Negative thermal expansion materials and composite materials

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

[Technical Field]

[0001] The present invention relates to a negative thermal expansion material and a composite material. [Background technology]

[0002] In devices that combine multiple materials, such as electronic devices, optical devices, fuel cells, and sensors, misalignment due to thermal expansion can be a problem. Differences in the thermal expansion coefficients of each material can lead to serious problems such as interfacial delamination and disconnections. For this reason, various near-zero thermal expansion materials and thermal expansion control technologies are being researched. Invar alloys, glass, cordierite, and other materials are widely known to have near-zero thermal expansion in a single phase, and are used in industrial and consumer products. In recent years, efforts have been made to reduce the thermal expansion of materials that are difficult to control on their own by compounding them with fillers with low thermal expansion coefficients. In particular, compounding with materials that have a negative thermal expansion coefficient (hereinafter also referred to as negative thermal expansion materials) has attracted attention because they can effectively offset thermal expansion at low compounding ratios.

[0003] In Patent Document 1, Bi is listed as a material having a negative thermal expansion coefficient. 1-x Sb x NiO3, where x is 0.02≦x≦0.20, is disclosed. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-48071 Summary of the Invention [Problem to be solved by the invention]

[0005] Various materials with negative thermal expansion coefficients have been reported to date, but most of them are primarily composed of precious metals or heavy metals, which means that they have not yet been able to achieve low cost or low density.

[0006] 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 achieve low cost and low density. [Means for solving the problem]

[0007] A negative thermal expansion material according to one embodiment of the present invention is a negative thermal expansion material having a negative thermal expansion coefficient, which includes at least one zeolite selected from the group consisting of MER zeolite, GIS zeolite, LTA zeolite, and FAU zeolite.

[0008] In the negative thermal expansion material, the MER zeolite is M (x-δ) [Al x Si 32-x O 64 ]·yH2O, where M is at least one selected from the group consisting of H, Li, Na, K, Ag, NH4, Mg, Ca, Sr, Ba, Cd, Ni, Zn, Cu, Hg, Fe, Co, Sn, Pb, Mn, Al, Cr, Y, Zr, Ti, a lanthanoid, and a tetraethylammonium ion, x satisfies 6.0≦x≦14.0, δ is a value determined so as to satisfy the charge neutrality condition, and y is an arbitrary value.

[0009] In the negative thermal expansion material, the MER zeolite is K x-δ [Al x Si 32-x O 64 ]·yH2O, where x satisfies 6.0≦x≦14.0, δ is a value determined to satisfy the charge neutrality condition, and y is an arbitrary value.

[0010] In the negative thermal expansion material, the x may be in the range of 6.7≦x≦13.5.

[0011] The negative thermal expansion material has a volume expansion coefficient of -236 ppmK at temperatures between 60°C and 140°C. -1 Over -98.6 ppmK -1 It may be the following:

[0012] The negative thermal expansion material may exhibit volumetric shrinkage due to a phase transition in the temperature range of 100°C or higher and 200°C or lower.

[0013] In the negative thermal expansion material described above, a portion of the K contained in the MER zeolite may be substituted with at least one selected from the group consisting of H, Li, Na, Ag, NH4, Mg, Ca, Sr, Ba, Cd, Ni, Zn, Cu, Hg, Fe, Co, Sn, Pb, Mn, Al, Cr, Y, Zr, Ti, lanthanoids, and tetraethylammonium ions.

[0014] In the negative thermal expansion material, the GIS-type zeolite is Na x-δ [Al x Si 16-x O 32 ]·yH2O, where x satisfies 4.5≦x≦7.5, δ is a value determined to satisfy the charge neutrality condition, and y is an arbitrary value.

[0015] In the negative thermal expansion material, the GIS-type zeolite is Na x-δ [Al x Si 16-x O 32 ]·yH2O, where x satisfies 5.0≦x≦7.0, δ is a value determined to satisfy the charge neutrality condition, and y is an arbitrary value.

[0016] In the negative thermal expansion material, the x may be in the range of 5.3≦x≦6.9.

[0017] In the above-mentioned negative thermal expansion material, a portion of the Na contained in the GIS-type zeolite may be substituted with at least one selected from the group consisting of H, Li, K, Ag, NH4, Mg, Ca, Sr, Ba, Cd, Ni, Zn, Cu, Hg, Fe, Co, Sn, Pb, Mn, Al, Cr, Y, Zr, Ti, and lanthanoids.

[0018] A composite material according to one aspect of the present invention includes the above-mentioned negative thermal expansion material and a material having a positive thermal expansion coefficient.

[0019] In the composite material described above, the material having a positive thermal expansion coefficient may be a resin material.

[0020] In the above-described composite material, the material having a positive thermal expansion coefficient may be a metal material. [Effects of the Invention]

[0021] The present invention can provide a negative thermal expansion material and a composite material that can achieve low cost and low density. [Brief explanation of the drawings]

[0022] [Figure 1] 1 is a flowchart showing an example of a method for producing a negative thermal expansion material (MER type) according to the present invention. [Figure 2] FIG. 1 is a diagram showing the results of HT-XRD measurement (temperature increase) of MER zeolite. [Figure 3] FIG. 1 is a diagram showing the results of HT-XRD measurement (lowering temperature) of MER zeolite. [Figure 4] 4 is a graph showing the temperature characteristics of a sample according to Example 1. [Figure 5] 10 is a graph showing the temperature characteristics of a sample according to Example 2. [Figure 6] 10 is a graph showing the temperature characteristics of a sample according to Example 3. [Figure 7] 10 is a graph showing the temperature characteristics of a sample according to Example 4. [Figure 8] 1 is a flowchart showing another example of a method for producing a negative thermal expansion material (MER type) according to the present invention. [Figure 9] 10 is a graph showing the temperature characteristics of a sample according to Example 5. [Figure 10] 10 is a graph showing the temperature characteristics of a sample according to Example 6. [Figure 11] 11 is a graph showing the temperature characteristics of a sample according to Example 7. [Figure 12]1 is a flowchart showing another example of a method for producing a negative thermal expansion material (MER type) according to the present invention. [Figure 13] FIG. 10 is a diagram showing the results of HT-XRD measurement of the sample according to Example 8. [Figure 14] 10 is a graph showing the temperature characteristics of a sample according to Example 8. [Figure 15] FIG. 10 is a diagram showing the results of XRD measurement of the sample according to Example 9. [Figure 16] FIG. 10 is a diagram showing the results of HT-XRD measurement of the sample according to Example 9. [Figure 17] 10 is a graph showing the temperature characteristics of a sample according to Example 9. [Figure 18] 1 is a flowchart showing another example of a method for producing a negative thermal expansion material (MER type) according to the present invention. [Figure 19] FIG. 10 is a diagram showing the results of XRD measurement of the sample according to Example 10. [Figure 20] 1 is a flowchart illustrating an example of a method for ion-exchanging MER zeolite (a method for producing M-MER zeolite). [Figure 21] 13 is a graph showing the temperature characteristics of a sample according to Example 11. [Figure 22] 13 is a graph showing the temperature characteristics of a sample according to Example 12. [Figure 23] 13 is a graph showing the temperature characteristics of a sample according to Example 13. [Figure 24] 1 is a flowchart showing an example of a method for producing a negative thermal expansion material (LTA type, FAU type) according to the present invention. [Figure 25] 13 is a graph showing the temperature characteristics of the sample according to Example 14. [Figure 26] 13 is a graph showing the temperature characteristics of a sample according to Example 15. [Figure 27] 1 is a flowchart showing an example of a method for producing a negative thermal expansion material (GIS type) according to the present invention. [Figure 28] 13 is a graph showing the temperature characteristics of a sample according to Example 16. [Figure 29] 13 is a graph showing the temperature characteristics of the sample according to Example 17. [Figure 30] 13 is a graph showing the temperature characteristics of the sample according to Example 18. [Figure 31] 1 is a flowchart for explaining an example of a method for ion exchanging GIS zeolite (a method for producing M-GIS zeolite). [Figure 32] 1 is a table summarizing the molar ratios, compositions, volume expansion coefficients, and temperature ranges of samples according to examples. [Figure 33] 1 is a table summarizing the molar ratios, compositions, volume expansion coefficients, and temperature ranges of samples according to examples. [Figure 34] 1 is a table summarizing the molar ratios, compositions, volume expansion coefficients, and temperature ranges of samples according to examples. DETAILED DESCRIPTION OF THE INVENTION

[0023] Hereinafter, an embodiment of the present invention will be described. The negative thermal expansion material according to this embodiment is characterized by containing at least one 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.

