CN115667150A - Compound, method for producing same, and composite material - Google Patents

Compound, method for producing same, and composite material Download PDF

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Publication number
CN115667150A
CN115667150A CN202180037455.9A CN202180037455A CN115667150A CN 115667150 A CN115667150 A CN 115667150A CN 202180037455 A CN202180037455 A CN 202180037455A CN 115667150 A CN115667150 A CN 115667150A
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compound
mixture
thermal expansion
volume
compound according
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米田佳弘
马渡芳夫
秋次宏二
矶部敏宏
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Mitsui Mining and Smelting Co Ltd
Tokyo Institute of Technology NUC
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Mitsui Mining and Smelting Co Ltd
Tokyo Institute of Technology NUC
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    • 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

Abstract

Disclosed is a novel compound which exhibits a negative thermal expansion coefficient and has high insulation resistance. Which is composed of the formula Zr 2.00‑ b M b S Y P Z O 12.00+δ (wherein M is at least 1 selected from Ti, ce, sn, mn, hf, ir, pb, pd, cr, W and Mo, and 0. Ltoreq. B<2.00、0<Y<0.30, Z.gtoreq.2.00, and delta is a value determined so as to satisfy the charge neutral condition), or a compound represented by the composition formula Zr 2.00‑b M b S Y P Z O 12.00+δ (wherein M is selected from Ti,Ce. At least 1 of Sn, mn, hf, ir, pb, pd, cr, W and Mo, and b is more than or equal to 0<2.00、0.30≤Y≤1.00、Z>2.00, δ is a value determined in such a manner as to satisfy a charge neutrality condition).

Description

Compound, method for producing same, and composite material
Technical Field
The present invention relates to a novel compound exhibiting a negative thermal expansion coefficient such that the volume decreases when the temperature rises, a method for producing the same, and a composite material using the novel compound.
Background
In the technical field of electronic devices, optical devices, fuel cells, sensors, and the like, where precision is required, for example, when a device is configured by combining a plurality of materials, if misalignment, interfacial separation, disconnection, or the like occurs due to a difference in thermal expansion coefficient between the materials, there is a possibility that this may be a serious problem. Therefore, a technique for controlling thermal expansion is required. As one of the thermal expansion control techniques, a technique of controlling the overall thermal expansion ratio by combining materials having a negative thermal expansion ratio (also referred to as "negative thermal expansion materials") has been attracting attention.
Most substances increase in volume due to thermal expansion if the temperature rises. In contrast, negative thermal expansion materials having the property of decreasing in volume when heated are rare.
However, even if it is called a negative thermal expansion material, generally, the following materials are most: the material exhibits negative thermal expansion only in a specific temperature range, and exhibits positive thermal expansion in other temperature ranges.
As negative thermal expansion materials, for example, beta-eucryptite and zirconium tungstate (ZrW) are known 2 O 8 ) Zirconium phosphotungstate (Zr) 2 WO 4 (PO 4 ) 2 )、Zn x Cd 1-x (CN) 2 Manganese nitride, bismuth-nickel-iron oxide, and the like.
Further, patent document 1 discloses Bi as a novel negative thermal expansion material 1-x Sb x NiO 3 (wherein x is 0.02. Ltoreq. X.ltoreq.0.20).
Patent document 2 discloses a compound containing Zr as a novel negative thermal expansion material 2- a M a S x P 2 O 12+δ (M is at least 1 selected from Ti, ce, sn, mn, hf, ir, pb, pd, cr, a is 0. Ltoreq. A<2, x is 0.4. Ltoreq. X.ltoreq.1, and δ is a value defined so as to satisfy a charge neutral condition (charge neutral condition).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2017-48071
Patent document 2: WO2019/167924A1
Disclosure of Invention
Problems to be solved by the invention
Currently, the negative thermal expansion materials as described above are used, and further excellent low thermal expansion properties are required. Further, as the size of the member is reduced, the wiring is becoming thinner, and higher insulation is required.
In addition, the negative thermal expansion material disclosed in the above patent document 2 is a material which is attracting attention as a useful material because it is the following: the sulfur-containing composition exhibits a negative thermal expansion coefficient in a range of room temperature to 500 ℃, and particularly exhibits a negative thermal expansion coefficient at 100 to 180 ℃ as the sulfur content (x) is increased, thereby enabling a reduction in density.
On the other hand, in specific applications, a material exhibiting a negative thermal expansion coefficient is required, particularly in a temperature range of room temperature to 100 ℃, room temperature to 200 ℃, or room temperature to 300 ℃. For example, in the case of controlling the thermal expansion coefficient of a resin material, when a negative thermal expansion material is added to a resin material as a positive thermal expansion material to adjust the thermal expansion coefficient, when the melting point or glass transition temperature of the resin material is low, a negative thermal expansion material exhibiting a negative thermal expansion coefficient in a temperature region of room temperature to 100 ℃, room temperature to 200 ℃, or room temperature to 300 ℃ is required.
Accordingly, the present invention provides a novel compound having a composition different from that of the conventional compound, a negative thermal expansion coefficient, and a high insulation resistance.
It is further preferable to provide a novel compound which has high insulation resistance and particularly exhibits a particularly excellent negative thermal expansion coefficient particularly in a temperature region of room temperature to 100 ℃, room temperature to 200 ℃, or room temperature to 300 ℃.
Means for solving the problems
In order to solve the above-mentioned problems, the present invention provides a compound (referred to as "the present compound 1") represented by the compositional formula Zr 2.00-b M b S Y P Z O 12.00+δ (in the formula, M is at least 1 selected from Ti, ce, sn, mn, hf, ir, pb, pd, cr, W and Mo, and b is not less than 0 and not more than<2.00、0<Y<0.30, Z.gtoreq.2.00, and δ is a value determined so as to satisfy the charge neutrality condition).
The invention also provides a compound (named as 'the compound 2') consisting of the composition formula Zr 2.00-b M b S Y P Z O 12.00+δ (wherein M is at least 1 selected from Ti, ce, sn, mn, hf, ir, pb, pd, cr, W and Mo, and 0. Ltoreq. B<2.00、0.30≤Y≤1.00、Z>2.00, δ is a value determined in such a manner as to satisfy the charge neutrality condition).
