WO2022097746A1 - Negative thermal expansion material and composite material - Google Patents

Abstract

The present invention provides: a negative thermal expansion material which is reduced in cost and density; and a composite material. A negative thermal expansion material according to one embodiment of the present invention has a negative thermal expansion coefficient, while containing at least one substance which is selected from the group consisting of MER type zeolite, GIS type zeolite, LTA type zeolite and FAU type zeolite. A composite material according to one embodiment of the present invention contains the above-described negative thermal expansion material and a material which has a positive thermal expansion coefficient.

Description

Negative thermal expansion materials and composite materials

The present invention relates to a negative thermal expansion material and a composite material.

In devices that combine multiple materials such as electronic devices, optical devices, fuel cells, and sensors, misalignment due to thermal expansion becomes a problem, and the difference in the coefficient of thermal expansion of each material causes serious obstacles such as interface peeling and disconnection. Connect. Therefore, various near-zero thermal expansion materials and thermal expansion control techniques are being researched. Invar alloys, glass, cordierite, etc. are widely known to have a single-phase, near-zero thermal expansion, and are applied to industrial products and consumer products. In recent years, it has been studied to reduce the thermal expansion of a substance whose thermal expansion rate is difficult to control by combining it with a filler material having a low coefficient of thermal expansion. In particular, since the thermal expansion can be effectively offset with a low compounding ratio, compounding with a material having a negative coefficient of thermal expansion (hereinafter, also referred to as a negative thermal expansion material) is drawing attention.

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.

Japanese Unexamined Patent Publication No. 2017-48071

Various materials have been reported so far as materials with a negative coefficient of thermal expansion, but since most of the materials are mainly composed of precious metals and heavy metals, cost reduction and density reduction have been realized. There is a problem that there is no such thing.

In view of the above problems, 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.

In the above-mentioned negative thermal expansion material, the MER-type zeolite may be M _(x-δ) [Al _x Si _32-x O ₆₄ ] · yH ₂ O. However, 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 δ is determined to satisfy the charge neutrality condition. It is a value, and y is an arbitrary value.

In the above-mentioned negative thermal expansion material, the MER-type zeolite may be K _x-δ [Al _x Si _32-x O ₆₄ ] · yH ₂ O. However, x is a value that satisfies 6.0 ≦ x ≦ 14.0, δ is a value that is determined so as to satisfy the charge neutrality condition, and y is an arbitrary value.

In the above-mentioned negative thermal expansion material, the x may be 6.7 ≦ x ≦ 13.5.

In the above-mentioned negative thermal expansion material, 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.

In the above-mentioned negative thermal expansion material, 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.

In the above-mentioned negative thermal expansion material, 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.

In the above-mentioned negative thermal expansion material, the GIS-type zeolite may be Na _x-δ [Al _x Si _16-x O ₃₂ ] · yH ₂ O. However, x satisfies 4.5 ≦ x ≦ 7.5, δ is a value determined so as to satisfy the charge neutrality condition, and y is an arbitrary value.

In the above-mentioned negative thermal expansion material, the GIS-type zeolite may be Na _x-δ [Al _x Si _16-x O ₃₂ ] · yH ₂ O. However, x satisfies 5.0 ≦ x ≦ 7.0, δ is a value determined so as to satisfy the charge neutrality condition, and y is an arbitrary value.

In the above-mentioned negative thermal expansion material, the x may be 5.3 ≦ x ≦ 6.9.

In the above-mentioned negative thermal expansion material, 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.

In the above-mentioned composite material, the material having a positive coefficient of thermal expansion may be a resin material.

In the above-mentioned composite material, the material having a positive coefficient of thermal expansion may be a metal material.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a negative thermal expansion material and a composite material that can realize low cost and low density.

