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WO2023136116A1 - Composé, sa méthode de production et matériau composite - Google Patents

Composé, sa méthode de production et matériau composite Download PDF

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Publication number
WO2023136116A1
WO2023136116A1 PCT/JP2022/047939 JP2022047939W WO2023136116A1 WO 2023136116 A1 WO2023136116 A1 WO 2023136116A1 JP 2022047939 W JP2022047939 W JP 2022047939W WO 2023136116 A1 WO2023136116 A1 WO 2023136116A1
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atomic ratio
composition formula
amount
compound
thermal expansion
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Japanese (ja)
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敏宏 磯部
綾介 上原
涼 金田
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Tokyo Institute of Technology NUC
Mitsui Kinzoku Co Ltd
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Mitsui Mining and Smelting Co Ltd
Tokyo Institute of Technology NUC
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Priority to JP2023573962A priority Critical patent/JP7626916B2/ja
Publication of WO2023136116A1 publication Critical patent/WO2023136116A1/fr
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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
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium

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  • the present invention relates to a novel compound exhibiting a negative coefficient of thermal expansion that decreases in volume as the temperature rises, a method for producing the same, and a composite material using the novel compound.
  • thermal expansion control techniques attention is paid to a technique of controlling the overall thermal expansion coefficient by combining materials having negative thermal expansion coefficients (also referred to as “negative thermal expansion materials”).
  • negative thermal expansion materials examples include ⁇ -eucryptite, zirconium tungstate (ZrW 2 O 8 ), zirconium phosphate tungstate (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 describes Zr 2-a M a S x P 2 O 12+ ⁇ (M is Ti, Ce, Sn, Mn, Hf, Ir, Pb, Pd, Cr) as a new negative thermal expansion material. is at least one selected, a is 0 ⁇ a ⁇ 2, x is 0.4 ⁇ x ⁇ 1, and ⁇ is a value determined so as to satisfy the charge neutrality condition.
  • M is Ti, Ce, Sn, Mn, Hf, Ir, Pb, Pd, Cr
  • the negative thermal expansion material disclosed in Patent Document 2 exhibits a negative thermal expansion coefficient in the range from room temperature to 500 ° C., and the larger the sulfur content (x), the negative thermal expansion is particularly at 100 to 180 ° C. It is attracting attention as a useful material because it is a material that exhibits a high density and can achieve low density.
  • certain applications require materials that exhibit a negative coefficient of thermal expansion, especially in the temperature range of 200°C to 400°C. For example, since the melting point of solder used for joining electric or electronic parts is around 170 to 300°C, it is necessary to control the coefficient of thermal expansion particularly in the temperature range of 200 to 400°C. There is a need for materials that exhibit
  • the present invention provides a compound having a composition different from that of conventional compounds and exhibiting a negative coefficient of thermal expansion, preferably a new compound exhibiting an excellent negative coefficient of thermal expansion particularly in the temperature range of 200°C to 400°C. is intended to provide
  • the present invention provides a composition formula ( 1 ) ZrwMxSzP2O12 + ⁇ (wherein M is Al, Fe, Ga, Y, In, Nb, Bi, Si, La, one or more elements selected from Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ge and Lu, 0 ⁇ w ⁇ 4, x is is the sum of the amounts (atomic ratio) of the elements constituting M, 0 ⁇ x ⁇ 3, 0 ⁇ z ⁇ 2, and ⁇ is a value determined so as to satisfy the charge neutrality condition). .
  • the present invention also provides a composition formula (2) Zr 2-x-y M x S z P 2 O 12+ ⁇ (wherein M is Al, Fe, Ga, Y, In, Nb, Bi, Si, Ge, La, One or more elements selected from Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.x is the amount of elements constituting M ( atomic ratio), 0 ⁇ x ⁇ 3, y is a value determined by the amount of Zr defects, -2 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 2, 0 ⁇ 2-xy ⁇ 4, ⁇ is a value determined so as to satisfy the charge neutrality condition).
  • the present invention also provides a composition formula (3) Zr 2-x-y M x S z P 2-a Q a O 12+ ⁇ (wherein M is Al, Fe, Ga, Y, In, Nb, Bi, Si, one or more elements selected from Ge, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; One or two or more elements selected from x is the total amount (atomic ratio) of the elements constituting M, 0 ⁇ x ⁇ 3, and y is a value determined by the amount of Zr defects , ⁇ 2 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 2, 0 ⁇ 2-xy ⁇ 4, a is the total amount (atomic ratio) of the elements constituting Q, and 0 ⁇ a ⁇ 2 , ⁇ is a value determined so as to satisfy the charge neutrality condition).
