JP2003238238A - Ceramics sintered compact, glaze, and manufacturing method for ceramics sintered compact - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low expansive cordierite ceramics sintered compact, particularly porcelain tableware, with superior heat shock resistance, and to provide ceramic sintered compact with superior heat shock resistance even if an Li-based glaze is applied, and its manufacturing method. <P>SOLUTION: For a base material, synthetic cordierite, and talc, kaolin and alumina are mixed for forming cordierite among crystalline particles of the synthetic cordierite. Petalite and zircon are mixed into the base material and a glaze material for obtaining a low expansive fine crystalline body between a base layer 10 and a glaze layer 20. The base material is glazed after biscuit firing, followed by glost firing. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a ceramic sintered body, and more particularly to a low expansion porcelain having high thermal shock resistance.

[0002]

2. Description of the Related Art Conventionally, cordierite (2MgO
There are low expansion ceramics sintered bodies using 2Al ₂ O ₃ .5SiO ₂ ), especially porcelain tableware. It is known that cordierite has a heat resistance of 1300 ° C. or higher and a small thermal expansion coefficient, and thus is excellent in thermal shock resistance.

[0003]

However, when porcelainizing a material containing cordierite as a main component, a large amount of a low-viscosity glass phase is generated during firing, and a finely-divided material with little deformation during firing. There is a problem in that a sintered body having a low expansion property cannot be obtained.

In addition, when a Li-based glaze is applied to a cordierite base material, a large amount of glass phase appears at the joint surface between the base material and the glaze, and the joint surface portion is highly expanded. The problem occurs.

Therefore, conventional porcelain tableware using cordierite, and further porcelain tableware glazed with a Li-based glaze using cordierite cannot obtain sufficient thermal shock resistance. However, it was not possible to perform the process of suddenly heating the frozen porcelain tableware in the freezer in the oven.

Therefore, the present invention provides a cordierite-based ceramics sintered body having low expansion and excellent thermal shock resistance, particularly porcelain tableware, and in particular, even when a Li-based glaze is glazed, It is intended to provide a ceramic sintered body having excellent thermal shock resistance.

[0007]

The present invention was created to solve the above problems, and firstly, a ceramics sintered body having a base layer and a glaze layer, which comprises: The base layer includes crystal grains of synthetic cordierite and microcrystals of cordierite existing between crystal grains of the synthetic cordierite, and between the base layer and the glaze layer. Is characterized in that an intermediate layer made of a low expansion crystal is formed.

In the ceramics sintered body of the first structure, the crystallites of cordierite are filled between the crystal grains of the synthetic cordierite, so that vitrification of the base layer is suppressed, Since the entire base layer is in a low expansion state, it is possible to obtain a ceramic sintered body having a low expansion and a high thermal shock resistance. Furthermore, since the intermediate layer made of a low-expansion crystal is formed between the base layer and the glaze layer, vitrification of the joint portion between the base layer and the glaze layer is suppressed, and the base and glaze layers are suppressed. Appropriate conformance of is possible. As a result, the ceramic sintered body can be made to have low expansion and high thermal shock resistance as a whole.

Secondly, in the first structure, the base layer further contains zircon. Therefore, since zircon is mixed in, it is possible to stabilize the crystal of cordierite during sintering or heating during manufacturing, and to maintain a good state of low expansion and high thermal shock resistance. Is possible.

Thirdly, the cordierite crystals existing between the crystal grains of the synthetic cordierite are:
It is characterized in that it is produced by reacting talc, kaolin, and alumina that have been blended as raw materials for the base layer.

Fourthly, in any one of the above-mentioned first to third structures, the low expansion crystal in the intermediate layer is a eulyptite type crystal and / or a silica-based crystal.
It is characterized by being an O-based crystal.

Fifthly, in any one of the first to fourth configurations, a lithium element-containing material that is a raw material having a lithium element is used as a raw material for the base layer and / or a raw material for the glaze layer. The low expansion crystal is formed around a predetermined crystal formation nucleus by the action of the lithium element in the lithium element-containing material.