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. 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. It is a graph which shows the temperature characteristic of the sample which concerns on Example 7. 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. It is a figure which shows the HT-XRD measurement result of the sample which concerns on Example 8. It is a graph which shows the temperature characteristic of the sample which concerns on Example 8. It is a figure which shows the XRD measurement result of the sample which concerns on Example 9. FIG. 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. It is a figure which shows the XRD measurement result of the sample which concerns on Example 10. It is a flowchart for demonstrating an example of the ion exchange method (method of manufacturing M-MER type zeolite) of MER type zeolite. It is a graph which shows the temperature characteristic of the sample which concerns on Example 11. It is a graph which shows the temperature characteristic of the sample which concerns on Example 12. It is a graph which shows the temperature characteristic of the sample which concerns on Example 13. It is a flowchart which shows an example of the manufacturing method of the negative thermal expansion material (LTA type, FAU type) which concerns on this invention. It is a graph which shows the temperature characteristic of the sample which concerns on Example 14. It is a graph which shows the temperature characteristic of the sample which concerns on Example 15. FIG. It is a flowchart which shows an example of the manufacturing method of the negative thermal expansion material (GIS type) which concerns on this invention. It is a graph which shows the temperature characteristic of the sample which concerns on Example 16. It is a graph which shows the temperature characteristic of the sample which concerns on Example 17. It is a graph which shows the temperature characteristic of the sample which concerns on Example 18. It is a flowchart for demonstrating an example of the ion exchange method (method of manufacturing M-GIS type zeolite) of GIS type zeolite. It is a table summarizing the charge ratio, composition, volume expansion coefficient, and temperature range of the sample which concerns on Example. It is a table summarizing the charge ratio, composition, volume expansion coefficient, and temperature range of the sample which concerns on Example. It is a table summarizing the charge ratio, composition, volume expansion coefficient, and temperature range of the sample which concerns on Example.

Hereinafter, embodiments of the present invention will be described.
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.

For example, the MER-type zeolite according to the present embodiment is a MER-type zeolite represented by M _(x-δ) [Al _x Si _32-x O ₆₄ ] · yH ₂ O. However, 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 δ is determined to satisfy the charge neutrality condition. It is a value, and y is an arbitrary value.

Further, for example, the MER-type zeolite according to the present embodiment is a MER-type zeolite represented by K _x-δ [Al _x Si _32-x O ₆₄ ] · yH ₂ O. However, x is a value that satisfies 6.0 ≦ x ≦ 14.0, δ is a value that is determined so as to satisfy the charge neutrality condition, and y is an arbitrary value.

In particular, in the MER-type zeolite according to the present embodiment, x is preferably 6.7 ≦ x ≦ 13.5, and more preferably 9.5 ≦ x ≦ 11.7 in the above chemical formula. In the negative thermal expansion material according to the present embodiment, the volume expansion coefficient of the negative thermal expansion material can be adjusted by changing the value of x. In other words, the volume expansion coefficient of the negative thermal expansion material according to the present embodiment changes according to the Si / Al ratio. For example, the larger Si / Al (that is, the smaller x), the more the absolute value of the negative volume expansion tendency tends to increase. 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.

Further, in the present embodiment, 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. In this way, by substituting a part of K contained in the MER-type zeolite with these elements, the volume expansion coefficient of the negative thermal expansion material can be adjusted.

In the negative thermal expansion material according to the present embodiment, 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.

Further, 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.

Further, the GIS-type zeolite according to the present embodiment is a GIS-type zeolite represented by Na _x-δ [Al _x Si _16-x O ₃₂ ] · yH ₂ O. However, x satisfies 4.5 ≦ x ≦ 7.5, δ is a value determined so as to satisfy the charge neutrality condition, and y is an arbitrary value.

Further, the GIS-type zeolite according to the present embodiment may be a GIS-type zeolite represented by Na _x-δ [Al _x Si _16-x O ₃₂ ] · yH ₂ O. However, x satisfies 5.0 ≦ x ≦ 7.0, δ is a value determined so as to satisfy the charge neutrality condition, and y is an arbitrary value.

In the above-mentioned GIS-type zeolite, x may be 5.3 ≦ x ≦ 6.9. Further, 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.

As described above, 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. , It is possible to form a composite material having a controlled coefficient of thermal expansion. For example, as the positive thermal expansion material, a resin material or a metal material can be used, but the material is not limited thereto. By reducing the density of the negative thermal expansion material to be mixed at this time, the negative thermal expansion material can be uniformly dispersed in the positive thermal expansion material.

Further, as described above, 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).

