WO2022097746A1 - Matériau à dilatation thermique négative et matériau composite - Google Patents

Matériau à dilatation thermique négative et matériau composite Download PDF

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WO2022097746A1
WO2022097746A1 PCT/JP2021/041006 JP2021041006W WO2022097746A1 WO 2022097746 A1 WO2022097746 A1 WO 2022097746A1 JP 2021041006 W JP2021041006 W JP 2021041006W WO 2022097746 A1 WO2022097746 A1 WO 2022097746A1
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thermal expansion
type zeolite
mer
coefficient
negative thermal
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PCT/JP2021/041006
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English (en)
Japanese (ja)
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敏宏 磯部
佑亮 松野
遥菜 井川
冬 二宮
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国立大学法人東京工業大学
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Priority to JP2022560837A priority Critical patent/JPWO2022097746A1/ja
Publication of WO2022097746A1 publication Critical patent/WO2022097746A1/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
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/14—Type A
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to a negative thermal expansion material and a composite material.
  • Patent Document 1 discloses Bi 1-x Sb x NiO 3 (where x is 0.02 ⁇ x ⁇ 0.20) as a material having a negative coefficient of thermal expansion.
  • an object of the present invention is to provide a negative thermal expansion material and a composite material that can realize low cost and low density.
  • the negative thermal expansion material according to one aspect of the present invention has a negative coefficient of thermal expansion including at least one selected from the group consisting of MER-type zeolite, GIS-type zeolite, LTA-type zeolite, and FAU-type zeolite. It is a material.
  • the MER-type zeolite may be M (x- ⁇ ) [Al x Si 32-x O 64 ] ⁇ yH 2 O.
  • M is H, Li, Na, K, Ag, NH 4 , Mg, Ca, Sr, Ba, Cd, Ni, Zn, Cu, Hg, Fe, Co, Sn, Pb, Mn, Al, Cr, At least one selected from the group consisting of Y, Zr, Ti, lanthanoids, and tetraethylammonium ions, x satisfies 6.0 ⁇ x ⁇ 14.0, and ⁇ is determined to satisfy the charge neutrality condition. It is a value, and y is an arbitrary value.
  • the MER-type zeolite may be K x- ⁇ [Al x Si 32-x O 64 ] ⁇ yH 2 O.
  • x is a value that satisfies 6.0 ⁇ x ⁇ 14.0
  • ⁇ is a value that is determined so as to satisfy the charge neutrality condition
  • y is an arbitrary value.
  • the x may be 6.7 ⁇ x ⁇ 13.5.
  • the volume expansion coefficient at least 60 ° C. or higher and 140 ° C. or lower may be -236 ppmK -1 or higher and -98.6 ppmK -1 or lower.
  • the volume shrinkage associated with the phase transition may be exhibited in the temperature range of 100 ° C. or higher and 200 ° C. or lower.
  • a part of K contained in the MER type zeolite is H, Li, Na, Ag, NH 4 , Mg, Ca, Sr, Ba, Cd, Ni, Zn, Cu, Hg, It may be substituted with at least one selected from the group consisting of Fe, Co, Sn, Pb, Mn, Al, Cr, Y, Zr, Ti, lanthanoids, and tetraethylammonium ions.
  • the GIS-type zeolite may be Na x- ⁇ [Al x Si 16-x O 32 ] ⁇ yH 2 O.
  • x satisfies 4.5 ⁇ x ⁇ 7.5
  • ⁇ is a value determined so as to satisfy the charge neutrality condition
  • y is an arbitrary value.
  • the GIS-type zeolite may be Na x- ⁇ [Al x Si 16-x O 32 ] ⁇ yH 2 O.
  • x satisfies 5.0 ⁇ x ⁇ 7.0
  • ⁇ is a value determined so as to satisfy the charge neutrality condition
  • y is an arbitrary value.
  • the x may be 5.3 ⁇ x ⁇ 6.9.
  • a part of Na contained in the GIS type zeolite is H, Li, K, Ag, NH 4 , Mg, Ca, Sr, Ba, Cd, Ni, Zn, Cu, Hg, It may be substituted with at least one selected from the group consisting of Fe, Co, Sn, Pb, Mn, Al, Cr, Y, Zr, Ti, and lanthanoids.
  • the composite material according to one aspect of the present invention includes the above-mentioned negative thermal expansion material and a material having a positive coefficient of thermal expansion.
  • the material having a positive coefficient of thermal expansion may be a resin material.
  • the material having a positive coefficient of thermal expansion may be a metal material.
  • FIG. 1 It is a flowchart which shows an example of the manufacturing method of the negative thermal expansion material (MER type) which concerns on this invention. It is a figure which shows the HT-XRD measurement result (heat temperature rise) of the MER type zeolite. It is a figure which shows the HT-XRD measurement result (lowering temperature) of the MER type zeolite. It is a graph which shows the temperature characteristic of the sample which concerns on Example 1. FIG. It is a graph which shows the temperature characteristic of the sample which concerns on Example 2. FIG. It is a graph which shows the temperature characteristic of the sample which concerns on Example 3. FIG. It is a graph which shows the temperature characteristic of the sample which concerns on Example 4. FIG.
  • FIG. 1 It is a flowchart which shows the other example of the manufacturing method of the negative thermal expansion material (MER type) which concerns on this invention. It is a graph which shows the temperature characteristic of the sample which concerns on Example 5.
  • FIG. It is a graph which shows the temperature characteristic of the sample which concerns on Example 6.
  • FIG. It is a flowchart which shows the other example of the manufacturing method of the negative thermal expansion material (MER type) which concerns on this invention.
  • FIG. 1 shows the manufacturing method of the negative thermal expansion material
  • FIG. 9 It is a figure which shows the HT-XRD measurement result of the sample which concerns on Example 9.
  • FIG. It is a graph which shows the temperature characteristic of the sample which concerns on Example 9.
  • FIG. It is a flowchart which shows the other example of the manufacturing method of the negative thermal expansion material (MER type) which concerns on this invention.