A sixth feature is that, in the fifth structure, the crystal formation nucleus is zircon. Therefore, it becomes possible to positively crystallize a low expansion crystal body using zircon as a crystal formation nucleus.

Seventh, in the fifth or sixth structure, the lithium element-containing material is at least one of petalite and spodumene.

Eighth, in any one of the first to seventh structures, the expansion coefficient of the low expansion crystal in the intermediate layer is 3.5 × 10 ⁻⁶ or less. Characterize.

Ninth, a glaze, which is a material containing a lithium element, which is a material having a lithium element, and a material which serves as a crystal formation nucleus when a low expansion crystal is produced by the action of the lithium element. And a material for crystal formation nuclei which is

In the ninth structure, since the lithium element-containing material and the crystal-forming nucleus material are contained, the function of the lithium element in the lithium element-containing material during firing after the glaze is applied is The low expansion crystals are formed around the crystal formation nuclei. Therefore, it is possible to suppress the high expansion of the intermediate layer between the base material and the glaze layer, and improve the compatibility between the base material and the glaze.

The tenth feature is that, in the ninth structure, the lithium element-containing material is at least one of petalite and spodumene.
That is, due to the action of the lithium element contained in petalite or spodumene, the low expansion crystal body is generated around a predetermined crystal formation nucleus. Therefore, it is possible to suppress the high expansion of the intermediate layer between the base material and the glaze layer, and improve the compatibility between the base material and the glaze.

Eleventh, in the ninth or tenth construction, the material for crystal formation nuclei is zircon. Therefore, it becomes possible to positively crystallize a low expansion crystal body using zircon as a crystal formation nucleus.

Twelfthly, in any one of the ninth to eleventh constitutions, the mixing ratio in the glaze is such that the lithium element-containing material is 50 to 85% by weight, and for the crystal formation nucleus. The material is characterized by 5 to 15% by weight.

The thirteenth is a glaze, which comprises at least one of petalite and spodumene and zircon, and the mixing ratio in the glaze is such that at least one of petalite and spodumene is 50 to 85% by weight.
And zircon is 5 to 15% by weight.

In the thirteenth constitution, since at least one of petalite and spodumene and zircon are contained, when the glaze is baked after glaze,
Due to the action of the lithium element in at least one of the petalite and the spodumene, the low-expansion crystalline substance is generated around the zircon as the crystal-forming nucleus. Therefore, it is possible to suppress the high expansion of the intermediate layer between the base material and the glaze layer, and improve the compatibility between the base material and the glaze.

The fourteenth aspect is characterized in that, in any of the ninth to thirteenth configurations, the glaze further comprises dolomite, talc, and kaolin.

Fifteenthly, in any one of the ninth to fourteenth constructions, the mixing ratio in the glaze is 2 to 10% by weight for dolomite and 2 for talc.
10 to 10% by weight and kaolin is 3 to 10% by weight.

Sixteenth, there is provided a method for producing a ceramics sintered body, which comprises, as a raw material, synthetic cordierite, and a material for producing cordierite in the gap between the synthetic cordierites. , A base material manufacturing step of manufacturing a base material, a forming step of forming the base material manufactured in the base material manufacturing step into a predetermined shape, and a step of firing the base material formed in the forming step. And a firing step.

According to the method for manufacturing a ceramics sintered body of the sixteenth structure, the material for producing cordierite in the gap between the synthetic cordierite is mixed with the base material, so that the firing step is performed. In the above, since the crystallites of cordierite are filled in the gaps between the crystal grains of the synthetic cordierite in a matrix, vitrification of the matrix can be suppressed.

The seventeenth method is a method for producing a ceramics sintered body, which comprises, as a base material, synthetic cordierite and a material for producing cordierite in the gap between the synthetic cordierites. A mixture of a lithium element-containing material that is a material having a lithium element and a crystal formation nucleus material that is a material that serves as a crystal formation nucleus when a low expansion crystal is generated by the action of the lithium element. A base material manufacturing step of manufacturing a raw material, a forming step of forming the base material manufactured in the base material manufacturing step into a predetermined shape, and a base material manufactured by firing the base material formed in the forming step With respect to the first firing step and the base material produced in the first firing step, the lithium element-containing material that is a material having a lithium element and the function of the lithium element A glazing step of glazing a glaze having a material for a crystal nucleation nucleus, which is a material serving as a crystal nucleation nucleus when generating a crystal having a low expansion, and a second firing step of firing the base material glazed by the glaze step And are included.

