • solid-liquid separation, removal of supernatant liquid, and further washing by adding water and repeating solid-liquid separation pour into an evaporating dish and heat the solid content with a hot air dryer in an atmosphere of 110 ° C. And dried.
  • the dried powder was placed in an electric furnace and calcined at 500 ° C. (product temperature) for 4 hours to obtain a compound (sample).
  • Example 13 Ammonium dihydrogen phosphate (NH 4 H 2 PO 4) was added 0.9 mol / L hexaammonium heptamolybdate tetrahydrate 0.90g aqueous solution 20ml was prepared, which, ZrCl 2 O ⁇ 8H 2 O was added and mixed with 20 ml of an aqueous solution prepared at 0.72 mol / L, and then 6 ml of 98% H 2 SO 4 was mixed with this aqueous solution and stirred with a stirrer for 90 minutes. Next, the stirred aqueous solution (mixture) was poured into a closed container made of Teflon (registered trademark) and set in a pressure-resistant stainless steel outer cylinder.
  • Teflon registered trademark
  • the container set in this outer cylinder was placed in a hot air circulation oven and heated, and the state was maintained at 130 ° C. for 12 hours for hydrothermal treatment.
  • hydrothermal treatment solid-liquid separation, removal of supernatant liquid, and further washing by adding water and repeating solid-liquid separation are performed, then poured into an evaporating dish and the solid content is heated with a hot air dryer at 110 ° C. It was dried. The dried powder was placed in an electric furnace and calcined at 500 ° C. (product temperature) for 4 hours to obtain a compound (sample).
  • composition analysis The composition (atomic ratio) of the prepared compound (sample) was analyzed using ICP-OES (Inductivity Coupled Plasma Optical Emission Spectrometry).
  • ICP-OES -ICP-OES equipment used: 700 series, ICP-OES (Agilent Technologies Co., Ltd.)
  • Example 5 The prepared compound (sample) was placed in pure water and irradiated with ultrasonic waves (40 W, 3 minutes) to disperse it, and then a particle size distribution measuring device (Microtrack (trade name) manufactured by Microtrac Bell Co., Ltd.). MT-3300EXII (model number) ”) was used to measure the volume cumulative particle size D50 at a cumulative volume of 50% by volume by a laser diffraction / scattering type particle size distribution measurement method.
  • Microtrack trade name
  • MT-3300EXII model number
  • BET specific surface area Using a specific surface area measuring device (“Macsorb (HM model-1201)” manufactured by Mountech Co., Ltd.), JIS R 1626: 1996 (method of measuring the specific surface area by the gas adsorption BET method of fine ceramic powder)
  • the BET specific surface area (SSA (BET)) of the prepared compound (sample) was measured in accordance with "(3.5) One-point method of the flow method". At that time, a mixed gas of helium as a carrier gas and nitrogen as an adsorbent gas was used. The degassing condition was 300 ° C. for 10 minutes.
  • the prepared compound (sample) was compressed at a pressure of 63 MPa using a powder resistance measuring system MCP-PD51 manufactured by Mitsubishi Chemical Analytech Co., Ltd., and the volume resistivity was measured according to the four-terminal method.
  • pellets compressed at a pressure of 63 MPa were separately prepared and measured using a high resistance meter Hiresta UX / MCP-HT800 manufactured by Mitsubishi Chemical Analytech.
  • the expansion coefficient of the lattice volume of the prepared compound (sample) was measured by the following method.
  • a multipurpose sample high temperature device unit was attached to the following powder X-ray diffractometer, and the X-ray diffraction pattern was measured at 30 ° C. and 100 ° C. The measurement was started after standing for 10 minutes after reaching the target temperature.
  • the crystal structure was refined using the obtained X-ray diffraction pattern and analysis software (PDXL2), and the lattice constant at each temperature was calculated.
  • the lattice volume was calculated from the lattice constant. In the table, the lattice volume expansion rate at 30 to 100 ° C., that is, the lattice volume at 100 ° C.
  • the compounds obtained in Examples 1, 2 and 5 have the ⁇ -Zr 2 SP 2 O 12 phase (ICDD card number: 00-038-0489) as the main phase in the diffraction pattern obtained by X-ray diffraction. It was confirmed that it existed.
  • the compounds obtained in Examples 3, 4, 6-13 and Reference Examples have the ⁇ -Zr 2 SP 2 O 12 phase (ICDD card number: 04-017-0937) in the diffraction pattern obtained by X-ray diffraction. ) was confirmed to exist as the main phase.
  • Examples 1, 2, 5 and 9 are characterized in that the amount of S (Y) is small and the amount of P is large as compared with Reference Examples 1 and 2. It was confirmed that these Examples 1, 5, and 9 showed a better negative coefficient of thermal expansion in the temperature range of 30 ° C to 100 ° C.
  • Examples 3, 4, 6-8, and 10-13 have a smaller amount of S (Y) and a larger amount of P than Reference Examples 1 and 2, while compared with Examples 1 and 2. And, it has a feature that the amount of S (Y) is large and the amount of P is large. It was confirmed that Examples 3, 4, 6-8, and 10-13 show a better negative coefficient of thermal expansion in the temperature range of 30 ° C to 200 ° C and the temperature range of 30 ° C to 300 ° C. Was done.
  • a compound in which a part of the compound is substituted with an element such as Ti, Ce, Sn, Mn, Hf, Ir, Pb, Pd, Cr, W, or Mo also exhibits a negative coefficient of thermal expansion like the above-mentioned compound. It can be inferred that high insulation resistance can be realized.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L'invention concerne un nouveau composé présentant un coefficient de dilatation thermique négatif, et ayant une grande résistance d'isolation.　La présente invention concerne le composé représenté par la formule de composition Zr2.00-bMbSYPZO12.00+δ (dans la formule, M représente au moins une espèce choisie parmi Ti, Ce, Sn, Mn, Hf, Ir, Pb, Pd, Cr, W et Mo, 0 ≤ b < 2,00, 0 < Y < 0,30, Z ≥ 2,00 et δ représentent une valeur déterminée de manière à satisfaire la condition de neutralité de charge), ou le composé représenté par la formule de composition Zr2.00-bMbSYPZO12.00+δ (dans la formule, M représente au moins une espèce choisie parmi Ti, Ce, Sn, Mn, Hf, Ir, Pb, Pd, Cr, W et Mo, 0 ≤ b < 2,00, 0,30 ≤ Y ≤ 1,00, Z > 2,00 et δ représente une valeur déterminée de manière à satisfaire la condition de neutralité de charge).
PCT/JP2021/014478 2020-06-22 2021-04-05 Composé, procédé de production associé et matériau composite WO2021261049A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020237002158A KR20230027217A (ko) 2020-06-22 2021-04-05 화합물 및 그 제조 방법, 그리고, 복합 재료
CN202180037455.9A CN115667150A (zh) 2020-06-22 2021-04-05 化合物及其制造方法以及复合材料
JP2021549561A JP7029576B1 (ja) 2020-06-22 2021-04-05 化合物及びその製造方法、並びに、複合材料