  • M is Al, Fe, Ga, Y, In, Nb, Bi, Si, one or more elements selected from Ge, La, Pr, N
  • the present invention also provides a composition formula (4) Zr 2-x1-x2-y M1 x1 M2 x2 S z P 2 O 12+ ⁇ (wherein M1 is Al, Fe, Ga, Y, In, Nb, Bi, Si, one or more selected from Ge, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and M2 is Al, Cr, Fe, Ga, Y, In, Nb, Bi, Si, Ge, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Ce, Sn, Mn, Hf, One or more elements selected from Ir, Pb and Pd, which are different from M1, x1 is the total amount (atomic ratio) of the elements constituting M1, and x2 is the total value of the amount (atomic ratio) of the elements constituting M2, 0 ⁇ x1+x2 ⁇ 3, 0 ⁇ x1 ⁇ 2,
  • the present invention also provides a composition formula (5) Zr 2-x1-x2-y M1 x1 M2 x2 S z P 2-a Q a O 12+ ⁇ (wherein M1 is Al, Fe, Ga, Y, In, Nb, one or more selected from Bi, Si, Ge, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, M2 is Al, Cr, Fe, Ga, Y, In, Nb, Bi, Si, Ge, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Ce, Sn, one or more selected from Mn, Hf, Ir, Pb, Pd, W and Mo, which is an element different from M1, and Q is selected from Si and Ge One or more elements, x1 is the total amount (atomic ratio) of the elements that make up M1, x2 is the total amount (atomic ratio) of the elements that make up M
  • All of the compounds proposed by the present invention that is, the compounds represented by the above compositional formulas (1) to (5) exhibit negative coefficients of thermal expansion. Therefore, it is possible to control the coefficient of thermal expansion of a composite material which is a mixture by mixing with a material exhibiting a positive coefficient of thermal expansion (referred to as a “positive thermal expansion material”).
  • All of the compounds proposed by the present invention that is, the compounds represented by the above compositional formulas (1) to (5), can exhibit an excellent negative coefficient of thermal expansion, particularly in the temperature range of 200°C to 400°C. . Therefore, it can be suitably used for controlling the coefficient of thermal expansion in the temperature range of 200°C to 400°C. For example, it is possible to control the coefficient of thermal expansion in the temperature range of 200° C. to 400° C. of a composite material obtained by mixing with a positive thermal expansion material.
  • FIG. 2 is a graph showing the relationship between temperature and lattice constant for Zr 2-xy Al x S z P 2 O 12+ ⁇ prepared in Examples 1-1 to 1-3.
  • 2 is a graph showing the relationship between temperature and lattice constant for Zr 2-xy Y x S z P 2 O 12+ ⁇ prepared in Examples 2-1 to 2-3.
  • FIG. 4 is a graph showing the relationship between temperature and lattice constant for Zr 2-xy Fe x S z P 2 O 12+ ⁇ produced in Example 3-1.
  • FIG. FIG. 4 is a graph showing the relationship between temperature and lattice constant for Zr 2-x ⁇ y La x S z P 2 O 12+ ⁇ prepared in Examples 4-1 and 4-2.
  • FIG. 4 is a graph showing the relationship between temperature and lattice constant for Zr 2-xy Gd x S z P 2 O 12+ ⁇ produced in Example 5-1.
  • FIG. 4 is a graph showing the relationship between temperature and lattice constant for Zr 2-xy In x S z P 2 O 12+ ⁇ produced in Examples 6-1 to 6-3.
  • FIG. 4 is a graph showing the relationship between temperature and lattice constant for Zr 2-xy Nb x S z P 2 O 12+ ⁇ produced in Examples 7-1 and 7-2.
  • FIG. FIG. 10 is a graph showing the relationship between temperature and lattice constant for Zr 2-xy Fe x1 Nb x2 S z P 2 O 12+ ⁇ produced in Examples 8-1 and 8-2.
  • FIG. 10 is a graph showing the relationship between temperature and lattice constant for Zr 2-xy Y x1 Nb x2 S z P 2 O 12+ ⁇ produced in Examples 9-1 and 9-2.
  • FIG. 10 is a graph showing the relationship between temperature and lattice constant for Zr 2-xy Gd x1 Nb x2 S z P 2 O 12+ ⁇ produced in Example 10-1.
  • FIG. 10 is a graph showing the relationship between temperature and lattice constant for Zr 2-x-y Si x S z P 2 O 12+ ⁇ produced in Example 11-1.
  • FIG. 10 is a graph showing the relationship between temperature and lattice constant for Zr 2-x-y Si x S z P 2 O 12+ ⁇ produced in Example 11-1.