According to the method for manufacturing a ceramics sintered body of the seventeenth structure, the material for generating cordierite in the gap between the synthetic cordierite is mixed with the base material, so In the firing step, the gaps between the crystal grains of the synthetic cordierite are filled with the cordierite microcrystals in a matrix, so that vitrification of the matrix can be suppressed. In addition, a lithium element-containing material that is a material having a lithium element, and a material for a crystal formation nucleus that is a material that becomes a crystal formation nucleus when a low expansion crystal is generated by the action of the lithium element, Since it is mixed with the glaze respectively, in the second firing step, at the joint between the base layer and the glaze layer, due to the function of the lithium element, the crystal-forming nucleus material is used as the crystal-forming nucleus to form a low expansion fine powder. Crystals can be crystallized. In this way, it is possible to manufacture a ceramic sintered body having a low expansion and a high thermal shock resistance as a whole.

The eighteenth aspect is characterized in that, in the seventeenth configuration, the lithium element-containing material is at least one of petalite and spodumene. That is, due to the action of the lithium element contained in petalite or spodumene, the low expansion crystal body is generated around a predetermined crystal formation nucleus. Therefore, it is possible to suppress the expansion of the joint portion between the base material and the glaze layer, and improve the compatibility between the base material and the glaze.

The nineteenth is the seventeenth or eighteenth.
In the above configuration, the material for crystal formation nuclei is zircon.

Twentieth, the seventeenth to nineteenth aspects described above.
In any one of the constitutions up to, the mixing ratio in the raw material is 10 to 30% by weight for the synthetic cordierite.
And the lithium element-containing material is 2 to 10% by weight.
And the content of the crystal-forming nucleus material is 5 to 10% by weight.

In the twenty-first, the seventeenth to twentieth described above.
In any one of the above configurations, the mixing ratio in the glaze is 50 to 85% by weight for the lithium element-containing material, and 5 to 15% by weight for the crystal-forming nucleus material.

Twenty-second, the seventeenth to twenty-first aspects described above.
In any of the configurations up to, the glaze further,
It is characterized by having dolomite, talc, and kaolin.

Twenty-third, in the twenty-second configuration, the mixing ratio in the glaze is 2 to 2 for dolomite.
10% by weight, talc 2-10% by weight, kaolin 3-10% by weight.

The 24th is the 16th to the 23rd.
In any one of the above constitutions, zircon is further mixed with the base material in the base material manufacturing step. As a result, since zircon is mixed in, it is possible to stabilize the crystal of cordierite during sintering during manufacturing or during heating, and maintain a good state of low expansion and high thermal shock resistance. It becomes possible.

The 25th is the 16th to 24th.
In any one of the above configurations, the material for producing cordierite in the gap between the synthetic cordierites is talc, kaolin, and alumina. That is, during firing, talc, kaolin, and alumina react with each other to produce cordierite.

The 26th is the 16th to the 24th.
In any one of the above configurations, the material for generating cordierite in the gap between the synthetic cordierites is talc and kaolin.

Twenty-seventh is a method for producing a ceramics sintered body, wherein at least one of petalite and spodumene, zircon, synthetic cordierite, talc and kaolin are mixed as a base material. And a base material manufacturing step of manufacturing the base material, a forming step of forming the base material manufactured in the base material manufacturing step into a predetermined shape, and firing the base material formed in the forming step to form a base material. A first firing step for producing, and a glaze step for applying a glaze having at least one of petalite and spodumene and zircon to the base body produced in the first firing step, and glazed by the glaze step. And a second firing step of firing the green body.