Further, in the negative thermal expansion material according to the present embodiment, 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. For example, 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.

In this embodiment, 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.

Further, as 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.

Next, a method for manufacturing a negative thermal expansion material according to the present embodiment will be described.
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. When producing the MER-type zeolite, first, colloidal silica and _H2O are put into the beaker A, and these are stirred and mixed (step S1). Further, 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). Then, the solution of beaker A and the solution of beaker B are mixed and stirred (step S3).

After that, the stirred aqueous solution (mixture) is poured into a container and subjected to hydrothermal treatment (step S4). In the hydrothermal treatment, for example, 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). For example, the temperature of the hydrothermal treatment can be 150 ° C., and 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.

After hydrothermal treatment, 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.

In the method for producing MER-type zeolite according to 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. In the production method shown in FIG. 8, first, KOH, Al (OH) ₃ , H ₃ PO ₄ , and H ₂ O are put into a beaker, and these are heated and stirred until they become transparent (step S11). Then, colloidal silica is mixed with the beaker and stirred (step S12).

After that, 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).

After the hydrothermal treatment, 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. In the production method shown in FIG. 8, 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. In the production method shown in FIG. 12, first, silica, a tetraethylammonium hydroxide (TEAOH) solution, and _H2O are added to the beaker A, and these are stirred and mixed (step S21). Further, KOH, Al (OH) ₃ and H ₂ O are put into the beaker B, and these are heated and stirred (step S22). Then, the solution of beaker A and the solution of beaker B are mixed and stirred (step S23).

After that, 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.

Next, 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. In the negative thermal expansion material according to the present embodiment, 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. First, a 0.1 M aqueous nitric acid solution (MNO ₃ aq.) Is prepared in a beaker using the replacement raw material A (step S41). Here, "M" is Mg, Ca, or Na. For example, when a part of K is replaced with Mg, Mg (NO ₃ ) _{2.6H 2 O} can be used as the replacement raw material A. When a part of K is replaced with Ca, Ca (NO ₃ ) _{2.4H 2 O} can be used as the replacement raw material A. When a part of K is replaced with Na, NaNO ₃ can be used as the replacement raw material A. When a part of K is replaced with an element other than these, the nitric acid aqueous solution of this element can be used as the replacement raw material A.

Then, the MER-type zeolite is put into a beaker and stirred at, for example, 80 ° C. for 24 hours (step S42). The stirring conditions (temperature, time) may be other than these conditions. Next, the stirred sample is suction-filtered with pure water to wash it with pure water (step S43). Then, 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. for 16 hours (step S44), 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.

When a part of K contained in the MER-type zeolite is substituted (ion exchange) with a predetermined element M, the substitution amount (amount of the substitution element M) 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.

Next, a method for producing an LTA-type zeolite and a FAU-type zeolite will be described. FIG. 24 is a flowchart showing an example of a method for producing an LTA-type zeolite and a FAU-type zeolite. When producing the 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).

Then, 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. Then, 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.

In the method for producing LTA-type zeolite and FAU-type zeolite according to 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.

Next, a method for producing a GIS-type zeolite will be described. FIG. 27 is a flowchart showing an example of a method for producing a GIS-type zeolite. In the production method shown in FIG. 27, first, NaAlO ₂ , NaOH, and _H2O are put into a beaker, and these are stirred and mixed (step S61). Then, colloidal silica is mixed with the beaker and stirred (step S62). Then, 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).

After the hydrothermal treatment, 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).

In the method for producing a GIS-type zeolite according to the present embodiment, the composition of the GIS-type zeolite can be changed by adjusting the composition ratio (charged molar ratio) of each raw material.

Next, a part of Na contained in the GIS-type zeolite is added to H, Li, K, 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, and lanthanoid will be described.

FIG. 31 is a flowchart for explaining an example of an ion exchange method for a GIS-type zeolite. First, a 1M aqueous hydrochloric acid solution (MCl aq.) Is prepared in a beaker using the replacement raw material B (step S71). Here, "M" is Mg, Ca, K, or Li. For example, when a part of Na is replaced with Mg, MgCl _{2.6H 2 O} can be used as the replacement raw material B. When a part of Na is replaced with Ca, CaCl _{2.2H 2 O} can be used as the replacement raw material B. When a part of Na is replaced with K, KCl can be used as the replacement raw material B. 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.