[0024] For example, the MER zeolite according to this embodiment is M (x-δ) [Al x Si 32-x O 64 ]·yH2O, where M is at least one selected from the group consisting of H, Li, Na, K, Ag, NH4, Mg, Ca, Sr, Ba, Cd, Ni, Zn, Cu, Hg, Fe, Co, Sn, Pb, Mn, Al, Cr, Y, Zr, Ti, lanthanoids, and tetraethylammonium ions, x satisfies 6.0≦x≦14.0, δ is a value determined so as to satisfy the charge neutrality condition, and y is an arbitrary value.

[0025] For example, the MER zeolite according to this embodiment is K x-δ [Al x Si 32-x O 64 ]·yH2O, where x satisfies the condition 6.0≦x≦14.0, δ is a value determined to satisfy the charge neutrality condition, and y is an arbitrary value.

[0026] In particular, in the MER zeolite according to this embodiment, in the above chemical formula, x preferably satisfies 6.7≦x≦13.5, and more preferably satisfies 9.5≦x≦11.7. The negative thermal expansion material according to this embodiment can adjust its volume expansion coefficient by changing the value of x. In other words, the negative thermal expansion material according to this embodiment has a volume expansion coefficient that changes depending on the Si / Al ratio. For example, the absolute value of the negative volume expansion coefficient tends to increase as the Si / Al ratio increases (i.e., as x decreases). The MER zeolite according to this embodiment may contain trace amounts of unavoidable impurities (e.g., Na) in addition to K, Al, and Si.

[0027] In this embodiment, a portion of the K contained in the MER zeolite may be substituted with at least one element selected from the group consisting of H, Li, Na, Ag, NH4, Mg, Ca, Sr, Ba, Cd, Ni, Zn, Cu, Hg, Fe, Co, Sn, Pb, Mn, Al, Cr, Y, Zr, Ti, lanthanoids, and tetraethylammonium ions. In this way, by substituting a portion of the K contained in the MER zeolite with these elements, the volume expansion coefficient of the negative thermal expansion material can be adjusted.

[0028] The negative thermal expansion material according to this embodiment has a volume expansion coefficient of -236 ppmK at least at a temperature of 60°C or higher and 140°C or lower. -1 More than -39ppmK -1 The following is the result.

[0029] Furthermore, the negative thermal expansion material according to this embodiment may exhibit volumetric shrinkage due to a phase transition in a temperature range of 100° C. to 200° C. In this way, by exhibiting volumetric shrinkage due to a phase transition, a large negative volumetric expansion coefficient can be realized.

[0030] In addition, the GIS-type zeolite according to this embodiment contains Na x-δ [Al x Si 16-x O 32 ]·yH2O, where x satisfies 4.5≦x≦7.5, δ is a value determined to satisfy the charge neutrality condition, and y is an arbitrary value.

[0031] In addition, the GIS-type zeolite according to this embodiment contains Na x-δ [Al x Si 16-x O 32 ]·yH2O, where 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.

[0032] In the above-described GIS zeolite, x may satisfy the condition 5.3≦x≦6.9. Furthermore, a portion of Na contained in the above-described GIS zeolite may be substituted with at least one element selected from the group consisting of H, Li, K, Ag, NH4, Mg, Ca, Sr, Ba, Cd, Ni, Zn, Cu, Hg, Fe, Co, Sn, Pb, Mn, Al, Cr, Y, Zr, Ti, and lanthanoids.

[0033] As described above, the negative thermal expansion material according to this embodiment is made of at least one zeolite selected from the group consisting of MER zeolite, GIS zeolite, LTA zeolite, and FAU zeolite. These materials are inexpensive and contain relatively light atoms as their main components, which allows for low cost and low density negative thermal expansion materials.

[0034] The negative thermal expansion material according to this embodiment can be mixed with a material having a positive thermal expansion coefficient (positive thermal expansion material), in other words, by dispersing the negative thermal expansion material in the positive thermal expansion material, to form a composite material with a controlled thermal expansion coefficient. For example, the positive thermal expansion material can be a resin material or a metal material, but is not limited to these. In this case, by reducing the density of the negative thermal expansion material to be mixed, the negative thermal expansion material can be uniformly dispersed in the positive thermal expansion material.

[0035] As described above, the negative thermal expansion material according to this embodiment has a thermal expansion coefficient that changes depending on the value of x. That is, the smaller the value of x, the smaller the volumetric expansion coefficient (in other words, the larger the absolute value of the negative volumetric expansion coefficient).

[0036] Furthermore, the negative thermal expansion material according to this embodiment can adjust the volumetric expansion coefficient of the negative thermal expansion material by substituting a portion of the K contained in the MER zeolite with H, Li, Na, Ag, NH4, Mg, Ca, Sr, Ba, Cd, Ni, Zn, Cu, Hg, Fe, Co, Sn, Pb, Mn, Al, Cr, Y, Zr, Ti, a lanthanoid, tetraethylammonium ion, etc. For example, by substituting Mg, Ca, or Na for K, the volumetric expansion coefficient of the negative thermal expansion material and the temperature range in which the negative volumetric expansion coefficient is exhibited can be adjusted.

[0037] In this embodiment, the value of x in the negative thermal expansion material and the element to replace K may be determined depending on the characteristics of the positive thermal expansion material used to form the composite material, the characteristics of the desired composite material, the temperature range in which the composite material will be used, etc.

[0038] Furthermore, the negative thermal expansion material according to the present embodiment includes materials that exhibit a large negative volume expansion coefficient in a relatively low temperature range (30°C to 80°C) (for example, Examples 2, 3, and 4). Such materials have unique properties and can be suitably used for specific applications.

[0039] Next, a method for producing the negative thermal expansion material according to this embodiment will be described. 1 is a flowchart showing an example of a method for producing a negative thermal expansion material (MER zeolite) according to the present invention. When producing MER zeolite, first, colloidal silica and HO are placed in beaker A and stirred to mix them (step S1). Then, KOH, Al(OH)3, and HO are placed in a separately prepared beaker B and heated and stirred until they become transparent (step S2). Thereafter, the solution in beaker A and the solution in beaker B are mixed and stirred (step S3).

[0040] Thereafter, the stirred aqueous solution (mixture) is poured into a container and subjected to hydrothermal treatment (step S4). 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 circulating oven and heated to perform the hydrothermal treatment (step S4). For example, the hydrothermal treatment temperature can be 150°C, and the hydrothermal treatment time can be 3 days. Note that these hydrothermal treatment conditions are merely examples, and other conditions may also be used in the present embodiment.