According to the method for producing a ceramics sintered body of the twenty-seventh structure, at least talc and kaolin are mixed with the raw material, so that in the first firing step, the gap between the crystal grains of the synthetic cordierite is generated. Since the cordierite microcrystals (strictly speaking, a composite of cordierite microcrystals and other minerals) are filled in a matrix, vitrification of the matrix can be suppressed. Further, at least one of petalite and spodumene, and zircon are respectively mixed with the base material and the glaze, so in the second firing step, the petalite and the spodumene are present at the joint between the base layer and the glaze layer. By the action of the lithium element in at least one of
A low-expansion microcrystal can be crystallized using the zircon as a crystal-forming nucleus. In this way, it is possible to manufacture a ceramic sintered body having a low expansion and a high thermal shock resistance as a whole.

Twenty-eighthly, in the twenty-seventh constitution, the mixing ratio in the raw material is 10 to 30% by weight of the synthetic cordierite, 5 to 15% by weight of the talc. The kaolin is 35 to 50% by weight, at least one of the petalite and spodumene is 5 to 10% by weight, and the zircon is 5 to 5% by weight.
The mixing ratio in the glaze is such that at least one of petalite and spodumene is 70 to 80% by weight, and zircon is 5 to 15% by weight.

Twenty-ninth, the twenty-seventh or the twenty-eighth above.
In the above configuration, the base material further contains alumina.

In the 30th, the 25th to the 29th.
In any one of the above configurations, the mixing ratio in the raw material is 5 to 15 wt% for talc, 35 to 50 wt% for kaolin, and 6 wt% or less for alumina. And

The 31st is the 16th to the 30th.
In any one of the above configurations, the base material further comprises feldspar. The mixing ratio in the raw material is preferably 5 to 10% by weight.

In the above, the "base layer" may be referred to as the "base part" and the "glaze layer" may be referred to as the "glaze part" (the same shall apply hereinafter).

[0045]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described with reference to the drawings. The ceramics sintered body A in this example is a dense ceramics sintered body,
As shown in FIGS. 1 (a) and 1 (b), it is a dish-shaped porcelain tableware.

The ceramics sintered body A is formed by molding a mixture of predetermined raw materials, firing (unbaking) to form a substrate, glazeing the substrate, and then firing again. It is a thing. That is, as shown in FIG.
And has a glaze layer 20 and the like.

Here, the base layer 10 is made of kaolin (Al₂
O₃・ 2SiO₂・ 2H₂O) and synthetic cordierite
(2MgO · 2Al₂O₃・ 5 SiO₂) And talc (3
MgO / 4SiO₂・ H₂O) and alumina (Al₂O₃)
And feldspar and petalite (Li ₂O ・ Al₂O₃・ 8Si
O₂) And zircon (ZrO₂・ SiO₂) And a predetermined percentage
After mixing and molding, fire (that is, unglazed)
And that was fired again during firing after glazing
Is.

Here, in the state of the ceramics sintered body A, glass material, cordierite and the like are present in the base layer 10. The cordierite is composed of crystal grains of synthetic cordierite and microcrystals of cordierite that are filled in a space between the crystal grains of the synthetic cordierite in a matrix. This cordierite microcrystal is formed by synthesizing the above talc, kaolin and alumina. The diameter of the microcrystals of cordierite is approximately 1 micron or less.
The microcrystals of cordierite correspond to the above-mentioned “crystallites of cordierite existing between the synthetic cordierite crystal grains”.

The glaze layer 20 is formed of petalite (Li ₂
And _{O · Al 2 O 3 · 8SiO} 2), and feldspar, dolomite (MgCO ₃ · CaCO _3), limestone (CaCO ₃₎
If, talc and _{(3MgO · 4SiO 2 · H 2} O), kaolin _{(Al 2 O 3 · 2SiO 2} · 2H 2 O), zircon (Z
rO ₂ · SiO ₂ ) is mixed at a predetermined ratio, and specifically, powders of the above respective raw materials are mixed at a predetermined ratio to produce a glaze. It is formed by producing a glaze slurry, applying the glaze slurry to a base material that has been unglazed, and firing the glaze slurry.

Here, in the state of the ceramics sintered body A, the glaze layer 20 contains vitreous substances, low expansion crystal substances and the like. The low expansion crystal is a eucryptite-based crystal and / or a silica-O-based crystal. This low expansion crystalline material is
By the action of the (lithium) element, zircon was crystallized as a crystal-forming nucleus.