After that, the GIS-type zeolite is put into a beaker and stirred at, for example, 80 ° C. for 24 hours (step S72). The stirring conditions (temperature, time) may be other than these conditions. Next, the stirred sample is filtered and washed with pure water (step S73). Then, 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. It should be noted that this drying condition is an example, and the drying condition may be other than these in the present embodiment.

Hereinafter, examples of the present invention will be described.

<Example 1>
As Example 1, a MER-type zeolite was prepared. FIG. 1 is a flowchart showing a method for producing a MER-type zeolite. First, colloidal silica (concentration 30 wt%: manufactured by Nissan Chemical Industries, Ltd., Snowtex Na type ST-30) and _H2O were put into the beaker A, and these were stirred and mixed (step S1). Further, 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). Then, the solution of beaker A and the solution of beaker B were mixed and stirred (step S3).

Then, 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.

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).

The composition ratio (charged molar ratio) of each raw material in Example 1 was SiO ₂ : Al (OH) ₃ : KOH: H ₂ O = 5: 1: 6: 100.

In addition, the composition (atomic ratio) of the prepared sample according to Example 1 was analyzed using ICP-OES (Inductivity Coupled Plasma Optical Emission Spectrometry).
[ICP-OES]
-ICP-OES equipment used: 5100 VDV ICP-OES (Agilent Technologies)
・ ICP ionization unit: Ar plasma

As a result of the composition analysis, 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

In addition, 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. In addition, Si (NIST SRM 640c) was used as the internal standard.
[High temperature XRD (HT-XRD)]
-Device used: Mini Flex 600 (Rigaku Co., Ltd.)
・ Atmosphere: Air
・ Tube current / tube voltage: 15mA / 40kV
・ Target: Cu
・ Step width: 0.02 °
-Measurement range (scanning speed): 5 to 75 ° (4 ° / min)
・ Measurement temperature: 30-220 ° C

The obtained X-ray diffraction pattern (HT-XRD measurement result: temperature rise) is shown in FIG. In addition, the X-ray diffraction pattern when the temperature of the sample was lowered after being heated was also measured. The obtained X-ray diffraction pattern (HT-XRD measurement result: temperature drop) is shown in FIG.

Using the obtained X-ray diffraction pattern and analysis software (HighScore Plus, PANalytical), 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 α _l and the volume coefficient of thermal expansion α _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.

<Example 2>
As Example 2, a MER-type zeolite was prepared. The sample according to Example 2 was also prepared by the same method as in Example 1. The composition ratio (charged molar ratio) of each raw material in Example 2 was SiO ₂ : Al (OH) ₃ : KOH: H ₂ O = 5: 2: 6: 100.

Moreover, when the composition (atomic ratio) of the prepared sample according to Example 2 was analyzed using ICP-OES in the same manner as in Example 1, the composition of the sample according to Example 2 was as follows.
K _10.3 [Al _10.6 Si _21.4 O ₆₄ ] · yH ₂ O ・ ・ ・ Example 2

Further, the coefficient of thermal expansion of the sample according to Example 2 was measured using the same method as in Example 1. 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>
As Example 3, a MER-type zeolite was prepared. The sample according to Example 3 was also prepared by the same method as in Example 1. The composition ratio (charged molar ratio) of each raw material in Example 3 was SiO ₂ : Al (OH) ₃ : KOH: H ₂ O = 5: 3: 6: 100.

Moreover, 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

Further, the coefficient of thermal expansion of the sample according to Example 3 was measured by using the same method as in Example 1. 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>
As Example 4, a MER-type zeolite was prepared. The sample according to Example 4 was also prepared by the same method as in Example 1. The composition ratio (charged molar ratio) of each raw material in Example 4 was SiO ₂ : Al (OH) ₃ : KOH: H ₂ O = 5: 2: 12: 100.

Moreover, 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

Further, the coefficient of thermal expansion of the sample according to Example 4 was measured by the same method as in Example 1. 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.