  • a compound according to an example of the embodiment of the present invention (referred to as “the present compound 1”) has a composition formula (1) ZrwMxSzP2O12 + ⁇ (wherein M is Al, Fe , Ga, Y , In, Nb, Bi, Si, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ge and Lu. 0 ⁇ w ⁇ 4, x is the total amount (atomic ratio) of the elements constituting M, 0 ⁇ x ⁇ 3, 0 ⁇ z ⁇ 2, ⁇ satisfies the charge neutrality condition. determined value).
  • Elements that can constitute M in the composition formula (1) include Al, Fe, Ga, Y, In, Nb, Bi, Si, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er , Tm, Yb, Ge and Lu, and these can constitute M of the composition formula (1) as one or a combination of two or more.
  • w indicating the amount of Zr (atomic ratio) may be 0 ⁇ w ⁇ 4 from the viewpoint of maintaining the crystal structure, especially 1 or more or 3 or less, Among them, it can be 1.5 or more or 2.2 or less.
  • x indicating the amount (atomic ratio) of the M element is the total amount (atomic ratio) of the elements constituting M, and from the viewpoint of maintaining the crystal structure , 0 ⁇ x ⁇ 3, preferably 0.1 or more or 2 or less, especially 0.2 or more or 0.7 or less.
  • composition formula (1) of the present compound 1 “z” indicating the amount (atomic ratio) of S (sulfur) may be 0 ⁇ z ⁇ 2, especially 0.2, from the viewpoint of maintaining the crystal structure. It can be greater than or equal to 1.5, or less than or equal to 1.5, preferably greater than or equal to 0.3 or less than or equal to 1.
  • ⁇ indicating the amount (atomic ratio) of O (oxygen) is a value determined to satisfy the charge neutrality condition, and is usually ⁇ 2.50 or more. 0.00 or less. -2.00 or more or -0.50 or less, -1.50 or more or -0.00 or less, -1.00 or more or -0.50 or less, -1.33 or more or -0. It may be 80 or less.
  • the "charge neutrality condition” does not have to be completely neutral, and a composition with oxygen deficiency or oxygen excess within the allowable range for a compound is allowed.
  • a compound according to an example of the embodiment of the present invention (referred to as “this compound 2”) has a composition formula (2) Zr 2-xy M x S z P 2 O 12+ ⁇ (wherein M is Al, Fe, one or two selected from Ga, Y, In, Nb, Bi, Si, Ge, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu x is the total amount (atomic ratio) of the elements constituting M, 0 ⁇ x ⁇ 3, y is a value determined by the amount of Zr defects, ⁇ 2 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 2, 0 ⁇ 2 ⁇ xy ⁇ 4, ⁇ is a value determined so as to satisfy the charge neutrality condition).
  • composition formula ( 2 ) relates to the present compound 1 represented by the composition formula ( 1 ).
  • Elements that can constitute M in the composition formula (2) include trivalent Al, Fe, Ga, Y, In, La, Gd, and other rare earth elements.
  • Other rare earth elements include Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb and Lu.
  • Other elements that can constitute M include tetravalent Si and Ge, and pentavalent Nb and Bi. These can constitute M of the compositional formula (2) as one type or a combination of two or more types.
  • composition formula (2) of the present compound 2 “2-xy” indicating the amount of Zr (atomic ratio) may be 0 ⁇ 2-xy ⁇ 4 from the viewpoint of maintaining the crystal structure. , preferably 1 or more or 3 or less, among which 1.5 or more or 2.2 or less.
  • x is the total value of the amount (atomic ratio) of the elements constituting M, preferably 0 ⁇ x ⁇ 3, especially 0.1 or more or 2 or less, more preferably 0.2 or more or 1 or less, more preferably 0.3 or more or 0.7 or less.
  • composition formula (2) of the present compound 2 "z” indicating the amount (atomic ratio) of S (sulfur) is preferably 0 ⁇ z ⁇ 2, especially 0.1 or more or 1.5 or less, Above all, it is more preferably 0.2 or more or 1.2 or less, more preferably 0.3 or more or 1 or less.
  • a compound according to another example of the embodiment of the present invention (referred to as “this compound 3”) has a composition formula (3) Zr 2-x-y M x S z P 2-a Q a O 12+ ⁇ (wherein, M is selected from Al, Fe, Ga, Y, In, Nb, Bi, Si, Ge, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu Q is one or two or more elements selected from Si and Ge.
  • x is the total amount (atomic ratio) of the elements constituting M , where 0 ⁇ x ⁇ 3, y is a value determined by the amount of Zr defects, -2 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 2, 0 ⁇ 2-xy ⁇ 4, a constitutes Q It is a compound represented by the total amount of elements (atomic ratio), 0 ⁇ a ⁇ 2, and ⁇ being a value determined so as to satisfy the charge neutrality condition.