[0041] After the hydrothermal treatment, the precipitate in the container is removed and washed with pure water (step S5). The washed precipitate is then dried (step S6) to obtain MER zeolite. The drying conditions can be, for example, about 110°C and 16 hours. Note that these drying conditions are merely an example, and other drying conditions may be used in this embodiment.

[0042] In the method for producing MER zeolite according to this embodiment, the composition of the MER zeolite can be changed by adjusting the composition ratio (charge molar ratio) of each raw material. In other words, the composition of the obtained MER zeolite can be changed by adjusting the ratio of SiO:Al(OH):KOH:HO.

[0043] Fig. 8 is a flowchart showing another example of a method for producing a negative thermal expansion material (MER zeolite) according to the present invention. In the production method shown in Fig. 8, first, KOH, Al(OH), HPO, and H0 are placed in a beaker, and the mixture is heated and stirred until transparent (step S11). Then, colloidal silica is added to the beaker and stirred (step S12).

[0044] The stirred aqueous solution (mixture) is then poured into a Teflon (registered trademark) container and set in a pressure-resistant stainless steel outer cylinder. The container is then placed in a hot air circulating oven and heated to perform hydrothermal treatment (step S13).

[0045] After the hydrothermal treatment, the precipitate in the removed Teflon container is washed with pure water (step S14), and then the washed precipitate is dried to obtain MER zeolite (step S15).

[0046] The manufacturing method shown in Figure 8 differs from the manufacturing method shown in Figure 1 in that phosphorus (H3PO4) is added. In the manufacturing method shown in Figure 8, phosphorus is added to the starting material, but phosphorus does not enter the finally obtained zeolite.

[0047] Fig. 12 is a flowchart showing another example of a method for producing a negative thermal expansion material (MER zeolite) according to the present invention. In the production method shown in Fig. 12, first, silica, a tetraethylammonium hydroxide (TEAOH) solution, and H2O are placed in beaker A and stirred to mix them (step S21). Then, KOH, Al(OH)3, and H2O are placed in beaker B and heated and stirred (step S22). Thereafter, the solution in beaker A and the solution in beaker B are mixed and stirred (step S23).

[0048] The stirred aqueous solution (mixture) is then placed in a Teflon (registered trademark) container and set in a pressure-resistant stainless steel outer cylinder. This container is then placed in a hot air circulating oven and heated for hydrothermal treatment (step S24). After the hydrothermal treatment, the precipitate in the removed Teflon container is washed with pure water (step S25). The washed precipitate is then dried to obtain MER zeolite (step S26). The manufacturing method shown in FIG. 12 differs from the manufacturing method shown in FIG. 1 in that TEAOH is used.

[0049] Next, a method for substituting (ion-exchanging) a portion of the K contained in the MER zeolite with at least one element selected from the group consisting of H, Li, Na, Ag, NH4, Mg, Ca, Sr, Ba, Cd, Ni, Zn, Cu, Hg, Fe, Co, Sn, Pb, Mn, Al, Cr, Y, Zr, Ti, lanthanoids, and tetraethylammonium ions will be described. In the negative thermal expansion material according to this embodiment, substituting a portion of the K contained in the MER zeolite with these elements makes it possible to adjust the volume expansion coefficient of the negative thermal expansion material.

[0050] FIG. 20 is a flowchart illustrating an example of an ion exchange method for MER zeolite. First, a 0.1 M aqueous nitric acid solution (MNO3 aq.) is prepared in a beaker using replacement raw material A (step S41). Here, "M" is Mg, Ca, or Na. For example, when replacing part of the K with Mg, Mg(NO3)2·6H2O can be used as replacement raw material A. When replacing part of the K with Ca, Ca(NO3)2·4H2O can be used as replacement raw material A. When replacing part of the K with Na, NaNO3 can be used as replacement raw material A. When replacing part of the K with an element other than these, a nitric acid aqueous solution of that element can also be used as replacement raw material A.

[0051] Thereafter, the MER zeolite is placed in a beaker and stirred, for example, at 80°C for 24 hours (step S42). Note that the stirring conditions (temperature, time) may be other than those described above. Next, the stirred sample is subjected to suction filtration with pure water and washed with pure water (step S43). Thereafter, the washed sample is again placed in a 0.1 M aqueous nitric acid solution (MNO3 aq.), and the process of stirring at 80°C for 24 hours (step S42) and the process of suction filtration and pure water washing (step S43) are repeated a total of seven times. Thereafter, the sample is dried at 110°C for 16 hours (step S44), thereby obtaining MER zeolite substituted with M ions (M-MER zeolite). Note that these drying conditions are merely an example, and other drying conditions may also be used in this embodiment.

[0052] When a portion of K contained in MER zeolite is substituted (ion exchanged) with a predetermined element M, the amount of substitution (amount of substitution element M) can be adjusted by using the concentration of the nitric acid aqueous solution prepared in step S41, the stirring time and temperature in step S42, the number of times steps S42 and S43 are repeated, etc. For example, the amount of substitution element M substituting for K can be increased by increasing the concentration of the nitric acid aqueous solution prepared in step S41, the longer the stirring time in step S42, the higher the stirring temperature in step S42, or the more times steps S42 and S43 are repeated.

[0053] Next, a method for producing LTA zeolite and FAU zeolite will be described. Fig. 24 is a flowchart showing an example of a method for producing LTA zeolite and FAU zeolite. When producing LTA zeolite and FAU zeolite, first, NaOH, NaAlO2, and HO are placed in a beaker and stirred until dissolved (step S51). Thereafter, colloidal silica is placed in the beaker and stirred for 24 hours (step S52).

[0054] The stirred aqueous solution (mixture) is then transferred to an autoclave and heated in an oven at 65°C for 7 days (step S53). It is then water-cooled at 25°C for 1 hour (step S54), and further cooled in a refrigerator (at 8°C) for 30 minutes (step S55). The cooled sample is then centrifuged at 13,000 rpm for 45 minutes (step S56). The residue obtained by centrifugation is then mixed with pure water for washing (step S57). These operations (steps S56 and S57) are repeated, for example, three times. The mixture is then dried overnight at room temperature (step S58), thereby obtaining the LTA zeolite and FAU zeolite according to this embodiment. The above conditions (temperature, time, and centrifugation conditions) are merely examples, and these conditions can be determined arbitrarily in this embodiment.

[0055] In the method for producing LTA zeolite and FAU zeolite according to this embodiment, the composition of the LTA zeolite and FAU zeolite can be changed by adjusting the composition ratio (charge molar ratio) of the respective raw materials. In other words, the composition of the obtained LTA zeolite and FAU zeolite can be changed by adjusting the values ​​of SiO:AlO:NaOH:H0.

[0056] Next, a method for producing GIS-type zeolite will be described. FIG. 27 is a flowchart showing an example of a method for producing GIS-type zeolite. In the production method shown in FIG. 27, first, NaAlO2, NaOH, and H2O are placed in a beaker and stirred to mix them (step S61). Then, colloidal silica is added to the beaker and stirred (step S62). 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 circulating oven and heated to perform hydrothermal treatment (step S63).

[0057] After the hydrothermal treatment, the precipitate in the removed Teflon container is washed with pure water (step S64), and then the washed precipitate is dried to obtain GIS-type zeolite (step S65).

[0058] In the method for producing GIS zeolite according to the present embodiment, the composition of GIS zeolite can be changed by adjusting the composition ratio (charge molar ratio) of each raw material.

[0059] Next, we will explain a method of substituting (ion-exchanging) a portion of the Na contained in GIS-type zeolite with at least one element selected from the group consisting of H, Li, K, Ag, NH4, Mg, Ca, Sr, Ba, Cd, Ni, Zn, Cu, Hg, Fe, Co, Sn, Pb, Mn, Al, Cr, Y, Zr, Ti, and lanthanoids.