Effects of the invention
Both the present compounds 1, 2 proposed by the present invention show negative thermal expansion rates. Therefore, the thermal expansion coefficient of the composite material as a mixture can be controlled by mixing the material exhibiting a positive thermal expansion coefficient (referred to as "positive thermal expansion material"). In addition, since both the present compounds 1 and 2 have excellent insulation resistance, they can be effectively used in the technical field where insulation resistance is required.
Furthermore, the present compound 1 proposed by the present invention exhibits a significantly excellent negative thermal expansion coefficient particularly in a temperature region of room temperature to 100 ℃. Thus, it can be suitably used for the control of the thermal expansion rate in the temperature region of room temperature to 100 ℃. For example, the thermal expansion coefficient of a composite material obtained by mixing the positive thermal expansion material with the positive thermal expansion material can be controlled in a temperature range of room temperature to 100 ℃.
In addition, the present compound 2 proposed by the present invention shows significantly excellent negative thermal expansion coefficients particularly in the temperature regions of room temperature to 200 ℃ and room temperature to 300 ℃. Therefore, the method can be suitably used for controlling the thermal expansion coefficient in the temperature region of room temperature to 200 ℃ and room temperature to 300 ℃. For example, the thermal expansion coefficient of a composite material obtained by mixing the positive thermal expansion material with the positive thermal expansion material can be controlled in a temperature range of room temperature to 200 ℃ and room temperature to 300 ℃.
Detailed Description
Next, the present invention will be explained based on embodiment examples. However, the present invention is not limited to the embodiments described below.
< Compound 1>
Hereinafter, a compound (referred to as "present compound 1") which is an example of an embodiment of the present invention will be described in detail.
The compound 1 is represented by the formula Zr 2.00-b M b S Y P Z O 12.00+δ (wherein 0. Ltoreq. B<2.00、0<Y<0.30, Z.gtoreq.2.00, and delta is a value determined so as to satisfy the charge neutrality condition).
In the composition formula of the present compound 1, when b =0, zr is obtained 2.00 S Y P Z O 12.00+δ (in the formula, 0<Y<0.30, Z.gtoreq.2.00, and delta is a value determined so as to satisfy the charge neutrality condition). On the other hand, when b is 0<b<In the case of 2.00, a part of Zr sites is substituted with M.
In the composition formula of the present compound 1, M is preferably a combination of 1 or 2 or more selected from Ti, ce, sn, mn, hf, ir, pb, pd, cr, W, and Mo.
Zr 2.00 S Y P Z O 12.00+δ (in the formula, 0<Y<0.30, Z.gtoreq.2.00) by the above-mentioned element M, and a compound in which a part of Zr sites is substituted with the element M exhibits a negative thermal expansion coefficient as in the case of the compound in which Zr sites contain only Zr, and can realize high insulation resistance.
In the composition formula of the present compound 1, "b" representing the amount (atomic ratio) of the M element is preferably 0 or more and less than 2.00, wherein 0 or more and less than 1.50 are further preferred, wherein 0 or more and 1.00 or less are still further preferred, and wherein 0 or more and 0.80 or less are still further preferred.
In the composition formula of the present compound 1, "Y" representing the amount (atomic ratio) of S (sulfur) is preferably more than 0 and less than 0.30, wherein more preferably 0.10 or more or less than 0.30, wherein still more preferably 0.15 or more or less than 0.30, wherein still more preferably 0.20 or more or less than 0.30.
Further, "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 still more preferably 2.80 or less.
Further, "δ" in the composition formula of the present compound 1 is a value defined so as to satisfy the charge neutrality condition, and is usually-2.50 to 1.00. In some cases, it is in particular from-2.00 or more or from 0.50 or less, in some cases from-1.50 or more or from 0.00 or less, in other cases from-1.50 or more or from-0.50 or less, in other cases from more than-1.33 or less than-0.80. The "charge neutral condition" may not be completely neutral, and a composition having oxygen deficiency and oxygen excess in a range allowed as a compound is acceptable.
The amounts of the elements other than oxygen, that is, the amounts of Zr, M, S and P can be measured by dissolving the total amount and using ICP-OES. Further, since it is difficult to strictly measure the oxygen amount, a composition ratio estimated to be electrically neutral from the chemical ratio of elements other than oxygen is used.
As the crystal phase present in the compound 1, there may be mentioned α -Zr 2 SP 2 O 12 Phase (ICDD card number: 04)017-0937 or/and ICDD card number: 00-038-0489), it is preferable that the crystal is a main phase, that is, the peak intensity derived from the crystal is highest in an X-ray diffraction pattern obtained by analyzing compound 1 by an X-ray diffraction method (XRD, cu radiation source). That is, a part may contain another crystal phase.
< Compound No. 2>
Hereinafter, another example of the compound (referred to as "present compound 2") according to the embodiment of the present invention will be described in detail.
The compound 2 is represented by the formula Zr 2.00-b M b S Y P Z O 12.00+δ (in the formula, b is 0. Ltoreq. B<2.00、0.30≤Y≤1.00、Z>2.00, δ is a value determined in such a manner as to satisfy the charge neutrality condition).
In the composition formula of the present compound 2, when b =0, zr is 2.00 S Y P Z O 12.00+δ (wherein, Y is 0.30. Ltoreq. Y.ltoreq.1.00, Z is 0.30. Ltoreq>2.00, δ is a value determined in such a manner as to satisfy the charge neutrality condition). On the other hand, when b is 0<b<2.00, the Zr site is partially substituted with M.
In the composition formula of the present compound 2, M is preferably 1 or a combination of 2 or more selected from Ti, ce, sn, mn, hf, ir, pb, pd, cr, W, and Mo.
Zr 2.00 S Y P Z O 12.00+δ (wherein Y is 0.30. Ltoreq. Y.ltoreq.1.00, Z>2.00 A compound in which a part of Zr sites in the group is substituted with these elements M) exhibits a negative thermal expansion coefficient as in the case of the compound in which Zr sites only contain Zr, and can realize high insulation resistance.
In the composition formula of the present compound 2, "b" indicating the amount (atomic ratio) of the M element is preferably 0 or more and less than 2.00, more preferably 0 or more and less than 1.50 among them, still more preferably 0 or more or 1.00 or less, and still more preferably 0 or more or 0.80 or less among them.