  • the composition formula (3) relates to the present compound 1 represented by the composition formula (1), in which a part of the zirconium site of “Zr 2 S z P 2 O 12+ ⁇ ” is substituted with the M element, and a part of the phosphorus site is is a composition estimated to be replaced by the Q element, and is a composition formula showing the atomic ratio of each element when the atomic ratio of P (phosphorus) is normalized by "2".
  • M in the composition formula (3) is, as described above, an element M that is presumed to substitute a part of the zirconium site, and an element that can constitute M is M in the composition formula (2) are the same as the elements that can constitute
  • elements that can constitute Q are one or more elements selected from Si and Ge. These Si and Ge can be assumed to replace part of the zirconium sites and part of the phosphorus sites. When P is normalized by 2, since Zr is larger than 2, it is considered that P is missing, so it is estimated that Si or Ge is substituted for part of the phosphorus site. can be done. This point is the same for this compound 5 as well.
  • “a” indicating the amount (atomic ratio) of Q is the total value of the amounts (atomic ratio) of the elements constituting Q, and preferably 0 ⁇ a ⁇ 2. It is more preferably 0.1 or more or 1 or less, more preferably 0.2 or more or 0.5 or less, and more preferably 0.3 or less.
  • a compound according to still another example of the embodiment of the present invention (referred to as “this compound 4”) has a composition formula (4) Zr 2-x1-x2-y M1 x1 M2 x2 S z P 2 O 12+ ⁇ (wherein , M1 is selected from Al, Fe, Ga, Y, In, Nb, Bi, Si, Ge, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu and M2 is Al, Cr, Fe, Ga, Y, In, Nb, Bi, Si, Ge, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho , Er, Tm, Yb, Lu, Ti, Ce, Sn, Mn, Hf, Ir, Pb and Pd, and is an element different from M1.
  • M1 is selected from Al, Fe, Ga, Y, In, Nb, Bi, Si, Ge, La, Pr, Nd, Sm, Eu, Gd, Tb
  • x2 is the sum of the amounts (atomic ratio) of the elements that make up M2, 0 ⁇ x1+x2 ⁇ 3, 0 ⁇ x1 ⁇ 2, 0 ⁇ x2 ⁇ 2, y is a value determined by the defect amount of Zr, -2 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 2, 0 ⁇ 2-x1-x2-y ⁇ 4, ⁇ satisfies the charge neutrality condition. It is a compound represented by a value determined by
  • Composition formula (4) relates to the present compound 1 represented by composition formula (1), and it is presumed that a part of the zirconium site of "Zr 2 S z P 2 O 12+ ⁇ " is replaced by M1 element and M2 element. It is a composition formula showing the atomic ratio of each element when the atomic ratio of P (phosphorus) is normalized by "2".
  • the elements that can constitute M1 are the same as the elements that can constitute M in the composition formula (2).
  • elements that can constitute M2 include Al, Cr, Fe, Ga, Y, In, Nb, Bi, Si, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, one or more elements selected from Ho, Er, Tm, Yb, Lu, Ti, Ce, Sn, Mn, Hf, Ir, Pb and Pd and different from M1; can be done.
  • composition formula (4) of the present compound 4 “2-x1-x2-y” indicating the amount (atomic ratio) of Zr is 0 ⁇ 2-x1-x2-y ⁇ 4 from the viewpoint of maintaining the crystal structure. 3 or less, 0.1 or more or 2 or less, 0.2 or more or 1 or less, 0.3 or more or 0.7 or less.
  • x1 is the total amount (atomic ratio) of the elements constituting M1
  • x2 is the amount (atomic ratio) of the elements constituting M2. It is the total value, and 0 ⁇ x1+x2 ⁇ 3, preferably 0 ⁇ x1 ⁇ 2, among which 0.1 or more or 1 or less, among which 0.2 or more or 0.75 or less, among which 0.3 or more Alternatively, it is more preferably 0.5 or less. Further, it is preferable that 0 ⁇ x2 ⁇ 2. preferable.
  • composition formula (4) The meanings and numerical ranges of "y”, "z” and “ ⁇ ” in composition formula (4) are the same as in composition formula (2) above.