[0060] FIG. 31 is a flowchart illustrating an example of an ion exchange method for GIS-type zeolite. First, a 1 M aqueous hydrochloric acid solution (MCi aq.) is prepared in a beaker using replacement raw material B (step S71). Here, "M" is Mg, Ca, K, or Li. For example, when replacing part of Na with Mg, MgCl2·6H2O can be used as replacement raw material B. When replacing part of Na with Ca, CaCl2·2H2O can be used as replacement raw material B. When replacing part of Na with K, KCl can be used as replacement raw material B. When replacing part of Na with Li, LiCl can be used as replacement raw material B. When replacing part of Na with an element other than these, an aqueous hydrochloric acid solution of that element can also be used as replacement raw material B.

[0061] Thereafter, the GIS zeolite is placed in a beaker and stirred, for example, at 80°C for 24 hours (step S72). Note that the stirring conditions (temperature, time) may be other than these conditions. Next, the stirred sample is filtered and washed with pure water (step S73). Thereafter, it is dried at 110°C for 16 hours (step S74), thereby obtaining GIS zeolite substituted with M ions (M-GIS zeolite). Note that these drying conditions are one example, and the drying conditions in this embodiment may be other than these conditions. [Example]

[0062] Examples of the present invention will be described below.

[0063] Example 1 MER zeolite was produced as Example 1. FIG. 1 is a flowchart showing a method for producing MER zeolite. First, colloidal silica (concentration 30 wt %: Snowtex Na type ST-30, manufactured by Nissan Chemical Co., Ltd.) and H2O were placed in beaker A and stirred to mix (step S1). Furthermore, KOH, Al(OH)3, and H2O were placed in beaker B and heated and stirred until they became transparent (step S2). Thereafter, the solution in beaker A and the solution in beaker B were mixed and stirred (step S3).

[0064] The stirred aqueous solution (mixture) was then poured into a Teflon (registered trademark) container (HUT-100, San-Ai Scientific Co., Ltd.) and placed in a pressure-resistant stainless steel outer tube (HUS-100, San-Ai Scientific Co., Ltd.). The container was then placed in a hot air circulating oven (KLO-45M, Koyo Thermo Systems Co., Ltd.) and heated to perform hydrothermal treatment (step S4). The hydrothermal treatment temperature was 150°C, and the hydrothermal treatment time was 3 days.

[0065] After the hydrothermal treatment, a precipitate was found in the Teflon container. This precipitate was washed with pure water (Step S5). The washed precipitate was then dried at a temperature of approximately 110°C for 16 hours to obtain a white solid (Step S6).

[0066] The composition ratio (charge molar ratio) of the raw materials in Example 1 was SiO2:Al(OH)3:KOH:H2O=5:1:6:100.

[0067] The composition (atomic ratio) of the sample prepared in 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

[0068] As a result of 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 ]·yH2O ···Example 1

[0069] The thermal expansion coefficient of the sample according to Example 1 was measured using the following method. A benchtop heating stage (BTS 500, AntonPaar) was attached to the following powder X-ray diffractometer, and X-ray diffraction patterns were measured at any temperature. A high-speed one-dimensional detector (D / teX Ultra2, Rigaku Corporation) was used as the detector, and measurements were performed under the following conditions. Si (NIST SRM 640c) was used as the internal standard. [High temperature XRD (HT-XRD)] Equipment used: Mini Flex 600 (Rigaku Corporation) Atmosphere: Air Tube current / voltage: 15mA / 40kV Target: Cu Step width: 0.02° Measurement range (scanning speed): 5 to 75° (4° / min) ·Measurement temperature: 30~220℃

[0070] The obtained X-ray diffraction pattern (HT-XRD measurement result: temperature increase) is shown in Figure 2. In addition, the X-ray diffraction pattern when the sample was cooled after heating was also measured. The obtained X-ray diffraction pattern (HT-XRD measurement result: temperature decrease) is shown in Figure 3.

[0071] 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 temperature, and the linear thermal expansion coefficient α for each crystal axis was calculated using the following equation within the linearly approximated temperature range. l and the volumetric thermal expansion coefficient α v was calculated.

[0072]

number

number

[0073] 4 shows the volumetric thermal expansion coefficient and the linear thermal expansion coefficient for each crystal axis. The volumetric thermal expansion coefficient of the sample according to Example 1 is −236 (ppmK) in the temperature range of 30 to 160° C. -1 ) was.

[0074] <Example 2> MER zeolite was produced as Example 2. The sample according to Example 2 was also produced using the same method as in Example 1. The composition ratio (charge molar ratio) of each raw material in Example 2 was SiO2:Al(OH)3:KOH:H2O = 5:2:6:100.

[0075] Furthermore, 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, and the composition of the sample according to Example 2 was found to be as follows. K 10.3 [Al 10.6 Si 21.4 O 64 ]·yH2O ···Example 2

[0076] The thermal expansion coefficient of the sample according to Example 2 was measured using the same method as in Example 1. Figure 5 shows the volumetric thermal expansion coefficient and the linear thermal expansion coefficient for each crystal axis. The volumetric thermal expansion coefficient of the sample according to Example 2 was -184 (ppmK) in the temperature range of 60 to 180°C. -1), -908 (ppmK) in the temperature range of 40 to 60°C -1 ) was.

[0077] Example 3 MER zeolite was produced as Example 3. The sample according to Example 3 was also produced using the same method as in Example 1. The composition ratio (charge molar ratio) of each raw material in Example 3 was SiO2:Al(OH)3:KOH:HO = 5:3:6:100.

[0078] Furthermore, 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, and the composition of the sample according to Example 3 was found to be as follows. K 11.6 [Al 11.6 Si 20.4 O 64 ]·yH2O ···Example 3

[0079] The thermal expansion coefficient of the sample according to Example 3 was measured using the same method as in Example 1. Figure 6 shows the volumetric thermal expansion coefficient and the linear thermal expansion coefficient for each crystal axis. The volumetric thermal expansion coefficient of the sample according to Example 3 was -98.6 (ppmK) in the temperature range of 60 to 160°C. -1 ), -942 (ppmK) in the temperature range of 40 to 60°C -1 ) was.

[0080] Example 4 MER zeolite was produced as Example 4. The sample according to Example 4 was also produced using the same method as in Example 1. The composition ratio (charge molar ratio) of each raw material in Example 4 was SiO2:Al(OH)3:KOH:H2O = 5:2:12:100.

[0081] Furthermore, 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, and the composition of the sample according to Example 4 was found to be as follows. K 11.7 [Al 11.7 Si 20.3 O 64]·yH2O ···Example 4

[0082] The thermal expansion coefficient of the sample according to Example 4 was measured using the same method as in Example 1. Figure 7 shows the volumetric thermal expansion coefficient and the linear thermal expansion coefficient for each crystal axis. The volumetric thermal expansion coefficient of the sample according to Example 4 was -106 (ppmK) in the temperature range of 60 to 140°C. -1 ), -925 (ppmK) in the temperature range of 40 to 60°C -1 ) was.

[0083] <Example 5> MER zeolite was produced as Example 5. Fig. 8 is a flowchart showing a method for producing MER zeolite. First, KOH, Al(OH)3, H3PO4, and HO were placed in a beaker, and the mixture was heated and stirred until transparent (Step S11). Then, colloidal silica (concentration 30 wt%: Snowtex Na type ST-30, manufactured by Nissan Chemical Co., Ltd.) was added to the beaker and stirred (Step S12).