<Example 5>
As Example 5, a MER-type zeolite was prepared. FIG. 8 is a flowchart showing a method for producing a MER-type zeolite. First, 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). Then, 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).

Then, 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.

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 composition ratio (charged molar ratio) of each raw material in Example 5 is SiO ₂ : Al (OH) ₃ : KOH: H ₃ PO ₄ : H ₂ O = 4.25: 2.375: 6: 0. It was set to 375: 100.

By using the above-mentioned production method, a single-phase MER-type zeolite could be produced. When the composition (atomic ratio) of the prepared sample was analyzed using ICP-OES, the composition of the sample according to Example 5 was as follows.
K _13.6 [Al _13.4 Si _18.6 O ₆₄ ] · yH ₂ O ... Example 5

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. In the production method according to Example 5, phosphorus was added to the starting material, but phosphorus was not contained in the finally obtained zeolite.

In addition, HT-XRD was measured to determine the lattice constant from room temperature to 250 ° C. (FIG. 9). When 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 ).

<Example 6>
As Example 6, a MER-type zeolite was prepared. The sample according to Example 6 was also prepared by the same method as in Example 5. The composition ratio (charged molar ratio) of each raw material in Example 6 is SiO ₂ : Al (OH) ₃ : KOH: H ₃ PO ₄ : H ₂ O = 4.5: 2.25: 6: 0. It was set to 25: 100. In this example as well, a single-phase MER-type zeolite could be produced.

When the composition (atomic ratio) of the prepared sample was analyzed using ICP-OES, the composition of the sample was as follows.
K _12.8 [Al _12.8 Si _19.2 O ₆₄ ] · yH ₂ O ... Example 6

In addition, HT-XRD was measured to determine the lattice constant from room temperature to 230 ° C. (FIG. 6). When the coefficient of thermal expansion is calculated from this result, 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.

<Example 7>
As Example 7, a MER-type zeolite was prepared. The sample according to Example 7 was also prepared by the same method as in Example 5. The composition ratio (charged molar ratio) of each raw material in Example 7 is SiO ₂ : Al (OH) ₃ : KOH: H ₃ PO ₄ : H ₂ O = 4.75: 2.125: 6: 0. It was set to 125: 100. In this example as well, a single-phase MER-type zeolite could be produced.

When the composition (atomic ratio) of the prepared sample was analyzed using ICP-OES, the composition of the sample was as follows.
K _11.5 [Al _11.5 Si _20.5 O ₆₄ ] · yH ₂ O ・ ・ ・ Example 7

In addition, HT-XRD was measured to determine the lattice constant from room temperature to 250 ° C. (FIG. 11). When 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.

<Example 8>
As Example 8, a MER-type zeolite was prepared. FIG. 12 is a flowchart showing a method for producing a MER-type zeolite. First, silica (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), a 35% tetraethylammonium hydroxide (TEAOH) solution, and _H2O were added to the beaker A, and these were stirred and mixed (step S21). Further, KOH, Al (OH) ₃ and H ₂ O were put into the beaker B, and these were heated and stirred (step S22). Then, the solution of beaker A and the solution of beaker B were mixed and stirred (step S23).

After that, 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).

The composition ratio (charged molar ratio) of each raw material in Example 8 was SiO ₂ : Al (OH) ₃ : KOH: TEAOH: H ₂ O = 5: 1: 3: 1: 150. By using the above-mentioned production method, 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.

When the composition (atomic ratio) of the prepared sample was analyzed using ICP-OES, the composition of the sample according to Example 8 was as follows.
K _8.4 [Al _9.0 Si _23.0 O ₆₄ ] · yH ₂ O ・ ・ ・ Example 8

Further, 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.

<Example 9>
As Example 9, a MER-type zeolite was prepared. The sample according to Example 9 was also prepared by the same method as in Example 8. The composition ratio (charged molar ratio) of each raw material in Example 9 was SiO ₂ : Al (OH) ₃ : KOH: TEAOH: H ₂ O = 5: 1: 1.5: y: 150. y was set to 0 to 9.5. In addition, a sample in which the composition ratio (preparation molar ratio) of each raw material was SiO ₂ : Al (OH) ₃ : KOH: TEAOH: H ₂ O = 5: 1: 1.0: 9.0: 150 was also prepared. ..