  • a compound according to still another example of the embodiment of the present invention (referred to as “this compound 5”) has a composition formula (5) Zr 2-x1-x2-y M1 x1 M2 x2 S z P 2-a Q a O 12 + ⁇ (wherein M1 is Al, Fe, Ga, Y, In, Nb, Bi, Si, Ge, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu is one or more selected from among, and M2 is Al, Cr, Fe, Ga, Y, In, Nb, Bi, Si, Ge, La, Pr, Nd, Sm, Eu, Gd, Tb , Dy, Ho, Er, Tm, Yb, Lu, Ti, Ce, Sn, Mn, Hf, Ir, Pb, Pd, W and Mo, wherein the M1 Q is one or more elements selected from Si and Ge.x1 is the total amount (atomic ratio) of the elements constituting M
  • composition formula (5) relates to the present compound 1 represented by the composition formula (1), in which a part of the zirconium site of "Zr 2 S z P 2 O 12+ ⁇ " is substituted with the M1 element and the M2 element, and the phosphorus
  • a composition formula showing the atomic ratio of each element when the atomic ratio of P (phosphorus) is normalized by "2" is.
  • the elements that can constitute M1 and the elements that can constitute M2 in the composition formula (5) are the same as the elements that can constitute M1 and the elements that can constitute M2 in the composition formula (4).
  • the elements that can constitute Q in the composition formula (5) are the same as the elements that can constitute Q in the composition formula (3).
  • composition formula (5) The meanings and numerical ranges of "x1", “x2”, “x1+x2" and "2-x1-x2-y” in composition formula (5) are the same as in composition formula (4).
  • composition formula (5) The meaning and numerical range of "a" in composition formula (5) are the same as in composition formula (3).
  • composition formula (5) The meanings and numerical ranges of "y”, "z” and “ ⁇ ” in composition formula (5) are the same as in composition formula (2) above.
  • the amount of each element except oxygen that is, the amount of Zr, M, S, P and Q can be measured by ICP-OES after dissolving the entire amount. Since it is difficult to strictly measure the amount of oxygen, a composition ratio that is estimated to be electrically neutral from the chemical ratios of elements other than oxygen is used.
  • Crystal phases present in Compounds 1, 2, 3, 4 and 5 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 is the main phase, that is, X-ray diffraction obtained by analyzing the present compounds 1, 2, 3, 4 and 5 by X-ray diffraction method (XRD, Cu ray source) In the pattern, it is preferable that the peak intensity derived from this crystal is the highest. In other words, it may partially contain other crystal phases. For example, a ⁇ phase ( ⁇ -Zr 2 SP 2 O 12 (ICDD card: 04-007-8019)) may be partially contained in addition to the ⁇ phase ( ⁇ -Zr 2 SP 2 O 12 ).
  • the present compounds 1, 2, 3, 4 and 5 exhibit negative coefficients of thermal expansion.
  • the temperature range of room temperature (30 ° C.) to 100 ° C. the temperature range of room temperature (30 ° C.) to 200 ° C.
  • the temperature range of room temperature (30 ° C.) to 300 ° C. the temperature range of room temperature (30 ° C.) to 400 ° C. It exhibits a negative coefficient of thermal expansion.
  • the present compounds 1, 2, 3, 4 and 5 are characterized by exhibiting a remarkably excellent negative coefficient of thermal expansion in the temperature range of 200°C to 400°C. Specifically, when heated to 200°C to 400°C, the volume at 400°C can shrink by 0.1% to 0.5% relative to the volume at 200°C.
  • M including M1 and M2
  • x is preferably 0.05 or more and 1 or less in Compounds 1, 2 and 3.
  • the volume at 400°C can shrink by 0.1% to 0.3% relative to the volume at 200°C when heated to 200°C to 400°C.
  • x is preferably 0.05 or more and 0.05 or more. If it is 5 or less, when heated to 200°C to 400°C, the volume at 400°C can shrink by 0.3% to 0.5% relative to the volume at 200°C.
  • M (including M1 and M2) in Compounds 1, 2, 3, 4 and 5 is Nb, preferably x in Compounds 1, 2 and 3 is 0.1 to 0.1. If it is 5 or less, when heated to 200°C to 400°C, the volume at 400°C can shrink by 0.2% to 0.5% relative to the volume at 200°C.
  • the present compounds 1, 2, 3, 4 and 5 are characterized by exhibiting a remarkably excellent negative coefficient of thermal expansion even in the temperature range of 100°C to 200°C. Specifically, when heated to 100°C to 200°C, the volume at 200°C can shrink by 0.5% to 1.5% relative to the volume at 100°C.
  • M (including M1 and M2) in the present compounds 1, 2, 3, 4 and 5 is Fe and Nb
  • M1 and M2 are preferably Fe and Nb
  • a1 and a2 are 0.2 or more and 0.5 or less
  • the volume at 200 ° C. is 1.1% to the volume at 100 ° C. It can shrink by 1.3%.