In the composition formula of the present compound 2, "Y" indicating the amount (atomic ratio) of S (sulfur) is preferably 0.30 or more and 1.00 or less, more preferably 0.30 or more or 0.80 or less, and still more preferably 0.30 or more or 0.50 or less.
Further, "Z" indicating the amount (atomic ratio) of P (phosphorus) needs to be more than 2.00. On the other hand, it is preferably 3.50 or less, more preferably 3.00 or less, and still more preferably 2.80 or less.
Further, "δ" in the composition formula of the present compound 2 is a value defined so as to satisfy the charge neutrality condition, and is usually from-2.50 to 1.00. In some cases, it is in particular from-2.00 or more or from 0.50 or less, in some cases from-1.50 or more or from 0.00 or less, in other cases from-1.50 or more or from-0.50 or less, in other cases from more than-1.33 or less than-0.80. The "charge neutral condition" may not be completely neutral, and a composition having oxygen deficiency and oxygen excess in a range allowed as a compound is acceptable.
The amounts of the elements other than oxygen, that is, the amounts of Zr, M, S and P can be measured by dissolving the total amount and using ICP-OES. Further, since it is difficult to strictly measure the oxygen amount, a composition ratio estimated to be electrically neutral from the chemical ratio of elements other than oxygen is used.
As the crystal phase present in the compound 2, there may be mentioned α -Zr 2 SP 2 O 12 The phase (ICDD card No. 04-017-0937 or/and ICDD card No. 00-038-0489) is preferably a phase in which the crystal is the main phase, that is, the peak intensity derived from the crystal is highest in an X-ray diffraction pattern obtained by analyzing Compound 2 by X-ray diffraction method (XRD, cu radiation source). That is, a part may contain another crystal phase.
< surface treatment >
Both the present compounds 1 and 2 may be surface-treated compounds.
Both of the compounds 1 and 2 are surface-treated with a predetermined surface-treating compound, thereby improving the insulation property and chemical resistance and contributing to the improvement of wettability to the resin.
As the surface-treating compound, in addition to a silane coupling agent, an aluminate coupling agent, a titanate coupling agent, a zirconium coupling agent, and the like as the surface-treating agent, any of organic compounds such as organic carboxylic acids and organic amines, and further inorganic compounds such as silica, alumina, zinc oxide, and titanium oxide can be used.
In particular, the use of a silane coupling agent as a surface treatment compound has significant effects in improving the insulation properties of the components constituting the compound of the present invention, preventing elution of the components, and improving wettability when mixed with a resin.
As the silane coupling agent as the surface treatment agent, various silane coupling agents such as epoxy, amino, vinyl, methacrylic, acrylic, mercapto, alkyl and the like can be used. Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 8-glycidoxyoctylmethyldimethoxysilane, 8-glycidoxyoctylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, N-propyltrimethoxysilane, N-propyltriethoxysilane, N-octylsilane, trimethoxysilane, and decyloxydiethyltrimethoxysilane. These silane coupling agents may be used alone, or 2 or more kinds may be used in combination.
Examples of the carboxylic acid as the surface treatment agent include caproic acid (hexane acid), caprylic acid (octanoic acid), capric acid (decane acid), lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), oleic acid, linoleic acid, linolenic acid, and the like.
Examples of the amine as the surface treatment agent include aliphatic amines. Aliphatic amines having 6 to 18 carbon atoms, particularly 10 to 18 carbon atoms, can be suitably used. Specific examples thereof include hexylamine, octylamine, decylamine, laurylamine, oleylamine and stearylamine.
<D50>
The volume cumulative particle diameter D50 of the present compounds 1 and 2 is preferably 0.05 μm to 100 μm when the cumulative volume is 50 vol% as measured by a laser diffraction scattering particle size distribution measurement method.
When the D50 of the present compounds 1 and 2 is 0.05 μm or more, the dispersibility in a base material such as a resin is favorable, and the like, and when it is 100 μm or less, the smoothness of a molded article is favorable, and the like.
From the above viewpoint, the D50 of the present compounds 1 and 2 is more preferably 0.1 μm or more, still more preferably 0.5 μm or more, and still more preferably 1 μm or more. On the other hand, it is more preferably 50 μm or less, particularly preferably 40 μm or less, and still more preferably 30 μm or less.
< BET specific surface area >
The BET specific surface area of each of the present compounds 1 and 2 is preferably 1m 2 /g～50m 2 /g。
If the BET specific surface area of the present compounds 1, 2 is 1m 2 When the amount is 50m or more, for example, the smoothness of the molded article is preferable because it is good 2 Lower than/g is preferable because, for example, dispersibility in a base material such as a resin is good.
From the above viewpoint, the BET specific surface area of the present compounds 1 and 2 is more preferably 2m 2 More than g, whereinIs selected as 5m 2 More than/g, preferably still more than 10m 2 More than/g, and still more preferably 15m 2 More than g. On the other hand, it is more preferably 45m 2 The ratio of the carbon atoms to the carbon atoms is below g.
< volume resistivity >
The volume resistivity of the present compounds 1 and 2 can be set to 2000 Ω · cm or more.
The volume resistivity is preferably higher in applications requiring insulation.
From the above viewpoint, the volume resistivity of the present compounds 1 and 2 is more preferably 10000 Ω · cm or more, still more preferably 100000 Ω · cm or more, and still more preferably 1000000 Ω · cm or more.
< negative thermal expansion Rate >
The present compounds 1 and 2 showed negative thermal expansion coefficients. For example, the film exhibits a negative thermal expansion coefficient in a temperature range of 30 to 100 ℃, a temperature range of 30 to 200 ℃, a temperature range of 30 to 300 ℃ and the like.
Among them, the present compound 1 shows a significantly excellent negative thermal expansion coefficient particularly in a temperature region of 30 to 100 ℃. Specifically, when heated from 30 ℃ to 100 ℃, the volume at 100 ℃ can be contracted by 0.15% to 2.0% relative to the volume at 30 ℃. Among them, the shrinkage is more preferably 0.15% to 1.0%, still more preferably 0.15% to 0.70%, and yet more preferably 0.15% to 0.45%.
The lower limit of each of the above ranges is 0.15%, but the lower limit is preferably 0.20%, and more preferably 0.25%.