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-106688 2020-06-22
JP2020106688 2020-06-22

Publications (1)

Publication Number Publication Date
WO2021261049A1 true WO2021261049A1 (fr) 2021-12-30

Family

ID=79282346

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/014478 WO2021261049A1 (fr) 2020-06-22 2021-04-05 Composé, procédé de production associé et matériau composite

Country Status (5)

Country Link
JP (1) JP7029576B1 (fr)
KR (1) KR20230027217A (fr)
CN (1) CN115667150A (fr)
TW (1) TWI836228B (fr)
WO (1) WO2021261049A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023136116A1 (fr) * 2022-01-17 2023-07-20 三井金属鉱業株式会社 Composé, sa méthode de production et matériau composite

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62138314A (ja) * 1985-12-10 1987-06-22 Mitsui Toatsu Chem Inc 固体酸化合物及びその製造方法
WO2019167924A1 (fr) * 2018-02-27 2019-09-06 国立大学法人東京工業大学 Matériau d'expansion thermique négative, matériau composite, et procédé de production de matériau d'expansion thermique négatif
JP2019151839A (ja) * 2018-03-05 2019-09-12 日産化学株式会社 エポキシ樹脂組成物
JP2020121895A (ja) * 2019-01-29 2020-08-13 日産化学株式会社 β−リン酸硫酸ジルコニウム粒子およびその製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5514360A (en) * 1995-03-01 1996-05-07 The State Of Oregon, Acting By And Through The Oregon State Board Of Higher Education, Acting For And On Behalf Of Oregon State University Negative thermal expansion materials
JP6555473B2 (ja) 2015-08-31 2019-08-07 国立大学法人東京工業大学 負熱膨張性材料、及び複合体
WO2017061402A1 (fr) * 2015-10-07 2017-04-13 日本化学工業株式会社 Procédé de production de phosphate de tungstène et de zirconium
JP6190023B1 (ja) * 2015-10-07 2017-08-30 日本化学工業株式会社 リン酸タングステン酸ジルコニウムの製造方法
CN107445202B (zh) * 2017-08-30 2019-08-06 华能国际电力股份有限公司 一种小尺寸、超分散纳米氧化锆基涂层粉体的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62138314A (ja) * 1985-12-10 1987-06-22 Mitsui Toatsu Chem Inc 固体酸化合物及びその製造方法
WO2019167924A1 (fr) * 2018-02-27 2019-09-06 国立大学法人東京工業大学 Matériau d'expansion thermique négative, matériau composite, et procédé de production de matériau d'expansion thermique négatif
JP2019151839A (ja) * 2018-03-05 2019-09-12 日産化学株式会社 エポキシ樹脂組成物
JP2020121895A (ja) * 2019-01-29 2020-08-13 日産化学株式会社 β−リン酸硫酸ジルコニウム粒子およびその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ISOBE, TOSHIHIRO ET AL.: "Synthesis of Phosphoric Acid Zirconium Sulfate Having Negative Thermal Expansion Coefficient, and Mechanisms Thereof", PROCEEDINGS OF THE 28TH SYMPOSIUM OF THE JAPANESE ASSOCIATION OF INORGANIC PHOSPHOROUS CHEMISTRY, 13 September 2019 (2019-09-13), pages 42 - 43 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023136116A1 (fr) * 2022-01-17 2023-07-20 三井金属鉱業株式会社 Composé, sa méthode de production et matériau composite