  • M (including M1 and M2) in compounds 1, 2, 3, 4 and 5 is La
  • x in compounds 1, 2 and 3 is 0.05 or more and 0.05 or more. If it is 1 or less, when heated to 100°C to 200°C, the volume at 200°C can shrink by 0.9% to 1.1% relative to the volume at 100°C.
  • M (including M1 and M2) is Fe and Nb
  • M1 and M2 are Fe and Nb
  • a1 and a2 are 0.05 or more and 0.2 or less, when heated to 100 ° C. to 200 ° C., the volume at 200 ° C. is 1.0% to the volume at 100 ° C. It can shrink by 1.2%.
  • the present compounds 1, 2, 3, 4 and 5 are represented by the "compositional formula Zr 2 SP 2 O 12.00 + ⁇ Zirconium phosphate sulfate is thought to exhibit a negative coefficient of thermal expansion due to different contraction mechanisms, the framework mechanism and the phase transition mechanism.
  • the shrinkage is mainly due to the framework mechanism.
  • the contraction is mainly due to the framework mechanism.
  • the framework mechanism is one of the mechanisms by which a material thermally contracts. As the bond angles of atoms change, the atomic groups are folded to fill the small spaces in the crystal structure, making the crystal smaller. mechanism.
  • the phase transition mechanism is one of the mechanisms by which a material thermally shrinks, and it is a mechanism that achieves volume reduction through continuous phase transition in a specific temperature range using a method such as element substitution. .
  • Zr raw materials include zirconium oxychloride and its hydrates, zirconium chloride and its hydrates, zirconium oxyacetate and its hydrates, zirconium acetate and its hydrates, zirconium sulfate and its hydrates, and oxynitric acid.
  • zirconium or its hydrate, zirconium nitrate or its hydrate, zirconium carbonate or its hydrate, zirconium ammonium carbonate or its hydrate, sodium zirconium carbonate or its hydrate, potassium zirconium carbonate or its hydrate, etc. can be used. However, it is not limited to these.
  • Phosphorus raw materials include 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 ( PO 4 ) 3 ), pyrophosphoric acid, polyphosphoric acid and the like can be used. However, it is not limited to these.
  • M raw material M1 raw material, M2 raw material, and Q raw material
  • a compound containing the element M a compound containing the element M1, a compound containing the element M2, a compound containing the element Q, for example, a sulfate of each element, a solution thereof, and a chloride Salts or solutions thereof, nitrates, acetates, oxides, polyacids or salts thereof, and hydrates thereof can be mentioned.
  • a compound containing the element M for example, a sulfate of each element, a solution thereof, and a chloride Salts or solutions thereof, nitrates, acetates, oxides, polyacids or salts thereof, and hydrates thereof
  • ammonium sulfate, sulfur powder, etc. can be blended as S (sulfur) raw materials as needed.
  • Step 1 Regarding the mixing of the raw materials, the Zr raw material, the phosphorus raw material, the sulfuric acid, the M raw material, or the M1 raw material and M2 raw material, and if necessary, the Q raw material and water may be mixed at once, or After dissolving the Zr raw material, the phosphorus raw material, the M raw material or the M1 raw material, the M2 raw material, and optionally the Q raw material in distilled water, sulfuric acid may be mixed with these aqueous solutions.
  • Step 2 the obtained mixture (aqueous solution) is hydrothermally treated to obtain a hydrothermally treated mixture.
  • the mixture (aqueous solution) is placed in a sealable container, heated to a temperature of 100 to 230 ° C., preferably 130 ° C. or higher, more preferably 180 ° C. or higher, and under pressure. It may be left still for 0.5 to 4 days, especially for 3 hours or longer.
  • the post-hydrothermal treatment mixture obtained by hydrothermal treatment may be subjected to solid-liquid separation and washing, if necessary.
  • solid-liquid separation water may be added for solid-liquid separation, or washing may be performed by passing water through the washing method. At this time, washing may be repeated as necessary.
  • washing may be repeated as necessary. By this washing, the excess S component can be washed away. However, the excess S component may be burned off by baking without washing.
  • Step 3 the hydrothermally treated mixture obtained by the hydrothermal treatment is dried. Drying of the hydrothermally treated mixture may be carried out by heating the hydrothermally treated mixture to a product temperature of 60 to 150° C., for example. Specifically, since a white precipitate is formed in the container after the hydrothermal treatment, the solution (mixture) containing this white precipitate is poured into an evaporating dish and heated with a heater of about 100°C to remove excess water. should be evaporated. However, any suitable drying method may be adopted.