On the other hand, the present compound 2 exhibits significantly excellent negative thermal expansion coefficients particularly in the temperature region of 30 ℃ to 200 ℃ and the temperature region of 30 ℃ to 300 ℃.
Specifically, when heated from 30 ℃ to 200 ℃, the volume at 200 ℃ can shrink by 1.0% to 3.0% relative to the volume at 30 ℃. Among them, the shrinkage is more preferably 1.0% to 2.0%, still more preferably 1.1% to 2.0%, and still more preferably 1.1% to 1.5%. The lower limit of each range is 1.0%, but the lower limit is preferably 1.05%, and more preferably 1.1%.
In addition, upon heating from 30 ℃ to 300 ℃, the 300 ℃ volume can shrink by 1.0% to 3.0% relative to the 30 ℃ volume. Among them, the shrinkage is more preferably 1.0% to 2.0%, still more preferably 1.1% to 2.0%, and still more preferably 1.1% to 1.5%.
The lower limit of each of the above ranges is 1.0%, but the lower limit is preferably 1.05%, and more preferably 1.1%.
< production method >
Next, a method for producing the present compounds 1 and 2 will be described. However, the production methods of the present compounds 1 and 2 are not limited to the production methods described below.
As an example of the method for producing the present compounds 1 and 2, there is a method for producing a compound characterized by subjecting a mixture containing at least a Zr raw material, a phosphorus raw material, sulfuric acid, water, and, if necessary, a raw material of M of the above composition formula (referred to as "M raw material") to a hydrothermal treatment to obtain a mixture after the hydrothermal treatment, subjecting the mixture after the hydrothermal treatment to solid-liquid separation and washing to obtain a washed mixture, drying the washed mixture to obtain a dried mixture, and firing the dried mixture at a temperature of 300 to 1000 ℃.
The following sequentially describes the production method.
Examples of the Zr raw material include zirconium oxychloride and its hydrate, zirconium chloride and its hydrate, zirconyl acetate and its hydrate, zirconium sulfate and its hydrate, zirconyl nitrate and its hydrate, zirconium carbonate and its hydrate, ammonium zirconium carbonate and its hydrate, sodium zirconium carbonate and its hydrate, and potassium zirconium carbonate and its hydrate. However, the present invention is not limited to these.
As the phosphorus raw material, phosphoric acid (H) can be used 3 PO 4 ) Diammonium hydrogen phosphate ((NH) 4 ) 2 HPO 4 ) Ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 ) Ammonium phosphate(NH 4 (PO 4 ) 3 ) Pyrophosphoric acid and polyphosphoric acid. However, the present invention is not limited to these.
Examples of the M raw material include compounds containing the element M, for example, sulfate salts and solutions thereof, chloride salts and solutions thereof, nitrate salts, acetate salts, oxides, polyacid and salts thereof, and the like of the element M. For example, when M is Ti, a titanium (IV) sulfate solution (Ti (SO) is mentioned 4 ) 2 ) Titanium (IV) chloride solution (TiCl) 4 ) When M is Ce, cerium sulfate (Ce (SO) 4 ) 2 ) Cerium chloride (CeCl) 3 ) When M is Sn, stannous chloride, stannic sulfate, and stannic oxide (SnO) may be mentioned 2 ) When M is Mn, manganese dioxide (MnO) is mentioned 2 ) When M is W, tungsten trioxide (WO) is mentioned 3 ) Ammonium paratungstate ((NH) 4 ) 10 (H 2 W 12 O 42 ) In the case where M is Mo, molybdenum trioxide (MoO) is exemplified 3 ) Hexaammonium heptamolybdate ((NH) 4 ) 6 Mo 7 O 24 ) Diammonium molybdate ((NH) 4 ) 2 MoO 4 ). However, the present invention is not limited to these. The compound is described as an anhydrate, but includes a hydrate.
As the S (sulfur) raw material, for example, ammonium sulfate, sulfur powder, or the like may be blended as necessary.
The Zr material, phosphoric acid, and if necessary, the M material, sulfuric acid, and water are mixed, stirred, and the obtained aqueous solution (mixture) is subjected to hydrothermal treatment to obtain a mixture after the hydrothermal treatment.
In this case, the phosphorus raw material (P raw material) and the Zr raw material may be set to have the same P/Zr molar ratio as the target compound or may be set to have a slightly larger amount of the phosphorus raw material.
As a method of the hydrothermal treatment, for example, the aqueous solution (mixture) may be placed in a sealable container and heated to 100 to 230 ℃ and left to stand with pressure for 3 hours to 3 days.
And then, subjecting the mixture after the hydrothermal treatment to solid-liquid separation and washing to obtain a washed mixture. That is, after the solid-liquid separation, washing may be performed by a method of further adding water to perform solid-liquid separation, or a method of washing with water or the like. In this case, it is preferable to repeat washing as necessary.
By this washing, the excess S component can be washed.
Then, the washed mixture is dried to obtain a dried mixture.
In this case, for example, the mixture after washing may be dried by heating so that the product temperature is 60 to 150 ℃. Wherein, the drying method can be adopted as long as appropriate.
Further, it was confirmed that: for example, in the case of using a box-type dryer such AS an ETTAS thermostatic dryer made of AS ONE, the set temperature of the drying device is substantially the same AS the product temperature.
Then, the dried mixture is fired to produce the present compound.
In this case, the dried mixture may be fired in the following manner: the product temperature is maintained at 300 to 1000 ℃, particularly at 400 ℃ or higher or 1000 ℃ or lower, more particularly at 400 ℃ or higher or 800 ℃ or lower, for 1 to 24 hours.
Further, it was confirmed that: for example, when a box-type electric furnace such as an electric furnace of KBF1150 ℃ series manufactured by KOYO THERMOS SYSTEMS is used, the furnace temperature, which is the set temperature of the firing apparatus, is substantially the same as the product temperature.
In the case of performing the surface treatment, the surface treatment may be performed after the firing and, if necessary, after the crushing or grinding.
The surface treatment may be carried out by using the above surface treatment compound.
As a specific method of the surface treatment, the present compounds 1 and 2 and the surface treatment compound may be dry-mixed or wet-mixed.