  • MER type negative thermal expansion material
  • the negative thermal expansion material according to this embodiment is selected from the group consisting of MER (Merlinoite) type zeolite, GIS type zeolite, LTA type (A type) zeolite, and FAU type (X type, Y type) zeolite. It is characterized by containing at least one type of zeolite.
  • the MER-type zeolite according to the present embodiment is a MER-type zeolite represented by M (x- ⁇ ) [Al x Si 32-x O 64 ] ⁇ yH 2 O.
  • M is H, Li, Na, K, Ag, NH 4 , Mg, Ca, Sr, Ba, Cd, Ni, Zn, Cu, Hg, Fe, Co, Sn, Pb, Mn, Al, Cr, It is at least one selected from the group consisting of Y, Zr, Ti, lanthanoid, and tetraethylammonium ion, x is determined to satisfy 6.0 ⁇ x ⁇ 14.0, and ⁇ is determined to satisfy the charge neutrality condition. It is a value, and y is an arbitrary value.
  • the MER-type zeolite according to the present embodiment is a MER-type zeolite represented by K x- ⁇ [Al x Si 32-x O 64 ] ⁇ yH 2 O.
  • x is a value that satisfies 6.0 ⁇ x ⁇ 14.0
  • ⁇ is a value that is determined so as to satisfy the charge neutrality condition
  • y is an arbitrary value.
  • x is preferably 6.7 ⁇ x ⁇ 13.5, and more preferably 9.5 ⁇ x ⁇ 11.7 in the above chemical formula.
  • the volume expansion coefficient of the negative thermal expansion material can be adjusted by changing the value of x.
  • the volume expansion coefficient of the negative thermal expansion material according to the present embodiment changes according to the Si / Al ratio.
  • the larger Si / Al that is, the smaller x
  • the MER-type zeolite according to this embodiment may contain a trace amount of unavoidable impurities (for example, Na) in addition to K, Al, and Si.
  • a part of K contained in the MER-type zeolite is contained in H, Li, Na, Ag, NH 4 , Mg, Ca, Sr, Ba, Cd, Ni, Zn, Cu, Hg, Fe. , Co, Sn, Pb, Mn, Al, Cr, Y, Zr, Ti, lanthanoids, and tetraethylammonium ions may be substituted with at least one selected from the group.
  • the volume expansion coefficient of the negative thermal expansion material can be adjusted.
  • the volume expansion coefficient at least at 60 ° C. or higher and 140 ° C. or lower is -236 ppmK -1 or higher and -39 ppmK -1 or lower.
  • the negative thermal expansion material according to the present embodiment may exhibit volume shrinkage associated with a phase transition in a temperature range of 100 ° C. or higher and 200 ° C. or lower. By showing the volumetric contraction associated with the phase transition in this way, a huge negative volume expansion coefficient can be realized.
  • the GIS-type zeolite according to the present embodiment is a GIS-type zeolite represented by Na x- ⁇ [Al x Si 16-x O 32 ] ⁇ yH 2 O.
  • x satisfies 4.5 ⁇ x ⁇ 7.5
  • ⁇ is a value determined so as to satisfy the charge neutrality condition
  • y is an arbitrary value.
  • the GIS-type zeolite according to the present embodiment may be a GIS-type zeolite represented by Na x- ⁇ [Al x Si 16-x O 32 ] ⁇ yH 2 O.
  • x satisfies 5.0 ⁇ x ⁇ 7.0
  • ⁇ is a value determined so as to satisfy the charge neutrality condition
  • y is an arbitrary value.
  • x may be 5.3 ⁇ x ⁇ 6.9.
  • a part of Na contained in the above-mentioned GIS type zeolite is H, Li, K, Ag, NH 4 , Mg, Ca, Sr, Ba, Cd, Ni, Zn, Cu, Hg, Fe, Co, Sn. , Pb, Mn, Al, Cr, Y, Zr, Ti, and at least one selected from the group consisting of lanthanoids.
  • the negative thermal expansion material according to the present embodiment is composed of at least one selected from the group consisting of MER type zeolite, GIS type zeolite, LTA type zeolite, and FAU type zeolite. Since these materials are inexpensive and contain relatively light atoms as the main component, it is possible to reduce the cost and density of the negative thermal expansion material.
  • the negative thermal expansion material according to the present embodiment is mixed with a material having a positive coefficient of thermal expansion (positive thermal expansion material), in other words, by dispersing the negative thermal expansion material in the positive thermal expansion material.
  • a material having a positive coefficient of thermal expansion positive thermal expansion material
  • the positive thermal expansion material a resin material or a metal material can be used, but the material is not limited thereto.
  • the coefficient of thermal expansion of the negative thermal expansion material according to the present embodiment changes according to the value of x. That is, the smaller the value of x, the smaller the volume expansion rate (in other words, the larger the absolute value of the negative volume expansion rate).
  • a part of K contained in the MER type zeolite is H, Li, Na, Ag, NH 4 , Mg, Ca, Sr, Ba, Cd, Ni, Zn, and
  • the volume expansion coefficient of the negative thermal expansion material can be adjusted by substituting with Cu, Hg, Fe, Co, Sn, Pb, Mn, Al, Cr, Y, Zr, Ti, lanthanoid, tetraethylammonium ion and the like. can.
  • K by substituting K with Mg, Ca, Na, the volume expansion rate of the negative thermal expansion material, the temperature range indicating the negative volume expansion rate, and the like can be adjusted.
  • the value of x of the negative thermal expansion material and the value of x of the negative thermal expansion material are determined according to the characteristics of the positive thermal expansion material used when forming the composite material, the characteristics of the target composite material, the temperature range in which the composite material is used, and the like.
  • the element that replaces K may be determined.
  • the negative thermal expansion material according to the present embodiment there is a material showing a huge negative volume expansion coefficient in a relatively low temperature region (30 ° C to 80 ° C) (for example, Examples 2, 3 and 4). .. Since such materials have unique properties, they can be suitably used for specific applications.
  • FIG. 1 is a flowchart showing an example of a method for producing a negative thermal expansion material (MER type zeolite) according to the present invention.
  • MER type zeolite a negative thermal expansion material
  • colloidal silica and H2O are put into the beaker A, and these are stirred and mixed (step S1).