Also Published As

Publication number Publication date
JPWO2021261049A1 (fr) 2021-12-30
TWI836228B (zh) 2024-03-21
JP7029576B1 (ja) 2022-03-03
TW202200504A (zh) 2022-01-01
CN115667150A (zh) 2023-01-31
KR20230027217A (ko) 2023-02-27

Similar Documents

Publication Publication Date Title
Gupta et al. A review on molten salt synthesis of metal oxide nanomaterials: Status, opportunity, and challenge
JP7017743B2 (ja) 負熱膨張材料、複合材料、及び負熱膨張材料の製造方法
JP5105503B2 (ja) ε酸化鉄の製法
JP6553831B1 (ja) 改質リン酸タングステン酸ジルコニウム、負熱膨張フィラー及び高分子組成物
Barudžija et al. Structural and magnetic properties of hydrothermally synthesized β-MnO2 and α-KxMnO2 nanorods
DE3633309A1 (de) Stabilisierte metalloxide
JP6645821B2 (ja) 酸化チタン及びその製造方法
Zhuk et al. Dielectric properties, Mössbauer study, ESR spectra of Bi2FeTa2O9. 5 with pyrochlore structure
JP7029576B1 (ja) 化合物及びその製造方法、並びに、複合材料
Balamurugan et al. Nanocrystalline Gd2Ti2O7 pyrochlore material for NIR reflective pigment application: micro-structural and optical studies
Guan et al. Carbon-reduction as an easy route for the synthesis of VO 2 (M1) and further Al, Ti doping
WO2001056927A1 (fr) Compose lamellaire hexagonal a base d&#39;oxyde d&#39;indium-zinc et son procede de production
Shehata et al. Effect of Gd3+ doping on structural and optical properties of MgO–MgAl2O4 nanocomposites synthesized via co-precipitation method
JP2007284716A (ja) ニッケルナノワイヤー及びその製造方法
Rios et al. Synthesis and characterization of manganese-cobalt solid solutions prepared at low temperature
Lee et al. Effects of solvent and chelating agent on synthesis of solid oxide fuel cell perovskite, La0. 8Sr0. 2CrO3− δ
Salek et al. A simple preparation process of pure Mn3-Xcoxo4 (X= 1, 1.5 and 2) desert rose-like nanoparticles and their optical properties.
Sultan et al. New nanoparticulate Gd1− xZrxFe1− yMnyO3 multiferroics: Synthesis, characterization and evaluation of electrical, dielectric and magnetic parameters
Madiyarova et al. SYNTHESIS AND PHYSICO–CHEMICAL CHARACTERISTICS OF COMPLEX FERRITE CrNaFe2O5
WO2023181781A1 (fr) Matériau à expansion thermique négative, son procédé de fabrication et matériau composite
JP2009057609A (ja) 磁性体ナノ粒子及びその製造方法
JP7410249B2 (ja) 負熱膨張材、その製造方法及び複合材料
Bushkova et al. Sol-gel synthesis, structure and optical properties of nickel-manganese ferrites
Donkova et al. Thermal magnetic investigation of the decomposition of NixMn1− xC2O4· 2H2O
JP7364418B2 (ja) 熱膨張抑制フィラー、その製造方法及びそれを含む複合材料

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2021549561

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21828407

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21828407

Country of ref document: EP

Kind code of ref document: A1