The wet mixing may be performed using water, a mixed solvent in which water and a water-soluble organic solvent are mixed within a range of solubility in water, an organic solvent, or the like.
However, the production method of the present compounds 1 and 2 is not limited to the above production method.
< use >
The present compounds 1 and 2 can be mixed as a negative thermal expansion material with a material having a positive thermal expansion coefficient (positive thermal expansion material), in other words, a composite material in which the thermal expansion coefficient is controlled by dispersing the negative thermal expansion material in the positive thermal expansion material.
Examples of the positive thermal expansion material include a resin material, a metal material, and a ceramic material.
< description of sentence >
In the present specification, when the expression "α to β" (α, β are arbitrary numbers), unless otherwise specified, the meaning of "α or more and β or less" is included, and the meaning of "preferably more than α" or "preferably less than β" is also included.
In addition, when the expression "α or more" (α is an arbitrary number) or "β or less" (β is an arbitrary number), the meaning of "preferably more than α" or "preferably less than β" is also included.
Examples
The invention is further illustrated by the following examples. However, the following examples are not intended to limit the invention in any way.
< example 1>
ZrCl 2 O·8H 2 O and phosphoric acid (H) 3 PO 4 ) Dissolving the above solutions in distilled water to 0.8 mol/L, mixing, and subjecting the resulting solutions to 98% H of 20ml and 6ml respectively 2 SO 4 Mix and stir for 90 minutes using a stirrer.
Next, the stirred aqueous solution (mixture) was poured into a teflon (registered trademark) closed container, and the container was placed in a pressure-resistant stainless steel outer cylinder. Then, the container placed in the outer tub was placed in a hot air circulating oven to be heated, and this state was maintained at 130 ℃ for 12 hours to perform hydrothermal treatment.
After the hydrothermal treatment, solid-liquid separation, removal of the supernatant, further washing with water and repeated solid-liquid separation were performed, and then the resulting mixture was poured into an evaporation pan, and the solid content was dried by heating with a hot air dryer set to 110 ℃ as an atmospheric temperature.
The dried powder was put into an electric furnace and calcined at 500 ℃ for 4 hours to obtain a compound (sample).
< example 2>
Reacting ZrCl 2 O·8H 2 O and phosphoric acid (H) 3 PO 4 ) Dissolving in distilled water to 0.8 mol/L, mixing, and mixing the solutions, respectively, 20ml and 4.5ml of each solution, 98% 2 SO 4 Mix and stir for 90 minutes using a stirrer.
Next, the stirred aqueous solution (mixture) was poured into a teflon (registered trademark) closed container, and the container was placed in a pressure-resistant stainless steel outer cylinder. Then, the container placed in the outer tub was placed in a hot air circulating oven to be heated, and this state was maintained at 130 ℃ for 12 hours to perform hydrothermal treatment.
After the hydrothermal treatment, solid-liquid separation, removal of supernatant, further washing by adding water and repeating solid-liquid separation was performed, and then the resulting solution was poured into an evaporation dish, and the solid content was dried by heating with a hot air dryer at 110 ℃.
The dried powder was put into an electric furnace and fired at 500 ℃ (product temperature) for 4 hours to obtain a compound (sample).
< reference example 1>
ZrCl 2 O·8H 2 O and NH 4 H 2 PO 4 Dissolving in distilled water to 0.8 mol/L, respectively, and then, 98% H of each of 20ml and 6ml of these aqueous solutions 2 SO 4 Mix and stir for 90 minutes using a stirrer.
Then, the stirred aqueous solution (mixture) was poured into a closed vessel made of teflon (registered trademark), and the vessel was placed in a pressure-resistant stainless steel outer cylinder. Then, the container placed in the outer tub was placed in a hot air circulation oven to be heated, and this state was maintained at 180 ℃ for 2 days to perform hydrothermal treatment.
After the hydrothermal treatment, a white precipitate was formed in the removed teflon (registered trademark) container. The solution containing the precipitate was flowed into an evaporation dish and heated on a heater at about 100 c to evaporate excess water. The mixture was further dried in an electric oven at 300 ℃ for 12 hours together with the evaporating dish. Then, the sample dried at 300 ℃ (product temperature) was further fired at 500 ℃ (product temperature) for 4 hours using an electric furnace to obtain a compound (sample).
< reference example 2>
A compound (sample) was obtained in the same manner as in reference example 1, except that the firing temperature was set to 700 ℃ (final temperature).
< example 3>
To react ZrCl 2 O·8H 2 O was prepared into a 0.8 mol/L aqueous solution 20ml and ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 ) 20ml of an aqueous solution prepared at 1.1 mol/L was mixed, and then, 6ml of the mixture was mixed with the aqueous solution to 98% H 2 SO 4 The mixture was stirred for 90 minutes using a stirrer.
Next, the stirred aqueous solution (mixture) was poured into a closed container made of teflon (registered trademark), and the container was placed in a pressure-resistant stainless steel outer cylinder. Then, the container placed in the outer tub was placed in a hot air circulating oven to be heated, and this state was maintained at 130 ℃ for 12 hours to perform hydrothermal treatment.
After the hydrothermal treatment, solid-liquid separation, removal of supernatant, further washing by adding water and repeating solid-liquid separation were performed, and then the resulting mixture was poured into an evaporation dish, and the solid content was dried by heating with a hot air dryer at 110 ℃.
The dried powder was put into an electric furnace and fired at 500 ℃ (product temperature) for 4 hours to obtain a compound (sample).
< example 4>
To react ZrCl 2 O·8H 2 Preparation of O20ml of an aqueous solution at 0.8 mol/L was mixed with ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 ) 20ml of the aqueous solution prepared at 0.9 mol/L was mixed, and then, 98% of 6ml was mixed with the aqueous solution 2 SO 4 The mixture was stirred for 90 minutes using a stirrer.
Next, the stirred aqueous solution (mixture) was poured into a teflon (registered trademark) closed container, and the container was placed in a pressure-resistant stainless steel outer cylinder. Then, the container placed in the outer tub was placed in a hot air circulating oven to be heated, and this state was maintained at 130 ℃ for 12 hours to perform hydrothermal treatment.
After the hydrothermal treatment, solid-liquid separation, removal of supernatant, further washing by adding water and repeating solid-liquid separation was performed, and then the resulting solution was poured into an evaporation dish, and the solid content was dried by heating with a hot air dryer at 110 ℃.