  • KOH, Al (OH) 3 and H 2 O are put into a separately prepared beaker B, and these are heated and stirred until they become transparent (step S2).
  • step S3 the solution of beaker A and the solution of beaker B are mixed and stirred.
  • the stirred aqueous solution (mixture) is poured into a container and subjected to hydrothermal treatment (step S4).
  • the stirred aqueous solution (mixture) is poured into a container and set in a pressure-resistant stainless steel outer cylinder. Then, this container is placed in a hot air circulation oven and heated to perform hydroheat treatment (step S4).
  • the temperature of the hydrothermal treatment can be 150 ° C.
  • the time of the hydrothermal treatment can be 3 days.
  • the conditions for these hydrothermal treatments are examples, and the conditions for hydrothermal treatment may be other than these in the present embodiment.
  • the precipitate in the removed container is washed with pure water (step S5). Then, the washed precipitate is dried (step S6) to obtain a MER-type zeolite.
  • the drying conditions can be, for example, about 110 ° C. for 16 hours. It should be noted that this drying condition is an example, and the drying condition may be other than this in the present embodiment.
  • the composition of MER-type zeolite can be changed by adjusting the composition ratio (charged molar ratio) of each raw material. That is, the composition of the obtained MER-type zeolite can be changed by adjusting the value of SiO 2 : Al (OH) 3 : KOH: H2O .
  • FIG. 8 is a flowchart showing another example of the method for producing a negative thermal expansion material (MER type zeolite) according to the present invention.
  • MER type zeolite negative thermal expansion material
  • the stirred aqueous solution (mixture) is poured into a Teflon (registered trademark) container and set in a pressure-resistant stainless steel outer cylinder. Then, this container is placed in a hot air circulation oven and heated to perform hydroheat treatment (step S13).
  • the precipitate in the removed Teflon container is washed with pure water (step S14). Then, the washed precipitate is dried to obtain a MER-type zeolite (step S15).
  • the production method shown in FIG. 8 differs from the production method shown in FIG. 1 in that phosphorus (H 3 PO 4 ) is added.
  • phosphorus is added to the starting material, but phosphorus is not contained in the finally obtained zeolite.
  • FIG. 12 is a flowchart showing another example of the method for producing a negative thermal expansion material (MER type zeolite) according to the present invention.
  • a negative thermal expansion material MER type zeolite
  • silica, a tetraethylammonium hydroxide (TEAOH) solution, and H2O are added to the beaker A, and these are stirred and mixed (step S21).
  • KOH, Al (OH) 3 and H 2 O are put into the beaker B, and these are heated and stirred (step S22).
  • the solution of beaker A and the solution of beaker B are mixed and stirred (step S23).
  • the stirred aqueous solution (mixture) is put into a Teflon (registered trademark) container and set in a pressure-resistant stainless steel outer cylinder. Then, this container is placed in a hot air circulation oven and heated to perform hydroheat treatment (step S24). After the hydrothermal treatment, the precipitate in the removed Teflon container is washed with pure water (step S25). Then, the washed precipitate is dried to obtain a MER-type zeolite (step S26).
  • the manufacturing method shown in FIG. 12 differs from the manufacturing method shown in FIG. 1 in that TEAOH is used.
  • a part of K contained in the MER-type zeolite is added to H, Li, Na, Ag, NH 4 , Mg, Ca, Sr, Ba, Cd, Ni, Zn, Cu, Hg, Fe, Co, Sn,
  • a method of substituting (ion exchange) with at least one selected from the group consisting of Pb, Mn, Al, Cr, Y, Zr, Ti, lanthanoid, and tetraethylammonium ion will be described.
  • the volume expansion coefficient of the negative thermal expansion material can be adjusted by substituting a part of K contained in the MER-type zeolite with these elements.
  • FIG. 20 is a flowchart for explaining an example of an ion exchange method for MER-type zeolite.
  • MNO 3 aq. a 0.1 M aqueous nitric acid solution
  • M is Mg, Ca, or Na.
  • Mg (NO 3 ) 2.6H 2 O can be used as the replacement raw material A.
  • Ca (NO 3 ) 2.4H 2 O can be used as the replacement raw material A.
  • NaNO 3 can be used as the replacement raw material A.
  • the nitric acid aqueous solution of this element can be used as the replacement raw material A.
  • the MER-type zeolite is put into a beaker and stirred at, for example, 80 ° C. for 24 hours (step S42).
  • the stirring conditions may be other than these conditions.
  • the stirred sample is suction-filtered with pure water to wash it with pure water (step S43).
  • the washed sample is put into a 0.1 M aqueous nitric acid solution (MNO 3 aq.) Again and stirred at 80 ° C. for 24 hours (step S42) and suction filtration / pure water washing (step S43). Is repeated 7 times in total. Then, by drying at 110 ° C.
  • a MER-type zeolite (M-MER-type zeolite) substituted with M ions can be obtained. It should be noted that this drying condition is an example, and the drying condition may be other than these in the present embodiment.
  • the substitution amount is the concentration of the nitrate aqueous solution prepared in step S41 and the stirring in step S42. It can be adjusted by using the time and temperature, the number of repetitions of steps S42 and S43, and the like. For example, the higher the concentration of the aqueous nitric acid solution prepared in step S41, the longer the stirring time in step S42, the higher the stirring temperature in step S42, and the larger the number of repetitions of steps S42 and S43, the more K The amount of the substituent M that replaces the above can be increased.
  • FIG. 24 is a flowchart showing an example of a method for producing an LTA-type zeolite and a FAU-type zeolite.
  • LTA-type zeolite and the FAU-type zeolite first, NaOH, NaAlO 2 , and H2O are put into a beaker and stirred until they are dissolved (step S51). Then, colloidal silica is put into a beaker and these are stirred for 24 hours (step S52).
  • the stirred aqueous solution (mixture) is transferred to an autoclave and heated in an oven at a temperature of 65 ° C. for 7 days (step S53). Then, it is water-cooled at a temperature of 25 ° C. for 1 hour (step S54), and further cooled in a refrigerator (temperature 8 ° C.) for 30 minutes (step S55). Then, the cooled sample is centrifuged at 13000 rpm for 45 minutes (step S56). Then, the residue formed by centrifugation is mixed with pure water for washing (step S57). These operations (operations of steps S56 and S57) are repeated, for example, three times.