  • Step 4 Then, if necessary, a second drying is carried out. If the mixture after the first drying contains excess sulfuric acid, it cannot be completely dried, so a second drying is performed. Specifically, for example, the evaporating dish may be placed in an electric furnace at 300° C. for the second drying. However, any suitable drying method may be adopted.
  • the compound 1, 2, 3, 4 or 5 can be obtained by firing the resulting dried mixture at a temperature of 300 to 1000°C.
  • the dried mixture may be fired at a temperature of 300 to 1000° C., especially 400° C. or higher or 1000° C. or lower, especially 450° C. or higher or 900° C. or lower for 1 to 24 hours.
  • a box-type electric furnace such as the KBF1150°C series electric furnace manufactured by Koyo Thermo Systems Co., Ltd., it has been confirmed that the set temperature of the baking apparatus, that is, the temperature inside the furnace, and the product temperature are almost the same.
  • the value of x in the above general formula can be adjusted. Specifically, the higher the firing temperature, the easier it is for the sulfur S in the general formula to escape, so the amount of sulfur S decreases. Also, at this time, the value of x (that is, the amount of S) in the above general formula may be adjusted by adjusting the firing time.
  • Any of the present compounds 1, 2, 3, 4 and 5 can be a composite material mixed with a material having a positive coefficient of thermal expansion (positive thermal expansion material) as a negative thermal expansion material. Furthermore, by allowing one of the negative thermal expansion material and the positive thermal expansion material to exist in the other in a dispersed state, a composite material having a coefficient of thermal expansion controlled within a predetermined range can be obtained. More preferably, a composite material having a highly controlled coefficient of thermal expansion can be formed by dispersing the negative thermal expansion material in the positive thermal expansion material.
  • positive thermal expansion materials examples include resin materials, metal materials, and ceramic materials.
  • Example/Comparative example> As raw materials, ZrCl 2 O.8H 2 O (Wako special grade, Wako Pure Chemical Industries, Ltd.), (NH 4 ) 2 HPO 4 (reagent special grade, Kanto Chemical Co., Ltd.), H 2 SO 4 (reagent special grade, Japanese Kojunyaku Co., Ltd.) and raw materials for the substitution elements shown in Table 1 were prepared. Then, ZrCl 2 O.8H 2 O and (NH 4 ) 2 HPO 4 were each dissolved in distilled water to 0.8M.
  • the hydrothermal treatment temperature was 180° C., and the hydrothermal treatment time was 12 hours.
  • a white precipitate was formed in the taken-out Teflon container.
  • the solution containing this precipitate was poured into an evaporating dish and heated on a heater of about 100° C. for 5 hours to evaporate excess water (step 3: first drying).
  • step 3 first drying
  • the sample since the sample contained excessive H 2 SO 4 , the sample was not completely dried and water remained. Therefore, it was further dried for 12 hours in an electric furnace (KDF-S80, Denken High Dental Co., Ltd.) at 300° C. together with the evaporating dish (step 4: second drying). Thereafter, the sample dried at 300° C. was calcined at 500° C.
  • Example 2 The resulting compound (sample) was subjected to X-ray diffraction and found to be a single phase with the composition shown in Table 2.
  • composition analysis The composition (atomic ratio) of the prepared compound (sample) was analyzed using ICP-OES (Inductivity Coupled Plasma Optical Emission Spectrometry) and is shown in Table 2.
  • ICP-OES ⁇ ICP-OES equipment used: 700 series, ICP-OES (Agilent Technologies, Inc.)
  • thermo expansion coefficient The coefficient of lattice volume expansion of the prepared compound (sample) was measured using the following method.
  • a multi-purpose sample high-temperature device unit was attached to the following powder X-ray diffractometer for high-temperature XRD, and X-ray diffraction patterns were measured at room temperature (30°C), 100°C, 200°C, and 400°C. The measurement was started after standing still for 10 minutes after reaching the target temperature.
  • X-ray diffraction pattern and analysis software (PDXL2)
  • the crystal structure was refined, and the lattice constant at each temperature was calculated.
  • the lattice volume was calculated from the lattice constant.
  • Table 2 shows the lattice volume expansion coefficient from room temperature (30 ° C.) to 100 ° C., that is, the lattice volume at 30 ° C. (referred to as “30 ° C. volume”) as a reference, and the lattice volume at 100 ° C.
  • the rate of change in volume that is, ((volume at 30°C - volume at 100°C)/volume at 30°C) x 100 was calculated as the volume expansion rate (%) and shown in Table 2 and the figure.
  • the coefficient of lattice volume expansion at 100° C. to 200° C. and the coefficient of lattice volume expansion at 400° C. were calculated and shown in Table 2 and FIGS. 1 to 11.