The dried powder was put into an electric furnace and fired at 500 ℃ (product temperature) for 4 hours to obtain a compound (sample).
< example 5>
5g of the compound (sample) obtained by the same procedure as in example 1 was mixed with 0.21g of 3-isocyanatopropyltriethoxysilane as a silane coupling agent as a surface-treated compound in a mixer (Force Mill FM-1, manufactured by OSAKA CHEMICAL) for 2 minutes, and then heat-treated at 140 ℃ for 1 hour to obtain a compound (sample).
< example 6>
5g of the compound (sample) obtained by the same procedure as in example 3 was mixed with 0.20g of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent as a surface treatment compound in a mixer for 2 minutes, and then heat-treated at 140 ℃ for 1 hour to obtain a compound (sample).
< example 7>
With respect to 5g of the compound (sample) obtained by the same procedure as in example 3, 0.19g of hexyltrimethoxysilane as a silane coupling agent was added as a surface treatment compound, and after mixing for 2 minutes by a mixer 4, heat treatment was performed under conditions of 140 ℃ for 1 hour to obtain a compound (sample).
< example 8>
In the presence of ZrCl 2 O·8H 2 O preparation to 0.72 mol/L aqueous solution 20ml adding 30% titanium sulfate solution 1.28g and mixing, to which mixed will be ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 ) Preparing into 0.9 mol/L aqueous solution 20ml, mixing into the aqueous solution 6ml of 98% 2 SO 4 The mixture was stirred for 90 minutes using a stirrer.
Next, the stirred aqueous solution (mixture) was poured into a teflon (registered trademark) closed container, and the container was placed in a pressure-resistant stainless steel outer cylinder. Then, the container placed in the outer tub was placed in a hot air circulation oven to be heated, and this state was maintained at 130 ℃ for 12 hours to perform hydrothermal treatment.
After the hydrothermal treatment, solid-liquid separation, removal of supernatant, further washing by adding water and repeating solid-liquid separation was performed, and then the resulting solution was poured into an evaporation dish, and the solid content was dried by heating with a hot air dryer at 110 ℃.
The dried powder was put into an electric furnace and fired at 500 ℃ (product temperature) for 4 hours to obtain a compound (sample).
< example 9>
In the presence of ZrCl 2 O·8H 2 O was prepared into a 0.64 mol/L aqueous solution 20ml, 2.56g of a 30% titanium sulfate solution was added thereto and mixed, and ammonium dihydrogen phosphate (NH) was mixed therewith 4 H 2 PO 4 ) 20ml of 0.9 mol/L aqueous solution was prepared, and then, 6ml of 98% H was mixed with the aqueous solution 2 SO 4 The mixture was stirred for 90 minutes using a stirrer.
Next, the stirred aqueous solution (mixture) was poured into a teflon (registered trademark) closed container, and the container was placed in a pressure-resistant stainless steel outer cylinder. Then, the container placed in the outer tub was placed in a hot air circulating oven to be heated, and this state was maintained at 130 ℃ for 12 hours to perform hydrothermal treatment.
After the hydrothermal treatment, solid-liquid separation, removal of supernatant, further washing by adding water and repeating solid-liquid separation were performed, and then the resulting mixture was poured into an evaporation dish, and the solid content was dried by heating with a hot air dryer at 110 ℃.
The dried powder was put into an electric furnace and fired at 500 ℃ (product temperature) for 4 hours to obtain a compound (sample).
< example 10>
In the presence of ZrCl 2 O·8H 2 O preparation to 0.72 mol/L aqueous solution 20ml added with 0.61g CeCl 3 ·7H 2 O and mixing, adding ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 ) 20ml of 0.9 mol/L aqueous solution was prepared, and then, 6ml of 98% H was mixed with the aqueous solution 2 SO 4 The mixture was stirred for 90 minutes using a stirrer.
Next, the stirred aqueous solution (mixture) was poured into a teflon (registered trademark) closed container, and the container was placed in a pressure-resistant stainless steel outer cylinder. Then, the container placed in the outer tub was placed in a hot air circulating oven to be heated, and this state was maintained at 130 ℃ for 12 hours to perform hydrothermal treatment.
After the hydrothermal treatment, solid-liquid separation, removal of supernatant, further washing by adding water and repeating solid-liquid separation were performed, and then the resulting mixture was poured into an evaporation dish, and the solid content was dried by heating with a hot air dryer at 110 ℃.
The dried powder was put into an electric furnace and fired at 500 ℃ (product temperature) for 4 hours to obtain a compound (sample).
< example 11>
In the presence of ZrCl 2 O·8H 2 O preparation to 0.64 mol/L aqueous solution 20ml adding 1.22g CeCl 3 ·7H 2 O and mixing, adding ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 ) Preparing into 0.9 mol/L aqueous solution 20ml, mixing into the aqueous solution 6ml of 98% 2 SO 4 The mixture was stirred for 90 minutes using a stirrer.
Next, the stirred aqueous solution (mixture) was poured into a teflon (registered trademark) closed container, and the container was placed in a pressure-resistant stainless steel outer cylinder. Then, the container placed in the outer tub was placed in a hot air circulation oven to be heated, and this state was maintained at 130 ℃ for 12 hours to perform hydrothermal treatment.
After the hydrothermal treatment, solid-liquid separation, removal of supernatant, further washing by adding water and repeating solid-liquid separation was performed, and then the resulting solution was poured into an evaporation dish, and the solid content was dried by heating with a hot air dryer at 110 ℃.
The dried powder was put into an electric furnace and fired at 500 ℃ (product temperature) for 4 hours to obtain a compound (sample).
< example 12>
In the presence of ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 ) Ammonium paratungstate 5 hydrate 1.57g was added to 20ml of an aqueous solution prepared at 0.9 mol/L, and ZrCl was added thereto 2 O·8H 2 O is prepared into 20ml of an aqueous solution of 0.72 mol/L and mixed, followed by mixing 6ml of 98% 2 SO 4 The mixture was stirred for 90 minutes using a stirrer.