  • step S58 by drying overnight at room temperature (step S58), the LTA-type zeolite and the FAU-type zeolite according to the present embodiment can be obtained.
  • the above conditions temperature, time, and centrifugation conditions are examples, and these conditions can be arbitrarily determined in the present embodiment.
  • the composition of LTA-type zeolite and FAU-type zeolite can be changed by adjusting the composition ratio (charged molar ratio) of each raw material. That is, the composition of the obtained LTA-type zeolite and FAU-type zeolite can be changed by adjusting the values of SiO 2 : Al 2 O 3 : NaOH: H 2 O.
  • FIG. 27 is a flowchart showing an example of a method for producing a GIS-type zeolite.
  • NaAlO 2 , NaOH, and H2O are put into a beaker, and these are stirred and mixed (step S61).
  • colloidal silica is mixed with the beaker and stirred (step S62).
  • the stirred aqueous solution (mixture) is poured into a Teflon (registered trademark) container and set in a pressure-resistant stainless steel outer cylinder. Then, this container is placed in a hot air circulation oven and heated to perform hydroheat treatment (step S63).
  • the precipitate in the removed Teflon container is washed with pure water (step S64). Then, the washed precipitate is dried to obtain a GIS-type zeolite (step S65).
  • the composition of the GIS-type zeolite can be changed by adjusting the composition ratio (charged molar ratio) of each raw material.
  • FIG. 31 is a flowchart for explaining an example of an ion exchange method for a GIS-type zeolite.
  • a 1M aqueous hydrochloric acid solution (MCl aq.) Is prepared in a beaker using the replacement raw material B (step S71).
  • M is Mg, Ca, K, or Li.
  • MgCl 2.6H 2 O can be used as the replacement raw material B.
  • CaCl 2.2H 2 O can be used as the replacement raw material B.
  • KCl can be used as the replacement raw material B.
  • LiCl When a part of Na is replaced with Li, LiCl can be used as the replacement raw material B. Even when a part of Na is replaced with an element other than these, the hydrochloric acid aqueous solution of this element can be used as the replacement raw material B.
  • the GIS-type zeolite is put into a beaker and stirred at, for example, 80 ° C. for 24 hours (step S72).
  • the stirring conditions may be other than these conditions.
  • the stirred sample is filtered and washed with pure water (step S73).
  • step S74 by drying at 110 ° C. for 16 hours (step S74), a GIS-type zeolite (M-GIS-type zeolite) substituted with M ions can be obtained.
  • this drying condition is an example, and the drying condition may be other than these in the present embodiment.
  • FIG. 1 is a flowchart showing a method for producing a MER-type zeolite.
  • colloidal silica concentration 30 wt%: manufactured by Nissan Chemical Industries, Ltd., Snowtex Na type ST-30
  • H2O colloidal silica
  • KOH, Al (OH) 3 and H 2 O were put into the beaker B, and these were heated and stirred until they became transparent (step S2).
  • the solution of beaker A and the solution of beaker B were mixed and stirred (step S3).
  • the stirred aqueous solution (mixture) is poured into a Teflon (registered trademark) container (HUT-100, San-ai Kagaku Co., Ltd.) and placed in a pressure-resistant stainless steel outer cylinder (HUS-100, San-ai Kagaku Co., Ltd.). I set it. Then, this container was placed in a hot air circulation oven (KLO-45M, Koyo Thermo System Co., Ltd.) and heated to perform hydrothermal treatment (step S4). The temperature of the hydrothermal treatment was 150 ° C., and the time of the hydrothermal treatment was 3 days.
  • step S6 After the hydrothermal treatment, a precipitate was formed in the Teflon container taken out. The precipitate was washed with pure water (step S5). Then, the washed precipitate was dried at a temperature of about 110 ° C. for 16 hours to obtain a white solid (step S6).
  • composition (atomic ratio) of the prepared sample according to Example 1 was analyzed using ICP-OES (Inductivity Coupled Plasma Optical Emission Spectrometry).
  • ICP-OES Inductivity Coupled Plasma Optical Emission Spectrometry
  • ICP-OES Inductivity Coupled Plasma Optical Emission Spectrometry
  • the composition of the sample according to Example 1 was as follows. K 9.2 [Al 9.5 Si 22.5 O 64 ] ⁇ yH 2 O ⁇ ⁇ ⁇ Example 1
  • the coefficient of thermal expansion of the sample according to Example 1 was measured using the following method.
  • a benchtop heating stage (BTS 500, AntonioPaar) was attached to the following powder X-ray diffractometer, and the X-ray diffraction pattern was measured at an arbitrary temperature.
  • a high-speed one-dimensional detector (D / teX Ultra2, Rigaku Co., Ltd.) was used as the detector, and the measurement was performed under the following conditions.
  • Si NIST SRM 640c was used as the internal standard.
  • the obtained X-ray diffraction pattern (HT-XRD measurement result: temperature rise) is shown in FIG.
  • HT-XRD measurement result: temperature drop The obtained X-ray diffraction pattern (HT-XRD measurement result: temperature drop) is shown in FIG.
  • the crystal structure was refined by the Rietveld method, and the lattice constant was calculated.
  • the calculated lattice constant was plotted against the temperature, and the linear thermal expansion coefficient ⁇ l and the volume coefficient of thermal expansion ⁇ v for each crystal axis were calculated using the following equations in a temperature range approximately linearly approximated.
  • FIG. 4 shows the volume coefficient of thermal expansion and the coefficient of linear thermal expansion for each crystal axis.
  • the volume coefficient of thermal expansion of the sample according to Example 1 was -236 (ppmK -1 ) in the temperature range of 30 to 160 ° C.
  • FIG. 5 shows the volume coefficient of thermal expansion and the coefficient of linear thermal expansion for each crystal axis.
  • the volumetric coefficient of thermal expansion of the sample according to Example 2 was -184 (ppmK -1 ) in the temperature range of 60 to 180 ° C. and -908 (ppmK -1 ) in the temperature range of 40 to 60 ° C.