FIG. 15 shows the XRD measurement results of the sample prepared in this way. From the results shown in FIG. 15, a single-phase MER-type zeolite could be produced in the range of y = 1.0 to 9.5. Moreover, when the composition (atomic ratio) of these samples was analyzed using ICP-OES, the composition was as follows.

y = 1.0: K _6.7 [Al _6.7 Si _25.2 O ₆₄ ] · yH ₂ O
y = 2.5: K _6.8 [Al _8.3 Si _23.7 O ₆₄ ] · yH ₂ O
y = 5.0: K _9.0 [Al _8.9 Si _23.1 O ₆₄ ] · yH ₂ O
y = 7.5: K _9.2 [Al _9.2 Si _22.8 O ₆₄ ] · yH ₂ O
y = 9.5: K _9.3 [Al _9.3 Si _22.7 O ₆₄ ] · yH ₂ O
y = 1.0: K _6.7 [Al _6.7 Si _25.2 O ₆₄ ] · yH ₂ O

Among the above-mentioned samples, 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. In addition, 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.

<Example 10>
As Example 10, a MER-type zeolite was prepared. FIG. 18 is a flowchart showing a method for producing a MER-type zeolite. First, silica (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and _H2O were put into the beaker A, and these were stirred and mixed (step S31). Further, KOH, Al (OH) ₃ and H ₂ O were put into the beaker B, and these were heated and stirred (step S32). Then, the solution of beaker A and the solution of beaker B were mixed and stirred (step S33).

After that, 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. 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). The composition ratio (charged molar ratio) of each raw material in Example 10 was SiO ₂ : Al (OH) ₃ : KOH: H ₂ O = 5: 1: z: 150. z is 1.25 to 12.0.

FIG. 19 shows the XRD measurement results of the sample prepared in this way. From the results shown in FIG. 19, a single-phase MER-type zeolite could be produced in the range of z = 2.25 to 12.0. Moreover, when the composition (atomic ratio) of these samples was analyzed using ICP-OES, the composition was as follows.

z = 2.25: K _6.7 [Al _7.0 Si _25.0 O ₆₄ ] · yH ₂ O
z = 2.5: K _6.8 [Al _7.1 Si _24.9 O ₆₄ ] · yH ₂ O
z = 3.0: K _7.2 [Al _7.7 Si _24.3 O ₆₄ ] · yH ₂ O
z = 4.0: K _9.3 [Al _9.5 Si _22.5 O ₆₄ ] · yH ₂ O
z = 12.0: K _11.2 [Al _12.8 Si _19.2 O ₆₄ ] · yH ₂ O

<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. First, as 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).

Then, the sample of 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.

When the composition (atomic ratio) of the prepared sample according to Example 11 was analyzed using ICP-OES in the same manner as in Example 1, the composition of the sample according to Example 11 was as follows.
K _5.0 Ca _2.6 [Al _10.7 Si _21.3 O ₆₄ ] · yH ₂ O ・ ・ ・ Example 11

Further, the coefficient of thermal expansion of the sample according to Example 11 was measured using the same method as in Example 1. 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>
As 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.

In 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. First, as 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).

Then, the sample of 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.

When the composition (atomic ratio) of the prepared sample according to Example 12 was analyzed using ICP-OES in the same manner as in Example 1, the composition of the sample according to Example 12 was as follows.
K _6.7 Mg _2.0 [Al _10.8 Si _21.2 O ₆₄ ] · yH ₂ O ・ ・ ・ Example 12

Further, the coefficient of thermal expansion of the sample according to Example 12 was measured using the same method as in Example 1. 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.

In 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. First, a 0.1 M sodium nitrate aqueous solution (NaNO ₃ aq.) Was prepared in 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).

Then, the sample of 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.

When the composition (atomic ratio) of the prepared sample according to Example 13 was analyzed using ICP-OES in the same manner as in Example 1, the composition of the sample according to Example 13 was as follows.
K _3.9 Na _6.5 [Al _10.8 Si _21.2 O ₆₄ ] · yH ₂ O ... Example 13

Further, the coefficient of thermal expansion of the sample according to Example 13 was measured using the same method as in Example 1. 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.