Next, the stirred aqueous solution (mixture) was poured into a teflon (registered trademark) closed container, and the container was placed in a pressure-resistant stainless steel outer cylinder. Then, the container placed in the outer tub was placed in a hot air circulation oven to be heated, and this state was maintained at 130 ℃ for 12 hours to perform hydrothermal treatment.
After the hydrothermal treatment, solid-liquid separation, removal of supernatant, further washing by adding water and repeating solid-liquid separation, the resulting mixture was poured into an evaporation pan, and the solid content was dried by heating with a hot air dryer in an atmosphere of 110 ℃.
The dried powder was put into an electric furnace and fired at 500 ℃ (product temperature) for 4 hours to obtain a compound (sample).
< example 13>
In the presence of ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 ) Preparation of0.90g of hexaammonium heptamolybdate 4 hydrate was added to 20ml of a 0.9 mol/L aqueous solution, and ZrCl was added thereto 2 O·8H 2 O is prepared into 20ml of an aqueous solution of 0.72 mol/L and mixed, followed by mixing 6ml of 98% 2 SO 4 The mixture was stirred for 90 minutes using a stirrer.
Next, the stirred aqueous solution (mixture) was poured into a closed container made of teflon (registered trademark), and the container was placed in a pressure-resistant stainless steel outer cylinder. Then, the container placed in the outer tub was placed in a hot air circulation oven to be heated, and this state was maintained at 130 ℃ for 12 hours to perform hydrothermal treatment.
After the hydrothermal treatment, solid-liquid separation, removal of supernatant, further washing by adding water and repeating solid-liquid separation were performed, and then the resulting mixture was poured into an evaporation dish, and the solid content was dried by heating with a hot air dryer at 110 ℃.
The dried powder was put into an electric furnace and calcined at 500 ℃ for 4 hours to obtain a compound (sample).
(composition analysis)
The composition (atomic ratio) of the prepared compound (sample) was analyzed by ICP-OES (inductively Coupled Plasma Emission spectrometer).
＝ICP-OES＝
The ICP-OES apparatus used: 700 series, ICP-OES (Agilent Technologies Co., ltd.)
(D50)
The prepared compound (sample) was dispersed in pure water by irradiation with ultrasonic waves (40W for 3 minutes), and then the volume cumulative particle diameter D50 at a cumulative volume of 50 vol% was measured by a particle size distribution measuring apparatus ("Microtrac (trade name) MT-3300EXII (model)") using a laser diffraction scattering particle size distribution measuring method.
(BET specific surface area)
Using a specific surface area measuring apparatus ("Macsorb (HM model-1201)" manufactured by MOUNTECH), the surface area was measured in accordance with JIS R1626:1996 (method of measuring specific surface area of fine ceramic powder by gas adsorption BET method) '(3.5) one-point method by 6.2 flow method', the BET specific surface area (SSA (BET)) of the prepared compound (sample) was measured. In this case, a mixed gas of helium as a carrier gas and nitrogen as an adsorbate gas is used. Further, the degassing conditions were set to 300 ℃ for 10 minutes.
(volume resistivity)
The prepared compound (sample) was compressed at a pressure of 63MPa using a model MCP-PD51, a powder resistivity measuring system of Mitsubishi Chemical Analytech, and the volume resistivity was measured by a four-terminal method. For a sample exceeding the upper limit of the measurement of the apparatus, pellets compressed at a pressure of 63MPa were prepared and measured using a high resistance meter Hiresta UX/MCP-HT800 manufactured by Mitsubishi Chemical Analytech.
(thermal expansion coefficient)
The expansion rate of the lattice volume of the prepared compound (sample) was measured by the following method.
A multi-purpose sample high-temperature apparatus unit was attached to a powder X-ray diffraction apparatus described below, and the X-ray diffraction pattern was measured at 30 ℃ and 100 ℃. The measurement was started after 10 minutes of standing after the target temperature was reached.
The crystal structure was refined using the obtained X-ray diffraction pattern and analysis software (PDXL 2), and the lattice constant at each temperature was calculated. The lattice volume was calculated from the lattice constant.
The table shows the lattice volume expansion ratio of 30 to 100 ℃, that is, the rate of change in the lattice volume at 100 ℃ (referred to as "100 ℃ volume") calculated based on the lattice volume at 30 ℃ (referred to as "30 ℃ volume"), that is, ((30 ℃ volume-100 ℃ volume)/30 ℃ volume) × 100 as the volume expansion ratio (%).
Similarly, the lattice volume expansion ratios at 30 to 200 ℃ and 30 to 300 ℃ were calculated and shown in the table.
[ high temperature XRD ]
Using the apparatus: ultimaIV (richaku corporation)
Atmosphere: air (Air)
Tube current/tube voltage: 40kV/40mA
Target: cu
Step amplitude: 0.02 degree
Measurement range (scan speed): 10-80 ° (4 °/min)
Measurement temperature: 30 deg.C, 100 deg.C, 200 deg.C, 300 deg.C
[ Table 1]
Figure BDA0003955986770000181
[ Table 2]
Figure BDA0003955986770000191
As is apparent from the above examples and the test results carried out by the inventors of the present invention so far: is composed of a composition formula of Zr 2.00-b M b S Y P Z O 12.00+δ (in the formula, M is at least 1 selected from Ti, ce, sn, mn, hf, ir, pb, pd, cr, W and Mo, and b is not less than 0 and not more than<2.00、0<Y<0.30, Z.gtoreq.2.00, and delta is a value determined so as to satisfy the charge neutral condition), and Zr represented by the composition formula 2.00-b M b S Y P Z O 12.00+δ (wherein M is at least 1 selected from Ti, ce, sn, mn, hf, ir, pb, pd, cr, W and Mo, and 0. Ltoreq. B<2.00、0.30≤Y≤1.00、Z>2.00, δ is a value determined so as to satisfy the charge neutral condition) exhibited a negative thermal expansion coefficient, and the insulation resistance was excellent.
It was confirmed that: in the diffraction patterns obtained by X-ray diffraction of the compounds obtained in examples 1, 2 and 5, α -Zr was present 2 SP 2 O 12 The phase (ICDD card number: 00-038-0489) serves as the main phase.
It was confirmed that: in the diffraction patterns obtained by X-ray diffraction of the compounds obtained in examples 3,4, 6 to 13 and the reference example, α -Zr was present 2 SP 2 O 12 The phase (ICDD card number: 04-017-0937) is used as the main phase.