  • Example 3 when the composition (atomic ratio) of the prepared sample according to Example 3 was analyzed using ICP-OES in the same manner as in Example 1, the composition of the sample according to Example 3 was as follows. K 11.6 [Al 11.6 Si 20.4 O 64 ] ⁇ yH 2 O ... Example 3
  • FIG. 6 shows the volume coefficient of thermal expansion and the coefficient of linear thermal expansion for each crystal axis.
  • the volumetric coefficient of thermal expansion of the sample according to Example 3 was ⁇ 98.6 (ppmK -1 ) in the temperature range of 60 to 160 ° C. and ⁇ 942 (ppmK -1 ) in the temperature range of 40 to 60 ° C.
  • Example 4 when the composition (atomic ratio) of the prepared sample according to Example 4 was analyzed using ICP-OES in the same manner as in Example 1, the composition of the sample according to Example 4 was as follows. K 11.7 [Al 11.7 Si 20.3 O 64 ] ⁇ yH 2 O ... Example 4
  • FIG. 7 shows the volume coefficient of thermal expansion and the coefficient of linear thermal expansion for each crystal axis.
  • the volumetric coefficient of thermal expansion of the sample according to Example 4 was ⁇ 106 (ppmK -1) in the temperature range of 60 to 140 ° C. and ⁇ 925 (ppmK -1 ) in the temperature range of 40 to 60 ° C.
  • FIG. 8 is a flowchart showing a method for producing a MER-type zeolite.
  • KOH, Al (OH) 3 , H 3 PO 4 , and H 2 O were put into a beaker, and these were heated and stirred until they became transparent (step S11).
  • colloidal silica concentration 30 wt%: manufactured by Nissan Chemical Industries, Ltd., Snowtex Na type ST-30 was mixed with the beaker and stirred (step S12).
  • the stirred aqueous solution (mixture) is poured into a Teflon (registered trademark) container (HUT-100, San-ai Kagaku Co., Ltd.) and placed in a pressure-resistant stainless steel outer cylinder (HUS-100, San-ai Kagaku Co., Ltd.). I set it. Then, this container was placed in a hot air circulation oven (KLO-45M, Koyo Thermo System Co., Ltd.) and heated to perform hydrothermal treatment (step S13). The temperature of the hydrothermal treatment was 150 ° C., and the time of the hydrothermal treatment was 3 days.
  • step S15 After the hydrothermal treatment, a precipitate was formed in the Teflon container taken out. The precipitate was washed with pure water (step S14). Then, the washed precipitate was dried at a temperature of about 110 ° C. for 16 hours to obtain a white solid (step S15).
  • the production method according to Example 5 is different from the production method according to Example 1 in that phosphorus (H 3 PO 4 ) is added.
  • phosphorus was added to the starting material, but phosphorus was not contained in the finally obtained zeolite.
  • HT-XRD was measured to determine the lattice constant from room temperature to 250 ° C. (FIG. 9).
  • the coefficient of thermal expansion is calculated from this result, it is -39 (ppmK -1 ) in the temperature range of 30 to 50 ° C, -76 (ppmK -1 ) in the temperature range of 70 to 130 ° C, and the temperature range of 150 to 230 ° C. It was -187 (ppmK -1 ).
  • HT-XRD was measured to determine the lattice constant from room temperature to 230 ° C. (FIG. 6).
  • the coefficient of thermal expansion is -105 (ppmK -1 ) in the temperature range of 70 to 150 ° C, and -45 (ppmK -1 ) in the temperature range of 170 to 230 ° C. there were.
  • HT-XRD was measured to determine the lattice constant from room temperature to 250 ° C. (FIG. 11).
  • the coefficient of thermal expansion is calculated from this result, it is -186 (ppmK -1) in the temperature range of 30 to 70 ° C, -42.2 (ppmK -1 ) in the temperature range of 90 to 150 ° C, and 170 to 250 ° C. It was -50 (ppmK -1 ) in the temperature range.
  • FIG. 12 is a flowchart showing a method for producing a MER-type zeolite.
  • silica manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • TEAOH tetraethylammonium hydroxide
  • H2O tetraethylammonium hydroxide
  • KOH, Al (OH) 3 and H 2 O were put into the beaker B, and these were heated and stirred (step S22).
  • step S23 the solution of beaker A and the solution of beaker B were mixed and stirred
  • the stirred aqueous solution (mixture) was put into a Teflon (registered trademark) container (HUT-100, San-ai Kagaku Co., Ltd.), and a pressure-resistant stainless steel outer cylinder (HUS-100, San-ai Kagaku Co., Ltd.). I set it to. Then, this container was placed in a hot air circulation oven (KLO-45M, Koyo Thermo System Co., Ltd.) and heated to perform hydrothermal treatment (step S24). The temperature of the hydrothermal treatment was 150 ° C., and the time of the hydrothermal treatment was 3 days. After the hydrothermal treatment, a precipitate was formed in the Teflon container taken out. The precipitate was washed with pure water (step S25). Then, the washed precipitate was dried at a temperature of about 110 ° C. for 16 hours to obtain a white solid (step S26).
  • a Teflon (registered trademark) container HUT-100, San-
  • a single-phase MER-type zeolite could be produced.
  • the manufacturing method according to Example 8 is different from the manufacturing method according to Example 1 in that TEAOH is used.
  • FIG. 13 shows the HT-XRD measurement results of the sample according to Example 8. As shown in FIG. 13, it was found that the sample according to Example 8 did not decompose up to 500 ° C. In addition, the lattice constant was determined from room temperature to 500 ° C. (FIG. 14). From this result, the coefficient of thermal expansion was calculated to be 430 (ppmK -1) in the temperature range of 30 to 230 ° C. and -193 (ppmK -1 ) in the temperature range of 70 to 150 ° C.
  • the HT-XRD measurement result of the sample with y 1.0 (K 6.7 [Al 6.7 Si 25.2 O 64 ], yH 2 O) is shown in FIG.