<Example 14>
An LTA-type zeolite was prepared as Example 14. FIG. 24 is a flowchart showing a method for producing an LTA-type zeolite. First, NaOH, NaAlO ₂ , and _H2O were put into a beaker and stirred until they were dissolved (step S51). Then, colloidal silica (concentration 30 wt%: manufactured by Nissan Chemical Industries, Ltd., Snowtex Na type ST-30) was put into a beaker, and these were stirred for 24 hours (step S52).

Then, 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.

The composition ratio (charged molar ratio) of each raw material in Example 14 was SiO ₂ : Al ₂ O ₃ : NaOH: H ₂ O = 1: 1: 11: 190.

Moreover, 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

Further, the coefficient of thermal expansion of the sample according to Example 14 was measured using the same method as in Example 1. 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.

<Example 15>
As Example 15, a FAU-type zeolite was prepared. The sample according to Example 15 was also prepared by the same method as in Example 14. The composition ratio (charged molar ratio) of each raw material in Example 15 was SiO ₂ : Al ₂ O ₃ : NaOH: H ₂ O = 3: 1: 11: 190.

Moreover, when the 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 ... Example 15

Further, the coefficient of thermal expansion of the sample according to Example 15 was measured using the same method as in Example 1. 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.

<Example 16>
A GIS-type zeolite was prepared as Example 16. FIG. 27 is a flowchart showing a method for producing a GIS-type zeolite. First, NaAlO ₂ , NaOH and _H2O were put into a beaker, and these were stirred and mixed (step S61). Then, 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). Then, 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.

After the hydrothermal treatment, a precipitate was formed in the Teflon container taken out. The precipitate was washed with pure water (step S64). Then, the washed precipitate was dried at a temperature of about 110 ° C. for 16 hours to obtain a white solid (step S65). The composition ratio (charged molar ratio) of each raw material in Example 16 was SiO ₂ : NaAlO ₂ : NaOH: H ₂ O = 3.7: 0.41: 9.5: 173.

By using the above-mentioned production method, a single-phase GIS-type zeolite could be produced. When the composition (atomic ratio) of the prepared sample was analyzed using ICP-OES, the composition of the sample according to Example 16 was as follows.
Na _6.5 [Al _6.9 Si _9.2 O ₃₂ ] · yH ₂ O ... Example 16

In addition, HT-XRD was measured to determine the lattice constant from room temperature to 500 ° C. (FIG. 28). When 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. The composition ratio (charged molar ratio) of each raw material in Example 17 was SiO ₂ : NaAlO ₂ : NaOH: H ₂ O = 10: 1.11: 8.6: 173.

By using the above-mentioned production method, a single-phase GIS-type zeolite could be produced. When the composition (atomic ratio) of the prepared sample was analyzed using ICP-OES, the composition of the sample according to Example 17 was as follows.
Na _5.2 [Al _5.3 Si _10.7 O ₃₂ ] · yH ₂ O ... Example 17

In addition, HT-XRD was measured to determine the lattice constant from room temperature to 500 ° C. (FIG. 29). When 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. The composition ratio (charged molar ratio) of each raw material in Example 18 was SiO ₂ : NaAlO ₂ : NaOH: H ₂ O = 10: 2.5: 6.9: 173.

By using the above-mentioned production method, a single-phase GIS-type zeolite could be produced. When the composition (atomic ratio) of the prepared sample was analyzed using ICP-OES, the composition of the sample according to Example 18 was as follows.
Na _5.8 [Al _5.9 Si _10.1 O ₃₂ ] · yH ₂ O ... Example 18

In addition, HT-XRD was measured to determine the lattice constant from room temperature to 500 ° C. (FIG. 30). When 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. First, as the replacement raw material B, 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).

Then, the sample of 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.