In particular, in the joint surface between the base layer 10 and the glaze layer 20, the intermediate layer 30 made of a low expansion crystal is used.
Are formed. This low-expansion crystal is crystallized by the action of Li element in petalite in the matrix, with zircon separately blended in the matrix as crystal-forming nuclei. And / or silica-O based crystal.

Next, the method for manufacturing the above tableware A will be described with reference to FIG.
Etc. will be described. First, powders of the respective raw materials for producing the base material are mixed in a predetermined ratio to produce the base material (S10, base material production step). That is, kaolin (A
1 ₂ O ₃ .2SiO ₂ .2H ₂ O) powder, synthetic cordierite (2MgO.2Al ₂ O ₃ .5SiO ₂ ) powder, talc (3MgO.4SiO ₂ .H ₂ O) powder,
Shows a powder alumina (Al ₂ O _3), and feldspar powder, a powder of petalite _{(Li 2 O · Al 2 O} 3 · 8SiO 2), and a powder of zircon (ZrO ₂ · SiO ₂₎ in Table 1 Mix by weight.

[0053]

[Table 1]

That is, the weight ratio of the whole base material is 35 to 50% by weight for kaolin, 10 to 30% by weight for synthetic cordierite, 5 to 15% by weight for talc, and 0 to 6% for alumina. %, 5 to 15% by weight for feldspar, 2 to 10% by weight for petalite, and 5 to 10% by weight for zircon, and the powders of the respective raw materials are mixed.

Here, the kaolin is a clay mineral and contains kaolinite, nacrite and the like.

The above synthetic cordierite was prepared by mixing talc, alumina and kaolin in a stoichiometric ratio,
It was produced by heating at 0 ° C or higher. In order to minimize firing deformation during heating in cordierite porcelain, it is a good idea to use pre-synthesized cordierite crystal powder as an aggregate. A synthetic cordierite such as

The talc is also called talc and is known as naturally occurring magnesium metasilicate. This talc is provided to fill the gaps between the crystal grains of the synthetic cordierite in the matrix composition with the microcrystals of cordierite. That is, since the base material contains kaolin and alumina in addition to talc, cordierite is synthesized from talc, kaolin, and alumina, and the gaps between the crystal grains of cordierite are formed into a matrix. It is filled with microcrystals of cordierite. The talc, kaolin, and alumina correspond to the above-mentioned "material for producing cordierite in the gap between the synthetic cordierites". The details of the synthesis of cordierite with talc, kaolin and alumina will be described later.

The petalite is used to prevent vitrification at the joint surface between the base material and the glaze layer. That is, due to the action of the Li element in petalite, zircon separately contained in the base material serves as crystal formation nuclei to crystallize low expansion microcrystals in the intermediate layer 30. This petalite corresponds to the "lithium element-containing material".

Zircon is mixed in to promote the stabilization of crystals of cordierite under heating. In other words, when cordierite is exposed to high temperatures, the crystals tend to decompose and vitrify, that is, to become amorphous, but by incorporating this zircon, vitrification is suppressed and the crystals are stable. And will exist. In addition, this zircon also functions as a crystal formation nucleus when the microcrystalline body crystallizes, as described above. That is, zircon corresponds to the above-mentioned "crystal nucleation material".

Further, the feldspar is used as a flux material in the production of the base material. The feldspars mentioned above are orthoclase (also called potassium feldspar) (K ₂ O · Al ₂ O ₃ ·.
6SiO ₂ ) and albite (also called soda feldspar) (NaO
・ Al ₂ O ₃ .6SiO ₂ ) and the like.

The composition range of the base material is shown in Table 2.

[0062]

[Table 2]

That is, SiO ₂ is 50.0 to 65.0% by weight, Al ₂ O ₃ is 20.0 to 30.0% by weight, and Mg is
O is 5.0 to 9.0 wt% and ZrO ₂ is 3.0 to 7.
At 0% by weight, Li ₂ O is 0.2 to 1.0% by weight.

The alumina may be omitted as described later, and in that case, the base material does not contain alumina.

Next, the base material is formed into a predetermined shape (S11, forming step). In this case, since the ceramics sintered body A has a dish shape, it is molded into that shape.