  • the lattice constant was determined from room temperature of the sample to 270 ° C (FIG. 17). From this result, the coefficient of thermal expansion was calculated to be -121.5 (ppmK -1 ) in the temperature range of 30 to 230 ° C. and -111.4 (ppmK -1 ) in the temperature range of 30 to 270 ° C.
  • FIG. 18 is a flowchart showing a method for producing a MER-type zeolite.
  • silica manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • H2O were put into the beaker A, and these were stirred and mixed (step S31).
  • KOH, Al (OH) 3 and H 2 O were put into the beaker B, and these were heated and stirred (step S32).
  • the solution of beaker A and the solution of beaker B were mixed and stirred (step S33).
  • the stirred aqueous solution (mixture) was put into a Teflon (registered trademark) container (HUT-100, San-ai Kagaku Co., Ltd.), and a pressure-resistant stainless steel outer cylinder (HUS-100, San-ai Kagaku Co., Ltd.). I set it to. Then, this container was placed in a hot air circulation oven (KLO-45M, Koyo Thermo System Co., Ltd.) and heated to perform hydrothermal treatment (step S34). The temperature of the hydrothermal treatment was 150 ° C., and the time of the hydrothermal treatment was 3 days. After the hydrothermal treatment, a precipitate was formed in the Teflon container taken out.
  • a Teflon (registered trademark) container HUT-100, San-ai Kagaku Co., Ltd.
  • a pressure-resistant stainless steel outer cylinder HUS-100, San-ai Kagaku Co., Ltd.
  • step S35 The precipitate was washed with pure water (step S35). Then, the washed precipitate was dried at a temperature of about 110 ° C. for 16 hours to obtain a white solid (step S36).
  • Example 11 As Example 11, a sample in which a part of K of the MER-type zeolite was replaced with Ca (ion exchange) was prepared. In Example 11, a part of K of the sample according to Example 2 was replaced with Ca.
  • FIG. 20 is a flowchart for explaining an ion exchange method of the MER-type zeolite.
  • the replacement raw material A 5.0 ⁇ 10 -3 mol of Ca (NO 3 ) 2.4H 2 O and 50 ml of H 2 O were used, and a 0.1 M aqueous solution of calcium nitrate (Ca (NO 3 ) 2 aq) was used. ) was prepared in the beaker (step S41).
  • Example 2 as a MER-type zeolite was put into a 3 g beaker and stirred at 80 ° C. for 24 hours (step S42). Then, the sample after stirring was suction-filtered with pure water and washed with pure water (step S43). Then, the washed sample is put into a 0.1 M aqueous calcium nitrate solution (Ca (NO 3 ) 2 aq.) And stirred at 80 ° C. for 24 hours (step S42) and suction filtration / pure water washing treatment (step S42). Step S43) was repeated 7 times in total. Then, it was dried at 110 ° C. for 16 hours (step S44) to obtain a MER-type zeolite (Ca-MER type) substituted with Ca ions.
  • Ca-MER type a MER-type zeolite
  • FIG. 21 shows the volume coefficient of thermal expansion and the coefficient of linear thermal expansion for each crystal axis.
  • the volume coefficient of thermal expansion of the sample according to Example 11 was -246 (ppmK -1 ) in the temperature range of 30 to 160 ° C.
  • Example 12 a sample in which a part of K of the MER-type zeolite was replaced with Mg (ion exchange) was prepared. In Example 12, a part of K of the sample according to Example 2 was replaced with Mg.
  • Example 12 similarly to Example 11, ion exchange of the MER-type zeolite was performed by using the method shown in the flowchart of FIG. 20.
  • the replacement raw material A 5.0 ⁇ 10 -3 mol of Mg (NO 3 ) 2.6H 2 O and 50 ml of H 2 O were used, and a 0.1 M magnesium nitrate aqueous solution (Mg (NO 3 ) 2 aq) was used. ) was prepared in the beaker (step S41).
  • Example 2 as a MER-type zeolite was put into a 3 g beaker and stirred at 80 ° C. for 24 hours (step S42). Then, the sample after stirring was suction-filtered with pure water and washed with pure water (step S43). Then, the washed sample is put into a 0.1 M magnesium nitrate aqueous solution (Mg (NO 3 ) 2 aq.) And stirred at 80 ° C. for 24 hours (step S42) and suction filtration / pure water washing treatment (step S42). Step S43) was repeated 7 times in total. Then, it was dried at 110 ° C. for 16 hours (step S44) to obtain a MER type zeolite (Mg-MER type) substituted with Mg ions.
  • Mg-MER type magnesium nitrate aqueous solution
  • FIG. 22 shows the volume coefficient of thermal expansion and the coefficient of linear thermal expansion for each crystal axis.
  • the volumetric coefficient of thermal expansion of the sample according to Example 12 was -427 (ppmK -1 ) in the temperature range of 30 to 80 ° C. and -39.7 (ppmK -1 ) in the temperature range of 80 to 220 ° C.
  • Example 13 As Example 13, a sample in which a part of K of the MER-type zeolite was replaced with Na (ion exchange) was prepared. In Example 13, a part of K of the sample according to Example 2 was replaced with Na.
  • Example 13 similarly to Example 11, ion exchange of the MER-type zeolite was performed by using the method shown in the flowchart of FIG. 20.
  • a 0.1 M sodium nitrate aqueous solution NaNO 3 aq.
  • a beaker using 5.0 ⁇ 10 -3 mol of NaNO 3 and 50 ml of H2 O as the raw material A for substitution (step S41).
  • Example 2 as a MER-type zeolite was put into a 3 g beaker and stirred at 80 ° C. for 24 hours (step S42). Then, the sample after stirring was suction-filtered with pure water and washed with pure water (step S43). Then, the washed sample is put into a 0.1 M magnesium nitrate aqueous solution (NaNO 3 aq.) And stirred at 80 ° C. for 24 hours (step S42) and suction filtration / pure water washing treatment (step S43). Was repeated 7 times in total. Then, it was dried at 110 ° C. for 16 hours (step S44) to obtain a MER-type zeolite (Na-MER type) substituted with Na ions.