[0084] The stirred aqueous solution (mixture) was then poured into a Teflon (registered trademark) container (HUT-100, San-Ai Scientific Co., Ltd.) and placed in a pressure-resistant stainless steel outer tube (HUS-100, San-Ai Scientific Co., Ltd.). The container was then placed in a hot air circulating oven (KLO-45M, Koyo Thermo Systems Co., Ltd.) and heated to perform hydrothermal treatment (step S13). The hydrothermal treatment temperature was 150°C, and the hydrothermal treatment time was 3 days.

[0085] After the hydrothermal treatment, a precipitate was formed in the Teflon container. This precipitate was washed with pure water (Step S14). The washed precipitate was then dried at a temperature of approximately 110°C for 16 hours to obtain a white solid (Step S15).

[0086] The composition ratio (charge molar ratio) of the raw materials in Example 5 was SiO2:Al(OH)3:KOH:H3PO4:H2O=4.25:2.375:6:0.375:100.

[0087] By using the above-mentioned production method, a single-phase MER zeolite was produced. The composition (atomic ratio) of the produced sample was analyzed using ICP-OES, and the composition of the sample according to Example 5 was as follows: K 13.6 [Al 13.4 Si 18.6 O 64 ]·yH2O ···Example 5

[0088] The production method of Example 5 differs from the production method of Example 1 in that phosphorus (H3PO4) is added. In the production method of Example 5, phosphorus is added to the starting material, but the finally obtained zeolite does not contain phosphorus.

[0089] In addition, HT-XRD measurements were performed to determine the lattice constant from room temperature to 250°C (Figure 9). From these results, the thermal expansion coefficient was calculated to be -39 (ppmK) in the temperature range of 30 to 50°C. -1 ), -76 (ppmK) in the temperature range of 70 to 130°C -1 ), -187 (ppmK) in the temperature range of 150 to 230°C -1 ) was.

[0090] Example 6 MER zeolite was produced as Example 6. The sample of Example 6 was also produced using the same method as in Example 5. The composition ratio (charge molar ratio) of the raw materials in Example 6 was SiO2:Al(OH)3:KOH:H3PO4:H2O = 4.5:2.25:6:0.25:100. Single-phase MER zeolite was also produced in this example.

[0091] The composition (atomic ratio) of the prepared sample was analyzed using ICP-OES, and the composition of the sample was found to be as follows: K 12.8 [Al 12.8 Si 19.2 O 64 ]·yH2O ···Example 6

[0092] In addition, HT-XRD measurements were performed to determine the lattice constant from room temperature to 230°C (Figure 6). From these results, the thermal expansion coefficient was calculated to be -105 (ppmK) in the temperature range of 70 to 150°C. -1 ), -45 (ppmK) in the temperature range of 170 to 230°C -1 ) was.

[0093] Example 7 MER zeolite was produced as Example 7. The sample of Example 7 was also produced using the same method as in Example 5. The composition ratio (charge molar ratio) of the raw materials in Example 7 was SiO2:Al(OH)3:KOH:H3PO4:H2O = 4.75:2.125:6:0.125:100. Single-phase MER zeolite was also produced in this example.

[0094] The composition (atomic ratio) of the prepared sample was analyzed using ICP-OES, and the composition of the sample was found to be as follows: K 11.5 [Al 11.5 Si 20.5 O 64 ]·yH2O ···Example 7

[0095] In addition, HT-XRD measurements were performed to determine the lattice constant from room temperature to 250°C (Fig. 11). From these results, the thermal expansion coefficient was calculated to be -186 (ppmK) in the temperature range of 30 to 70°C. -1 ), -42.2 (ppmK) in the temperature range of 90 to 150°C -1 ), -50 (ppmK) in the temperature range of 170 to 250°C -1 ) was.

[0096] Example 8 MER zeolite was produced as Example 8. Fig. 12 is a flowchart showing a method for producing MER zeolite. First, silica (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), a 35% tetraethylammonium hydroxide (TEAOH) solution, and H2O were placed in beaker A and stirred to mix (step S21). Furthermore, KOH, Al(OH)3, and H2O were placed in beaker B and heated and stirred (step S22). Thereafter, the solution in beaker A and the solution in beaker B were mixed and stirred (step S23).

[0097] The stirred aqueous solution (mixture) was then placed in a Teflon (registered trademark) container (HUT-100, San-Ai Scientific Co., Ltd.) and placed in a pressure-resistant stainless steel outer tube (HUS-100, San-Ai Scientific Co., Ltd.). This container was then placed in a hot air circulating oven (KLO-45M, Koyo Thermo Systems Co., Ltd.) and heated to perform hydrothermal treatment (step S24). The hydrothermal treatment temperature was 150°C, and the hydrothermal treatment time was 3 days. After the hydrothermal treatment, a precipitate was formed in the removed Teflon container. This precipitate was washed with pure water (step S25). The washed precipitate was then dried at a temperature of approximately 110°C for 16 hours to obtain a white solid (step S26).

[0098] The composition ratio (charge molar ratio) of each raw material in Example 8 was SiO2:Al(OH)3:KOH:TEAOH:HO=5:1:3:1:150. By using the above-mentioned production method, a single-phase MER zeolite was produced. The production method in Example 8 differs from the production method in Example 1 in that TEAOH is used.

[0099] The composition (atomic ratio) of the prepared sample was analyzed using ICP-OES, and the composition of the sample according to Example 8 was found to be as follows. K 8.4 [Al 9.0 Si 23.0 O 64 ]·yH2O ···Example 8

[0100] The HT-XRD measurement results for the sample according to Example 8 are shown in FIG. 13. As shown in FIG. 13, it was found that the sample according to Example 8 did not decompose up to 500°C. The lattice constant was also calculated from room temperature to 500°C (FIG. 14). The thermal expansion coefficient was calculated from these results and was found to be -430 (ppmK) in the temperature range of 30 to 230°C. -1 ), -193 (ppmK) in the temperature range of 70 to 150°C -1 ) was.

[0101] Example 9 MER-type zeolite was prepared as Example 9. The sample of Example 9 was also prepared using the same method as in Example 8. The composition ratio (charge molar ratio) of the raw materials in Example 9 was SiO2:Al(OH)3:KOH:TEAOH:H2O = 5:1:1.5:y:150, where y was set to 0 to 9.5. A sample was also prepared in which the composition ratio (charge molar ratio) of the raw materials was SiO2:Al(OH)3:KOH:TEAOH:H2O = 5:1:1.0:9.0:150.

[0102] The results of XRD measurement of the samples prepared in this manner are shown in Figure 15. From the results shown in Figure 15, it can be seen that single-phase MER-type zeolites could be prepared in the range of y = 1.0 to 9.5. Furthermore, when the compositions (atomic ratios) of these samples were analyzed using ICP-OES, the compositions were as follows:

[0103] y=1.0: K 6.7 [Al 6.7 Si 25.2 O 64 ]·yH2O y=2.5: K 6.8 [Al 8.3 Si 23.7 O 64 ]·yH2O y=5.0: K 9.0 [Al 8.9 Si 23.1 O 64 ]·yH2O y=7.5: K 9.2 [Al 9.2 Si 22.8 O 64 ]·yH2O y=9.5: K 9.3 [Al 9.3 Si 22.7 O 64 ]·yH2O y=1.0: K 6.7 [Al 6.7 Si 25.2 O 64 ]·yH2O

[0104] Among the above samples, the sample with y=1.0 (K 6.7 [Al 6.7 Si 25.2 O 64 The HT-XRD measurement results of the sample (Fig. 16) are shown. The lattice constant of the sample was also calculated from room temperature to 270°C (Fig. 17). The thermal expansion coefficient was calculated from these results and was found to be -121.5 (ppmK) in the temperature range of 30 to 230°C. -1 ), -111.4 (ppmK) in the temperature range of 30 to 270°C -1 ) was.