When the composition (atomic ratio) of the prepared sample according to Example 19 was analyzed using ICP-OES in the same manner as in Example 1, the composition of the sample according to Example 19 was as follows.
Mg-GIS type: Na _3.9 Mg _1.2 [Al _6.1 Si _9.9 O ₃₂ ] · yH ₂ O
Ca-GIS type: Na _0.8 Ca _2.8 [Al _6.2 Si _9.8 O ₃₂ ] · yH ₂ O
K-GIS type: K _5.3 [Al _6.0 Si _10.0 O ₃₂ ] · yH ₂ O
Li-GIS type: Na _4.0 Li _2.0 [Al _6.2 Si _9.8 O ₃₂ ] · yH ₂ O

<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.

When the composition (atomic ratio) of the prepared sample according to Example 20 was analyzed using ICP-OES in the same manner as in Example 1, the 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). ..

Further, in 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. In 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).

Further, in Examples 14 (LTA-type zeolite), Example 15 (FAU-type zeolite), and 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. In particular, the sample according to Example 14 showed a stable negative volume expansion rate at 300 ° C. or higher.

As described above, 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.

Although the present invention has been described above in accordance with the above-described embodiment, the present invention is not limited to the configuration of the above-described embodiment, and those skilled in the art are within the scope of the claimed invention. Of course, it includes various modifications, corrections, and combinations that can be made.

This application claims priority based on Japanese application Japanese Patent Application No. 2020-186229 filed on November 9, 2020, and incorporates all of its disclosures herein.

Claims (14)

1. A negative thermal expansion material having 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.
2. The negative thermal expansion material according to claim 1, wherein the MER-type zeolite is M _(x-δ) [Al _x Si _32-x O ₆₄ ] · yH ₂ O. However, 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 δ is determined to satisfy the charge neutrality condition. It is a value, and y is an arbitrary value.
3. The negative thermal expansion material according to claim 1, wherein the MER-type zeolite is K _x-δ [Al _x Si _32-x O ₆₄ ] · yH ₂ O. However, x is a value that satisfies 6.0 ≦ x ≦ 14.0, δ is a value that is determined so as to satisfy the charge neutrality condition, and y is an arbitrary value.
4. The negative thermal expansion material according to claim 3, wherein x is 6.7 ≦ x ≦ 13.5.
5. The negative thermal expansion material according to claim 3 or 4, wherein the volume expansion coefficient at least at 60 ° C. or higher and 140 ° C. or lower is -236 ppmK ^-1 or higher and -98.6 ppmK ^-1 or lower.
6. The negative thermal expansion material according to any one of claims 2 to 5, characterized in that it exhibits volume shrinkage associated with a phase transition in a temperature range of 100 ° C. or higher and 200 ° C. or lower.
7. 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, Fe, Co, Sn, Pb, The negative thermal expansion material according to any one of claims 3 to 6, wherein the negative thermal expansion material is substituted with at least one selected from the group consisting of Mn, Al, Cr, Y, Zr, Ti, lanthanoid, and tetraethylammonium ion. ..
8. The negative thermal expansion material according to claim 1, wherein the GIS-type zeolite is Na _x-δ [Al _x Si _16-x O ₃₂ ] · yH ₂ O. However, x satisfies 4.5 ≦ x ≦ 7.5, δ is a value determined so as to satisfy the charge neutrality condition, and y is an arbitrary value.
9. The negative thermal expansion material according to claim 1, wherein the GIS-type zeolite is Na _x-δ [Al _x Si _16-x O ₃₂ ] · yH ₂ O. However, x satisfies 5.0 ≦ x ≦ 7.0, δ is a value determined so as to satisfy the charge neutrality condition, and y is an arbitrary value.
10. The negative thermal expansion material according to claim 8 or 9, wherein x is 5.3 ≦ x ≦ 6.9.
11. 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, Fe, Co, Sn, Pb, The negative thermal expansion material according to any one of claims 8 to 10, wherein the negative thermal expansion material is substituted with at least one selected from the group consisting of Mn, Al, Cr, Y, Zr, Ti, and lanthanoid.
12. The negative thermal expansion material according to any one of claims 1 to 11.
    A composite material comprising, and a material having a positive coefficient of thermal expansion.
13. The composite material according to claim 12, wherein the material having a positive coefficient of thermal expansion is a resin material.
14. The composite material according to claim 12, wherein the material having a positive coefficient of thermal expansion is a metallic material.

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