  • a MER-type zeolite Na-MER type
  • FIG. 23 shows the volume coefficient of thermal expansion and the coefficient of linear thermal expansion for each crystal axis.
  • the volumetric coefficient of thermal expansion of the sample according to Example 13 was -189 (ppmK -1 ) in the temperature range of 30 to 100 ° C. and -594 (ppmK -1 ) in the temperature range of 120 to 220 ° C.
  • FIG. 24 is a flowchart showing a method for producing an LTA-type zeolite.
  • NaOH, NaAlO 2 , and H2O were put into a beaker and stirred until they were dissolved (step S51).
  • colloidal silica concentration 30 wt%: manufactured by Nissan Chemical Industries, Ltd., Snowtex Na type ST-30
  • step S52 colloidal silica
  • step S53 the stirred aqueous solution (mixture) was transferred to an autoclave and heated in an oven at a temperature of 65 ° C. for 7 days (step S53). Then, it was water-cooled at a temperature of 25 ° C. for 1 hour (step S54), and further cooled in a refrigerator (temperature 8 ° C.) for 30 minutes (step S55). Then, the cooled sample was centrifuged at 13000 rpm for 45 minutes (step S56). Then, the residue formed by centrifugation was mixed with pure water for washing (step S57). These operations (operations of steps S56 and S57) were repeated three times. Then, it was dried overnight at room temperature (step S58) to obtain the LTA-type zeolite according to Example 14.
  • Example 14 when the composition (atomic ratio) of the prepared sample according to Example 14 was analyzed using ICP-OES in the same manner as in Example 1, the composition of the sample according to Example 14 was as follows. Na 12.1 [Al 13.2 Si 10.8 O 48 ] ⁇ yH 2 O ... Example 14
  • FIG. 25 shows the volume coefficient of thermal expansion and the coefficient of linear thermal expansion for each crystal axis.
  • the volumetric coefficient of thermal expansion of the sample according to Example 14 was ⁇ 160 (ppmK -1 ) in the temperature range of 30 to 80 ° C. and -20.6 (ppmK -1 ) in the temperature range of 250 to 500 ° C.
  • composition (atomic ratio) of the prepared sample according to Example 15 was analyzed using ICP-OES in the same manner as in Example 1, the composition of the sample according to Example 15 was as follows. Na 82.1 [Al 87.5 Si 104.5 O 384 ] ⁇ yH 2 O ...
  • FIG. 26 shows the volume coefficient of thermal expansion and the coefficient of linear thermal expansion for each crystal axis.
  • the volumetric coefficient of thermal expansion of the sample according to Example 15 was -69.2 (ppmK -1 ) in the temperature range of 30 to 80 ° C. and -13.6 (ppmK -1 ) in the temperature range of 350 to 500 ° C. rice field.
  • FIG. 27 is a flowchart showing a method for producing a GIS-type zeolite.
  • NaAlO 2 , NaOH and H2O were put into a beaker, and these were stirred and mixed (step S61).
  • colloidal silica concentration 30 wt%: manufactured by Nissan Chemical Industries, Ltd., Snowtex Na type ST-30 was mixed with the beaker and stirred (step S62).
  • the stirred aqueous solution (mixture) is poured into a Teflon (registered trademark) container (HUT-100, San-ai Kagaku Co., Ltd.) and placed in a pressure-resistant stainless steel outer cylinder (HUS-100, San-ai Kagaku Co., Ltd.). I set it. Then, this container was placed in a hot air circulation oven (KLO-45M, Koyo Thermo System Co., Ltd.) and heated to perform hydrothermal treatment (step S63). The temperature of the hydrothermal treatment was 100 ° C., and the time of the hydrothermal treatment was 7 days.
  • HT-XRD was measured to determine the lattice constant from room temperature to 500 ° C. (FIG. 28).
  • the coefficient of thermal expansion is calculated from this result, it is -61 (ppmK -1 ) in the temperature range of 30 to 70 ° C, -101 (ppmK -1 ) in the temperature range of 90 to 140 ° C, and the temperature range of 150 to 350 ° C. It was -126 (ppmK -1 ). In the temperature range of 30 to 350 ° C., it was -552 (ppmK -1 ).
  • Example 17 A GIS-type zeolite was prepared as Example 17.
  • the sample according to Example 17 was also prepared by the same method as in Example 16.
  • HT-XRD was measured to determine the lattice constant from room temperature to 500 ° C. (FIG. 29).
  • the coefficient of thermal expansion is calculated from this result, it is -40 (ppmK -1 ) in the temperature range of 30 to 50 ° C, -98 (ppmK -1 ) in the temperature range of 70 to 90 ° C, and 110 to 140 ° C.
  • It was -53 (ppmK -1 ) and -106 (ppmK -1 ) in the temperature range of 150 to 350 ° C. In the temperature range of 30 to 350 ° C., it was ⁇ 529 (ppmK -1 ).
  • Example 18 A GIS-type zeolite was prepared as Example 18.
  • the sample according to Example 18 was also prepared by the same method as in Example 16.
  • HT-XRD was measured to determine the lattice constant from room temperature to 500 ° C. (FIG. 30).
  • the coefficient of thermal expansion is calculated from this result, it is -74 (ppmK -1 ) in the temperature range of 50 to 70 ° C, -96 (ppmK -1 ) in the temperature range of 90 to 140 ° C, and the temperature range of 150 to 350 ° C. It was -113 (ppmK -1 ). In the temperature range of 30 to 350 ° C., it was -458 (ppmK -1 ).
  • Example 19 As Example 19, a sample was prepared by substituting (ion exchange) a part of Na of the GIS-type zeolite with Mg, Ca, K, or Li. In Example 19, a part of Na in the sample according to Example 16 was replaced with Mg, Ca, K, or Li.
  • FIG. 31 is a flowchart for explaining an ion exchange method of the GIS-type zeolite.
  • 1 M magnesium hydrochloride aqueous solution (MgCl) using 1.5 ⁇ 10 ⁇ 2 mol, H 2 O 15 ml of MgCl 2.6H 2 O, CaCl 2.4H 2 O , KCl , or LiCl. 2 aq.), An aqueous solution of calcium chloride (CaCl 2 aq.), An aqueous solution of potassium chloride (KCl aq.), And an aqueous solution of lithium hydrochloride (LiCl aq.) Were prepared in a beaker (step S71).