[0105] Example 10 MER zeolite was produced as Example 10. Fig. 18 is a flowchart showing a method for producing MER zeolite. First, silica (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and HO were placed in beaker A and stirred to mix them (step S31). Furthermore, KOH, Al(OH) and HO were placed in beaker B and heated and stirred (step S32). Thereafter, the solution in beaker A and the solution in beaker B were mixed and stirred (step S33).

[0106] The stirred aqueous solution (mixture) was then placed in a Teflon (registered trademark) container (HUT-100, San-Ai Scientific Co., Ltd.) and placed in a pressure-resistant stainless steel outer tube (HUS-100, San-Ai Scientific Co., Ltd.). The container was then placed in a hot air circulating oven (KLO-45M, Koyo Thermo Systems Co., Ltd.) and heated for hydrothermal treatment (step S34). The hydrothermal treatment temperature was 150°C, and the hydrothermal treatment time was 3 days. After the hydrothermal treatment, a precipitate was formed in the removed Teflon container. This precipitate was washed with pure water (step S35). The washed precipitate was then dried at approximately 110°C for 16 hours to obtain a white solid (step S36). The composition ratio (charge molar ratio) of each raw material in Example 10 was SiO2:Al(OH)3:KOH:HO = 5:1:z:150, where z was 1.25 to 12.0.

[0107] The results of XRD measurement of the samples prepared in this manner are shown in Figure 19. From the results shown in Figure 19, it is possible to prepare single-phase MER-type zeolites in the range of z = 2.25 to 12.0. Furthermore, when the compositions (atomic ratios) of these samples were analyzed using ICP-OES, the compositions were as follows:

[0108] z=2.25: K 6.7 [Al 7.0 Si 25.0 O 64 ]·yH2O z=2.5: K 6.8 [Al 7.1 Si 24.9 O 64 ]·yH2O z=3.0: K 7.2 [Al 7.7 Si 24.3 O 64 ]·yH2O z=4.0: K 9.3 [Al 9.5 Si 22.5 O 64 ]·yH2O z=12.0: K 11.2 [Al 12.8 Si 19.2 O 64 ]·yH2O

[0109] Example 11 A sample in which part of the K in the MER zeolite was substituted with Ca (ion-exchanged) was prepared as Example 11. In Example 11, part of the K in the sample of Example 2 was substituted with Ca.

[0110] 20 is a flow chart for explaining the ion exchange method for MER zeolite. First, as a replacement raw material A, 5.0 × 10 -3 Using 50 ml of HCl and 50 ml of H2O, a 0.1 M aqueous solution of calcium nitrate (Ca(NO3)2aq.) was prepared in a beaker (step S41).

[0111] Thereafter, 3 g of the sample according to Example 2 as MER zeolite was placed in a beaker and stirred at 80°C for 24 hours (step S42). Next, the stirred sample was subjected to suction filtration with pure water and washed with pure water (step S43). Thereafter, the washed sample was placed in a 0.1 M aqueous solution of calcium nitrate (Ca(NO3)2 aq.), and the process of stirring at 80°C for 24 hours (step S42) and the process of suction filtration and pure water washing (step S43) were repeated a total of seven times. Thereafter, the sample was dried at 110°C for 16 hours (step S44) to obtain MER zeolite substituted with Ca ions (Ca-MER).

[0112] The composition (atomic ratio) of the prepared sample of Example 11 was analyzed using ICP-OES in the same manner as in Example 1, and the composition of the sample of Example 11 was found to be as follows. K 5.0 Ca 2.6 [Al 10.7 Si 21.3 O 64 ]·yH2O ···Example 11

[0113] The thermal expansion coefficient of the sample according to Example 11 was measured using the same method as in Example 1. FIG. 21 shows the volumetric thermal expansion coefficient and the linear thermal expansion coefficient for each crystal axis. The volumetric thermal expansion coefficient of the sample according to Example 11 was −246 (ppmK) in the temperature range of 30 to 160°C.-1 ) was.

[0114] Example 12 A sample was prepared as Example 12 in which part of the K in the MER zeolite was replaced with Mg (ion-exchanged). In Example 12, part of the K in the sample of Example 2 was replaced with Mg.

[0115] In Example 12, as in Example 11, ion exchange of MER zeolite was carried out using the method shown in the flowchart of Figure 20. First, as a replacement raw material A, 5.0 × 10 Mg(NO3)2·6H2O was added. -3 Using 50 ml of HCl and 50 ml of H2O, a 0.1 M aqueous solution of magnesium nitrate (Mg(NO3)2aq.) was prepared in a beaker (step S41).

[0116] Thereafter, 3 g of the sample according to Example 2 as MER zeolite was placed in a beaker and stirred at 80°C for 24 hours (Step S42). Next, the stirred sample was subjected to suction filtration with pure water and washed with pure water (Step S43). Thereafter, the washed sample was placed in a 0.1 M magnesium nitrate aqueous solution (Mg(NO3)2 aq.), and the process of stirring at 80°C for 24 hours (Step S42) and the process of suction filtration and pure water washing (Step S43) were repeated a total of seven times. Thereafter, the sample was dried at 110°C for 16 hours (Step S44) to obtain MER zeolite substituted with Mg ions (Mg-MER).

[0117] The composition (atomic ratio) of the prepared sample of Example 12 was analyzed by ICP-OES in the same manner as in Example 1, and the composition of the sample of Example 12 was found to be as follows. K 6.7 Mg 2.0 [Al 10.8 Si 21.2 O 64 ]·yH2O ···Example 12

[0118] The thermal expansion coefficient of the sample according to Example 12 was measured using the same method as in Example 1. FIG. 22 shows the volumetric thermal expansion coefficient and the linear thermal expansion coefficient for each crystal axis. The volumetric thermal expansion coefficient of the sample according to Example 12 was −427 (ppmK) in the temperature range of 30 to 80°C. -1 ), -39.7 (ppmK) in the temperature range of 80 to 220°C -1 ) was.

[0119] Example 13 A sample was prepared as Example 13 in which part of the K in the MER zeolite was substituted with Na (ion-exchanged). In Example 13, part of the K in the sample of Example 2 was substituted with Na.

[0120] In Example 13, as in Example 11, ion exchange of MER zeolite was carried out using the method shown in the flowchart of Figure 20. First, as a replacement raw material A, NaNO3 was added to 5.0 × 10 -3 Using 50 ml of HCl and 50 ml of H2O, a 0.1 M aqueous solution of sodium nitrate (NaNO3 aq.) was prepared in a beaker (step S41).

[0121] Thereafter, 3 g of the sample according to Example 2 as MER zeolite was placed in a beaker and stirred at 80°C for 24 hours (Step S42). Next, the stirred sample was subjected to suction filtration with pure water and washed with pure water (Step S43). Thereafter, the washed sample was placed in a 0.1 M magnesium nitrate aqueous solution (NaNO3 aq.), and the process of stirring at 80°C for 24 hours (Step S42) and the process of suction filtration and pure water washing (Step S43) were repeated a total of seven times. Thereafter, the sample was dried at 110°C for 16 hours (Step S44) to obtain a MER zeolite substituted with Na ions (Na-MER).

[0122] The composition (atomic ratio) of the prepared sample of Example 13 was analyzed by ICP-OES in the same manner as in Example 1, and the composition of the sample of Example 13 was found to be as follows. K 3.9 Na 6.5 [Al 10.8 Si21.2 O 64 ]·yH2O ···Example 13

[0123] The thermal expansion coefficient of the sample according to Example 13 was measured using the same method as in Example 1. FIG. 23 shows the volumetric thermal expansion coefficient and the linear thermal expansion coefficient for each crystal axis. The volumetric thermal expansion coefficient of the sample according to Example 13 was −189 (ppmK) in the temperature range of 30 to 100°C. -1 ), -594 (ppmK) in the temperature range of 120 to 220°C -1 ) was.