With respect to negative thermal expansion rates, it is known that: the present compounds 1 and 2 both exhibit negative thermal expansion coefficients in the temperature ranges of 30 to 100 ℃,30 to 200 ℃ and 30 to 300 ℃.
Among these, in particular, are known: the present compound 1 exhibits a significantly excellent negative thermal expansion coefficient in a temperature range of room temperature (30 ℃) to 100 ℃.
For example, examples 1, 2, 5, and 9 have a feature that the amount (Y) of S is small and the amount of P is large, as compared with reference examples 1 and 2. It was confirmed that: these examples 1, 2, 5 and 9 showed more excellent negative thermal expansion coefficient in the temperature region of 30 ℃ to 100 ℃. This is presumably due to: when the atomic ratio (Y) of S is less than 0.30 and the atomic ratio (Z) of P is 2.00 or more, the structure as a compound is stable and a significantly excellent negative thermal expansion coefficient is exhibited in a temperature range of room temperature (30 ℃) to 100 ℃.
On the other hand, it is known that: the present compound 2 exhibits a significantly excellent negative thermal expansion coefficient in a temperature range from room temperature (30 ℃) to 200 ℃ and in a temperature range from room temperature (30 ℃) to 300 ℃.
For example, examples 3,4, 6 to 8, and 10 to 13 have a feature that the amount (Y) of S is small and the amount of P is large as compared with reference examples 1 and 2, and on the other hand, the amount (Y) of S is large and the amount of P is large as compared with examples 1 and 2. Further, it was confirmed that: these examples 3,4, 6-8, and 10-13 showed more excellent negative thermal expansion coefficients in the temperature region of 30 ℃ to 200 ℃ and in the temperature region of 30 ℃ to 300 ℃. This is presumably due to: when the atomic ratio (Y) of S is 0.30 to 1.00 and the atomic ratio (Z) of P is more than 2.00, the alloy exhibits significantly excellent negative thermal expansion coefficients in a temperature range of room temperature to 200 ℃ and a temperature range of room temperature to 300 ℃.
Further, regarding the composition formula: zr 2.00 S Y P Z O 12.00+δ (in the formula, 0<Y<0.30, Z is more than or equal to 2.00) and Zr 2.00 S Y P Z O 12.00+δ (wherein, Y is 0.30. Ltoreq. Y.ltoreq.1.00, Z is 0.30. Ltoreq>2.00 A compound represented by the above patent document 2 (WO 2019/167924A)1) The findings disclosed in (a) and (b) can be presumed to be: compounds in which a part of the Zr sites is substituted with elements such as Ti, ce, sn, mn, hf, ir, pb, pd, cr, W, and Mo also exhibit negative thermal expansion coefficients in the same manner as the above compounds, and can achieve high insulation resistance.

Claims (15)

1. A compound represented by the formula Zr 2.00-b M b S Y P Z O 12.00+δ Wherein M is at least 1 selected from Ti, ce, sn, mn, hf, ir, pb, pd, cr, W and Mo, and 0. Ltoreq. B<2.00、0<Y<0.30, Z.gtoreq.2.00, and delta is a value determined in such a manner as to satisfy the charge neutrality condition.
2. A compound represented by the formula Zr 2.00-b M b S Y P Z O 12.00+δ In the formula, M is at least 1 selected from Ti, ce, sn, mn, hf, ir, pb, pd, cr, W and Mo, and b is more than or equal to 0<2.00、0.30≤Y≤1.00、Z>2.00, δ is a value determined in such a way that the charge neutrality condition is satisfied.
3. Compound according to claim 1, characterized in that it exhibits a negative thermal expansion rate.
4. Compound according to claim 2, characterized in that it exhibits a negative thermal expansion rate.
5. A compound according to claim 1 or claim 3, wherein upon heating from 30 ℃ to 100 ℃, the 100 ℃ volume shrinks by 0.15% to 2.0% relative to the 30 ℃ volume.
6. The compound of claim 2 or claim 4, wherein upon heating from 30 ℃ to 200 ℃, the 200 ℃ volume shrinks by 1.0% to 3.0% relative to the 30 ℃ volume.
7. The compound of any one of claims 1 to 6, wherein upon heating from 30 ℃ to 300 ℃, the 300 ℃ volume shrinks by 1.0% to 3.0% relative to the 30 ℃ volume.
8. The compound according to any one of claims 1 to 7, which has a volume resistivity of 2000 Ω · cm or more.
9. The compound according to any one of claims 1 to 8, which has a volume cumulative particle diameter D50 of 0.05 μm to 100 μm when a cumulative volume is 50 vol% as measured by a laser diffraction scattering particle size distribution measurement method.
10. The compound according to any one of claims 1 to 9, having a BET specific surface area of 1m 2 /g～50m 2 /g。
11. The compound according to any one of claims 1 to 10, which is surface-treated with a surface-treating compound.
12. The compound of claim 11, wherein the surface treatment compound is a silane coupling agent.
13. A composite material obtained by mixing or/and dispersing the compound according to any one of claims 1 to 12 with or in a positive thermal expansion material.
14. A method for producing a compound according to any one of claims 1 to 10,
wherein a mixture containing at least a Zr raw material, a phosphorus raw material, sulfuric acid, water and, if necessary, a raw material of M of the composition formula is subjected to a hydrothermal treatment to obtain a mixture after the hydrothermal treatment, the mixture after the hydrothermal treatment is subjected to solid-liquid separation and washing to obtain a washed mixture, the washed mixture is dried to obtain a dried mixture, and the dried mixture is fired at a temperature of 300 to 1000 ℃.
15. A method for producing a compound according to claim 11 or 12,
wherein a mixture containing at least a Zr raw material, a phosphorus raw material, sulfuric acid, water, and, if necessary, a raw material of the composition formula M is subjected to a hydrothermal treatment to obtain a mixture after the hydrothermal treatment, the mixture after the hydrothermal treatment is subjected to solid-liquid separation and washing to obtain a washed mixture, the washed mixture is dried to obtain a dried mixture, the dried mixture is fired at a temperature of 300 to 1000 ℃, and then a surface treatment is performed using a surface treatment compound.
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