  • MgCl magnesium hydrochloride aqueous solution
  • Example 16 as a GIS-type zeolite was put into a 0.5 g beaker and stirred at 80 ° C. for 24 hours (step S72). Then, the stirred sample was filtered and washed with pure water (step S73). Then, the GIS-type zeolite (Mg-GIS type, Ca-GIS type, K-GIS type, or Li-) substituted with Mg, Ca, K, or Li ion by drying at 110 ° C. for 16 hours (step S74). GIS type) was obtained.
  • Example 20 As Example 20, a sample was prepared by substituting (ion exchange) a part of Na of the GIS-type zeolite with Mg, Ca, K, or Li. The sample according to Example 20 was also prepared by the same method as in Example 19. In Example 20, a part of Na in the sample according to Example 17 was replaced with Mg, Ca, K, or Li.
  • composition of the sample according to Example 20 was as follows.
  • Mg-GIS type Na 3.8 Mg 0.7 [Al 5.4 Si 10.6 O 32 ] ⁇ yH 2 O
  • Ca-GIS type Na 0.8 Ca 2.2 [Al 5.4 Si 10.6 O 32 ] ⁇ yH 2 O
  • K-GIS type K 4.5 [Al 5.3 Si 10.7 O 32 ] ⁇ yH 2 O
  • Li-GIS type Na 3.4 Li 1.8 [Al 5.3 Si 10.7 O 32 ] ⁇ yH 2 O
  • ⁇ Summary> 32 to 34 are tables summarizing the charged molar ratio, composition, volume expansion coefficient and the temperature range of the samples according to Examples 1 to 18.
  • the samples according to Examples 1 to 18 show various volume expansion rates depending on the composition. Further, in the samples according to Examples 2, 3, 4, 12, and 13, the values of the coefficient of thermal expansion differ between the high temperature side and the low temperature side. Further, in the samples according to Examples 1 to 4 and 11 to 15, the volume expansion coefficient changes according to the Si / Al ratio. For example, in the temperature region on the high temperature side (60 to 160 ° C.), the absolute value of the negative volume expansion rate tends to increase as Si / Al increases (that is, as x decreases) (Examples 1 to 4). reference). In particular, in Example 1 in which the Si / Al value was the largest, the coefficient of thermal expansion was the lowest in the temperature region (60 to 160 ° C.) on the high temperature side (the absolute value of the negative coefficient of thermal expansion was the largest). ..
  • Example 11 in which a part of K was replaced with Ca, the volume coefficient of thermal expansion was -246 (ppmK -1 ) in the temperature range of 30 to 160 ° C.
  • the characteristics of Example 11 were similar to those of Example 1.
  • Example 13 in which a part of K was replaced with Na the coefficient of thermal expansion was ⁇ 594 (ppmK -1 ) in the temperature range of 120 to 220 ° C., and the coefficient of thermal expansion was the lowest in this temperature range (negative). The absolute value of the volume expansion rate of was the largest).
  • Example 14 LTA-type zeolite
  • Example 15 FAU-type zeolite
  • Examples 16 to 18 GIS-type zeolite
  • negative volume expansion even in a relatively high temperature region for example, 300 ° C. or higher. Shown the rate.
  • the sample according to Example 14 showed a stable negative volume expansion rate at 300 ° C. or higher.
  • the negative thermal expansion materials according to Examples 1 to 18 showed various volume expansion rates depending on the composition, the element to be substituted, and the like. Therefore, by adjusting the composition, the element to be substituted, and the like, a material having a negative volume expansion coefficient according to the intended use can be produced.

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Abstract

La présente invention concerne : un matériau à dilatation thermique négative qui est réduit en termes de coût et de densité ; et un matériau composite. Un matériau à dilatation thermique négative selon un mode de réalisation de la présente invention présente un coefficient de dilatation thermique négatif, tout en contenant au moins une substance qui est choisie dans le groupe constitué par une zéolite de type MER, une zéolite de type GIS, une zéolite de type LTA et une zéolite de type FAU. Un matériau composite selon un mode de réalisation de la présente invention contient le matériau à dilatation thermique négative décrit ci-dessus et un matériau qui a un coefficient de dilatation thermique positif.
PCT/JP2021/041006 2020-11-09 2021-11-08 Matériau à dilatation thermique négative et matériau composite WO2022097746A1 (fr)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2007313389A (ja) * 2006-05-23 2007-12-06 Asahi Kasei Corp マーリノアイト型ゼオライト複合膜及びその製造方法
JP2019073704A (ja) * 2017-10-16 2019-05-16 三菱ケミカル株式会社 樹脂複合材及び電子デバイス
WO2019194321A1 (fr) * 2018-04-06 2019-10-10 株式会社アドマテックス Charge pour composition de résine, composition de suspension épaisse contenant une charge, composition de résine contenant une charge, et procédé de production de charge pour composition de résine
WO2019202933A1 (fr) * 2018-04-16 2019-10-24 旭化成株式会社 Zéolite de type gis

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JP2007313389A (ja) * 2006-05-23 2007-12-06 Asahi Kasei Corp マーリノアイト型ゼオライト複合膜及びその製造方法
JP2019073704A (ja) * 2017-10-16 2019-05-16 三菱ケミカル株式会社 樹脂複合材及び電子デバイス
WO2019194321A1 (fr) * 2018-04-06 2019-10-10 株式会社アドマテックス Charge pour composition de résine, composition de suspension épaisse contenant une charge, composition de résine contenant une charge, et procédé de production de charge pour composition de résine
WO2019202933A1 (fr) * 2018-04-16 2019-10-24 旭化成株式会社 Zéolite de type gis

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OOKAWA, MASASHI ET AL.: "Molecular dynamics simulation studies on thermal expansion behavior of siliceous faujasite", JOURNAL OF COMPUTER CHEMISTRY JAPAN, vol. 14, no. 4, 2015, pages 105 - 110, XP055643935, DOI: 10.2477/jccj.2015-0020 *

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