[0124] Example 14 LTA zeolite was produced as Example 14. Fig. 24 is a flowchart showing a method for producing LTA zeolite. First, NaOH, NaAlO2, and HO were placed in a beaker and stirred until dissolved (step S51). Thereafter, colloidal silica (concentration 30 wt%: Snowtex Na type ST-30, manufactured by Nissan Chemical Industries, Ltd.) was placed in the beaker and stirred for 24 hours (step S52).

[0125] The stirred aqueous solution (mixture) was then transferred to an autoclave and heated in an oven at 65°C for 7 days (step S53). It was then water-cooled at 25°C for 1 hour (step S54), and further cooled in a refrigerator (at 8°C) for 30 minutes (step S55). The cooled sample was then centrifuged at 13,000 rpm for 45 minutes (step S56). The residue obtained by centrifugation was then mixed with pure water for washing (step S57). These steps (steps S56 and S57) were repeated three times. The mixture was then dried overnight at room temperature (step S58), yielding an LTA zeolite according to Example 14.

[0126] The composition ratio (charge molar ratio) of the raw materials in Example 14 was SiO2:Al2O3:NaOH:H2O=1:1:11:190.

[0127] Furthermore, the composition (atomic ratio) of the prepared sample of Example 14 was analyzed using ICP-OES in the same manner as in Example 1, and the composition of the sample of Example 14 was found to be as follows. Na 12.1 [Al 13.2 Si 10.8 O 48 ]·yH2O Example 14

[0128] The thermal expansion coefficient of the sample according to Example 14 was measured using the same method as in Example 1. Figure 25 shows the volumetric thermal expansion coefficient and the linear thermal expansion coefficient for each crystal axis. The volumetric thermal expansion coefficient of the sample according to Example 14 was -160 (ppmK) in the temperature range of 30 to 80°C. -1 ), -20.6 (ppmK) in the temperature range of 250 to 500°C -1 ) was.

[0129] Example 15 FAU-type zeolite was produced as Example 15. The sample of Example 15 was also produced using the same method as in Example 14. The composition ratio (charge molar ratio) of each raw material in Example 15 was SiO2:Al2O3:NaOH:H2O = 3:1:11:190.

[0130] Furthermore, the composition (atomic ratio) of the prepared sample of Example 15 was analyzed using ICP-OES in the same manner as in Example 1, and the composition of the sample of Example 15 was found to be as follows. Na 82.1 [Al 87.5 Si 104.5 O 384 ]·yH2O Example 15

[0131] The thermal expansion coefficient of the sample according to Example 15 was measured using the same method as in Example 1. FIG. 26 shows the volumetric thermal expansion coefficient and the linear thermal expansion coefficient for each crystal axis. The volumetric thermal expansion coefficient of the sample according to Example 15 was −69.2 (ppmK) in the temperature range of 30 to 80°C. -1 ), -13.6 (ppmK) in the temperature range of 350 to 500°C -1 ) was.

[0132] Example 16 GIS-type zeolite was produced as Example 16. FIG. 27 is a flowchart showing a method for producing GIS-type zeolite. First, NaAlO, NaOH, and H2O were placed in a beaker and stirred to mix (step S61). Then, colloidal silica (concentration 30 wt%: Snowtex Na Type ST-30, manufactured by Nissan Chemical Co., Ltd.) was added to the beaker and stirred (step S62). The stirred aqueous solution (mixture) was then poured into a Teflon (registered trademark) container (HUT-100, San-ai Scientific Co., Ltd.) and set in a pressure-resistant stainless steel outer cylinder (HUS-100, San-ai Scientific Co., Ltd.). The container was then placed in a hot air circulation oven (KLO-45M, Koyo Thermo Systems Co., Ltd.) and heated to perform hydrothermal treatment (step S63). The hydrothermal treatment temperature was 100°C, and the hydrothermal treatment time was 7 days.

[0133] After the hydrothermal treatment, a precipitate was formed in the removed Teflon container. This precipitate was washed with pure water (step S64). The washed precipitate was then dried at a temperature of approximately 110°C for 16 hours to obtain a white solid (step S65). The composition ratio (charge molar ratio) of each raw material in Example 16 was SiO2:NaAlO2:NaOH:H2O = 3.7:0.41:9.5:173.

[0134] By using the above-mentioned production method, a single-phase GIS-type zeolite was produced. The composition (atomic ratio) of the produced sample was analyzed using ICP-OES, and the composition of the sample according to Example 16 was as follows: Na 6.5 [Al 6.9 Si 9.2 O 32 ]·yH2O Example 16

[0135] In addition, HT-XRD was measured to determine the lattice constant from room temperature to 500°C (Fig. 28). From these results, the thermal expansion coefficient was calculated to be -61 (ppmK) in the temperature range of 30 to 70°C. -1 ), -101 (ppmK) in the temperature range of 90 to 140°C-1 ), -126 (ppmK) in the temperature range of 150 to 350°C -1 ) in the temperature range of 30 to 350°C. -1 ) was.

[0136] Example 17 GIS-type zeolite was produced as Example 17. The sample of Example 17 was also produced using the same method as in Example 16. The composition ratio (charge molar ratio) of the raw materials in Example 17 was SiO2:NaAlO2:NaOH:H2O = 10:1.11:8.6:173.

[0137] By using the above-mentioned production method, a single-phase GIS-type zeolite was produced. The composition (atomic ratio) of the produced sample was analyzed using ICP-OES, and the composition of the sample according to Example 17 was as follows: Na 5.2 [Al 5.3 Si 10.7 O 32 ]·yH2O Example 17

[0138] In addition, HT-XRD was measured to determine the lattice constant from room temperature to 500°C (Fig. 29). From these results, the thermal expansion coefficient was calculated to be -40 (ppmK) in the temperature range of 30 to 50°C. -1 ), -98 (ppmK) in the temperature range of 70 to 90°C -1 ), -53 (ppmK) in the temperature range of 110 to 140°C -1 ), -106(ppmK in the temperature range of 150 to 350°C -1 ) in the temperature range of 30 to 350°C. -1 ) was.

[0139] Example 18 GIS-type zeolite was produced as Example 18. The sample of Example 18 was also produced using the same method as in Example 16. The composition ratio (charge molar ratio) of the raw materials in Example 18 was SiO2:NaAlO2:NaOH:H2O = 10:2.5:6.9:173.

[0140] By using the above-mentioned production method, a single-phase GIS-type zeolite was produced. The composition (atomic ratio) of the produced sample was analyzed using ICP-OES, and the composition of the sample according to Example 18 was as follows: Na 5.8 [Al 5.9 Si 10.1 O 32 ]·yH2O Example 18

[0141] In addition, HT-XRD was measured to determine the lattice constant from room temperature to 500°C (Fig. 30). From these results, the thermal expansion coefficient was calculated to be -74 (ppmK) in the temperature range of 50 to 70°C. -1 ), -96(ppmK in the temperature range of 90 to 140°C -1 ), -113 (ppmK) in the temperature range of 150 to 350°C -1 ) in the temperature range of 30 to 350°C. -1 ) was.

[0142] Example 19 As Example 19, a sample was prepared in which part of the Na in GIS-type zeolite was substituted (ion exchanged) with Mg, Ca, K, or Li. In Example 19, part of the Na in the sample of Example 16 was substituted with Mg, Ca, K, or Li.