  • composition formula (2) Zr 2-xy M x S z P 2 O 12 + ⁇ (wherein M is Al, Fe, Ga, Y, One or more elements selected from In, Nb, Bi, Si, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
  • x is the total value of the amount (atomic ratio) of elements constituting M, 0 ⁇ x ⁇ 3, y is a value determined by the amount of Zr defects, ⁇ 2 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 2, 0 ⁇ 2-xy ⁇ 4, ⁇ is a value determined to satisfy the charge neutrality condition)
  • Compound 1 represented by Composition formula (3) Zr 2-x-y M x S z P 2-a Q a O 12+ ⁇ (wherein M is Al, Fe, Ga, Y, In, Nb, Bi, Si, La, Pr, Nd , Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and Q is one selected from Si and Ge Or two or more elements, x is the total value of the amount (atomic ratio) of the elements constituting M, 0 ⁇ x ⁇ 3, y is a value determined by the amount of Zr defects, -2 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 2, 0 ⁇ 2-xy ⁇
  • x1 is the total amount (atomic ratio) of the elements constituting M1
  • x2 is the total amount (atomic ratio) of the elements constituting M2.
  • 0 ⁇ x1+x2 ⁇ 3, 0 ⁇ x1 ⁇ 2, 0 ⁇ x2 ⁇ 2, y is a value determined by the amount of Zr defects, ⁇ 2 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 2, 0 ⁇ 2 ⁇ x1 -x2-y ⁇ 4, a is the total amount (atomic ratio) of the elements that make up Q, 0 ⁇ a ⁇ 2, and ⁇ is a value that satisfies the charge neutrality condition). 4 exhibit a negative coefficient of thermal expansion, particularly in the temperature range of 200° C. to 400° C., which is superior to the compound represented by the composition formula Zr 2 SP 2 O 12.00+ ⁇ . can be considered to indicate

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Abstract

L'invention concerne un nouveau composé qui a une composition différente des composés classiques et présente un coefficient de dilatation thermique négatif, de préférence, un composé qui présente un excellent coefficient de dilatation thermique négatif, en particulier dans la plage de température de 200 à 400°C. L'invention concerne un composé représenté par la formule de composition (1) : ZrwMxSzP2O12+δ [dans laquelle : M représente un ou plusieurs éléments choisis parmi Al, Fe, Ga, Y, In, Nb, Bi, Si, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ge et Lu ; 0 < w ≤ 4 ; x est la quantité totale (rapport atomique) d'éléments constituant M ; 0 < x < 3 ; 0 < z ≤ 2 ; et δ est une valeur qui est déterminée pour satisfaire la condition de neutralité de charge].
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020004072A1 (fr) * 2018-06-26 2020-01-02 日本化学工業株式会社 Matériau d'expansion thermique négative, sa méthode de fabrication et matériau composite
WO2021261049A1 (fr) * 2020-06-22 2021-12-30 三井金属鉱業株式会社 Composé, procédé de production associé et matériau composite

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020004072A1 (fr) * 2018-06-26 2020-01-02 日本化学工業株式会社 Matériau d'expansion thermique négative, sa méthode de fabrication et matériau composite
WO2021261049A1 (fr) * 2020-06-22 2021-12-30 三井金属鉱業株式会社 Composé, procédé de production associé et matériau composite

Non-Patent Citations (2)

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Title
ISOBE TOSHIHIRO, HAYAKAWA YUKO, ADACHI YURI, UEHARA RYOSUKE, MATSUSHITA SACHIKO, NAKAJIMA AKIRA: "Negative thermal expansion in α-Zr2SP2O12 based on phase transition- and framework-type mechanisms", NPG ASIA MATERIALS, NATURE JAPAN KK, JP, vol. 12, no. 1, 1 December 2020 (2020-12-01), JP , pages 80, XP093079278, ISSN: 1884-4049, DOI: 10.1038/s41427-020-00266-9 *
S. G. THOMA, JACKSON N. B., NENOFF T. M., MAXWELL R. S.: "MIXED METAL PHOSPHO-SULFATES FOR ACID CATALYSIS", NANOTUBES AND RELATED NANOSTRUCTURES : NOVEMBER 26 - 30, 2007, BOSTON, MASSACHUSETTS, USA; IN: MATERIALS RESEARCH SOCIETY SYMPOSIUM PROCEEDINGS (MRS PROCEEDINGS); ISSN 0272-9172, MATERIALS RESEARCH SOCIETY, US, vol. 497, 1 January 1997 (1997-01-01), US , pages 191 - 200, XP055635472, ISSN: 0272-9172, ISBN: 978-1-60560-826-6, DOI: 10.1557/PROC-497-191 *

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