[0143] 31 is a flowchart for explaining the ion exchange method for GIS-type zeolite. First, as the raw material B for substitution, 1.5 × 10 -2 Using 15 ml of HCl, 1 M aqueous magnesium chloride solution (MgCl2 aq.), 1 M aqueous calcium chloride solution (CaCl2 aq.), 1 M aqueous potassium chloride solution (KCl aq.), and 1 M aqueous lithium chloride solution (LiCl aq.) were prepared in beakers (step S71).

[0144] Thereafter, 0.5 g of the sample according to Example 16 as GIS zeolite was placed in a beaker and stirred at 80°C for 24 hours (step S72). Next, the stirred sample was filtered and washed with pure water (step S73). Thereafter, it was dried at 110°C for 16 hours (step S74) to obtain GIS zeolite substituted with Mg, Ca, K, or Li ions (Mg-GIS, Ca-GIS, K-GIS, or Li-GIS).

[0145] The composition (atomic ratio) of the prepared sample of Example 19 was analyzed by ICP-OES in the same manner as in Example 1, and the composition of the sample of Example 19 was found to be as follows. Mg-GIS type:Na 3.9 Mg 1.2 [Al 6.1 Si 9.9 O 32 ]·yH2O Ca-GIS type: Na 0.8 Ca 2.8 [Al 6.2 Si 9.8 O 32 ]·yH2O K-GIS type :K 5.3 [Al 6.0 Si 10.0 O 32 ]·yH2O Li-GIS type: Na 4.0 Li 2.0 [Al 6.2 Si 9.8 O 32 ]·yH2O

[0146] Example 20 As Example 20, a sample was prepared in which part of the Na in GIS-type zeolite was replaced (ion-exchanged) with Mg, Ca, K, or Li. The sample according to Example 20 was also prepared using the same method as in Example 19. In Example 20, part of the Na in the sample according to Example 17 was replaced with Mg, Ca, K, or Li.

[0147] The composition (atomic ratio) of the prepared sample of Example 20 was analyzed by ICP-OES in the same manner as in Example 1, and the composition of the sample of Example 20 was found to be as follows. Mg-GIS type:Na 3.8 Mg 0.7 [Al 5.4 Si 10.6 O 32 ]·yH2O Ca-GIS type: Na 0.8 Ca 2.2 [Al 5.4 Si 10.6 O 32 ]·yH2O K-GIS type :K 4.5 [Al 5.3 Si 10.7 O 32 ]·yH2O Li-GIS type: Na 3.4 Li 1.8 [Al 5.3 Si 10.7 O 32 ]·yH2O

[0148] <Summary> 32 to 34 are tables summarizing the molar ratios, compositions, volume expansion coefficients, and temperature ranges of the samples of Examples 1 to 18. The samples of Examples 1 to 18 exhibit various volume expansion coefficients depending on their compositions. Furthermore, the samples of Examples 2, 3, 4, 12, and 13 have different volume expansion coefficients at high and low temperatures. Furthermore, the samples of Examples 1 to 4 and 11 to 15 have different volume expansion coefficients depending on the Si / Al ratio. For example, in the high-temperature range (60 to 160°C), the absolute value of the negative volume expansion coefficient tends to increase as the Si / Al ratio increases (i.e., as x decreases) (see Examples 1 to 4). In particular, Example 1, which has the largest Si / Al ratio, exhibited the lowest volume expansion coefficient (the largest absolute value of the negative volume expansion coefficient) in the high-temperature range (60 to 160°C).

[0149] In addition, in Example 11, in which part of the K was replaced with Ca, the volumetric thermal expansion coefficient was -246 (ppmK) in the temperature range of 30 to 160°C. -1The properties of Example 11 were similar to those of Example 1. In Example 13, in which part of the K was replaced with Na, the coefficient of volumetric thermal expansion was -594 (ppmK) in the temperature range of 120 to 220°C. -1 ) and the volume expansion coefficient was the lowest in this temperature range (the absolute value of the negative volume expansion coefficient was the largest).

[0150] Furthermore, in Example 14 (LTA zeolite), Example 15 (FAU zeolite), and Examples 16 to 18 (GIS zeolite), negative volume expansion coefficients were observed even in a relatively high temperature range (e.g., 300°C or higher). In particular, the sample of Example 14 exhibited a stable negative volume expansion coefficient at 300°C or higher.

[0151] As explained above, the negative thermal expansion materials according to Examples 1 to 18 exhibited various volume expansion coefficients depending on the composition, the substituting elements, etc. Therefore, by adjusting the composition, the substituting elements, etc., it is possible to prepare a material having a negative volume expansion coefficient suited to the application.

[0152] The present invention has been described above in accordance with the above-described embodiments, but the present invention is not limited to the configurations of the above-described embodiments, and naturally includes various modifications, alterations, and combinations that can be made by a person skilled in the art within the scope of the invention claimed in the claims of this application.

[0153] This application claims priority based on Japanese Patent Application No. 2020-186229, filed on November 9, 2020, the disclosure of which is incorporated herein in its entirety.

Claims

1. A negative thermal expansion material having a negative thermal expansion coefficient, comprising MER-type zeolite, The MER type zeolite is M （ｘ－δ） [Al ｘ Si ３２－ｘ O ６４ ]・yH ２ O, where 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, Y, Zr, Ti, lanthanoids, and tetraethylammonium ions, x satisfies 6.0≦x≦14.0, δ is a value determined so as to satisfy the charge neutrality condition, and y is an arbitrary value.

2. A negative thermal expansion material having a negative thermal expansion coefficient, comprising MER-type zeolite, The MER type zeolite is K ｘ－δ [Al ｘ Si ３２－ｘ O ６４ ]・yH ２ 0, where x satisfies 6.0≦x≦14.0, δ is a value determined so as to satisfy the charge neutrality condition, and y is an arbitrary value.

3. 3. The negative thermal expansion material according to claim 2, wherein x satisfies the condition 6.7≦x≦13.

5.

4. The volume expansion coefficient at least between 60°C and 140°C is -236 ppmK. －１ Above -98.6 ppmK －１ 4. The negative thermal expansion material according to claim 2 or 3, wherein:

5. The negative thermal expansion material according to any one of claims 1 to 4, characterized in that it exhibits volumetric shrinkage due to phase transition in a temperature range of 100°C or higher and 200°C or lower.

6. A part of the K contained in the MER zeolite is replaced by 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. The negative thermal expansion material according to any one of claims 2 to 4, wherein the negative thermal expansion material is substituted with at least one selected from the group consisting of ammonium ions.

7. A negative thermal expansion material having a negative thermal expansion coefficient, comprising GIS-type zeolite, The GIS type zeolite is Na ｘ－δ [Al ｘ Si １６－ｘ O ３２ ]・yH ２ 0, where 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.

8. A negative thermal expansion material having a negative thermal expansion coefficient, comprising GIS-type zeolite, The GIS type zeolite is Na ｘ－δ [Al ｘ Si １６－ｘ O ３２ ]・yH ２ 0, where 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.

9. The negative thermal expansion material according to claim 7 or 8, wherein x satisfies the condition 5.3≦x≦6.

9.

10. A part of the Na contained in the GIS type zeolite is replaced with 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 lanthanides. The negative thermal expansion material according to any one of claims 7 to 9, substituted with at least one selected from the group consisting of lanthanides.

11. The negative thermal expansion material according to any one of claims 1 to 10, and a material having a positive coefficient of thermal expansion.

12. The composite material according to claim 11 , wherein the material having a positive coefficient of thermal expansion is a resin material.

13. 12. The composite material of claim 11, wherein the material having a positive coefficient of thermal expansion is a metallic material.

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