Next, after drying the formed base material (S12), it is fired (S13, first firing step). That is, unglazed is performed to generate a base material in the unglazed state.
The firing temperature in this case is 700 to 900 ° C.

Next, glazing is performed (S14, glazing step).
When applying glaze, naturally glaze is manufactured in advance. That is, the glaze is manufactured as follows.

That is, petalite (Li ₂ O.Al ₂ O
₃ / 8SiO ₂ ) powder, feldspar powder, dolomite (MgCO ₃ · CaCO ₃ ) powder, limestone (CaCO
A powder of _3), talc _{(3MgO · 4SiO 2 · H 2} O)
Powder and kaolin (Al ₂ O ₃ · 2SiO ₂ · 2H ₂ O)
And the powder of zircon (ZrO ₂ .SiO ₂ ) are mixed in the weight ratio shown in Table 3.

[0069]

[Table 3]

That is, the weight ratio of the whole glaze was 50-85% by weight for petalite, 0-10% by weight for feldspar, 2-10% by weight for dolomite, 0-10% by weight for limestone, and 0% for talc. Is 2 to 10% by weight, kaolin is 3 to 10% by weight, and zircon is 5 to 15% by weight.

The petalite used in the glaze is used to prevent vitrification in the glaze layer 20 and the intermediate layer 30. That is, L in petalite
Due to the action of the i element, a low expansion crystal is crystallized using zircon similarly contained in the glaze as a crystal forming nucleus. The low expansion crystal is a eucryptite-based crystal and / or a silica-O-based crystal.

Further, zircon in the glaze serves as a crystal formation nucleus when crystallizing a low expansion crystal as described above, and has a function of promoting crystallization of the crystal.

Further, dolomite, talc and limestone in the above glaze are mixed to adjust the Ca and Mg components of the glaze composition. The feldspar in the glaze is used as a flux material. The feldspar and limestone may be omitted from the mixing.

The composition range of the glaze having the above composition is
As shown in.

[0075]

[Chemical 1]

After the glaze is produced as described above, a sizing agent having a predetermined water content is added to the glaze, and then wet pulverization is performed to produce a glaze slurry. Then, the glaze slurry is glazed on the base material in the unglazed state manufactured in step S13.

After the glaze is applied, the glazed substrate is then fired in an oxidizing atmosphere (S15, second firing step). The firing temperature is 1250 to 1350 ° C. Through the above steps, the ceramic sintered body A is manufactured.

In the firing process in the above manufacturing process, particularly in step S13, the talc, kaolin, and alumina react to produce cordierite microcrystals. The model formula of this reaction is shown in Chemical formula 2.

[0079]

[Chemical 2]

As a result, the gaps between the synthetically mixed cordierite crystal grains originally mixed are filled with the cordierite microcrystals in a matrix form. That is, the synthetic cordierite functions as an aggregate, and the gaps between the crystal grains of the synthetic cordierite are filled with the microcrystals of cordierite. Further, since zircon is mixed in the base material, cordierite, that is, the above synthetic cordierite or microcrystalline cordierite can be prevented from vitrifying during firing. As a result, the generation of the matrix glass phase can be minimized and the crystallites of cordierite can be stabilized, so that a ceramic sintered body with low expansion and high thermal shock resistance can be obtained. it can. Further, even when the ceramics sintered body A is heated during cooking or the like, since the base layer 10 contains zircon, it is possible to stabilize the crystal of cordierite.

When alumina is not mixed with the base material, only talc and kaolin react with each other to form a composite material in which cordierite and another mineral (for example, mullite or quartz) are combined. Will be. Since this composite substance also contains cordierite, it can be said that talc and kaolin alone are “materials for producing cordierite in the gaps between synthetic cordierites”.

Further, at the time of firing in step S15, L in petalite contained in the base material is
By the action of the i element and the Li element in petalite contained in the glaze, the zircon contained in the base material and the glaze is crystallized in the joint surface between the base layer 10 and the glaze layer 20, that is, in the intermediate layer 30. As a nucleus, a low expansion microcrystal is crystallized. This low expansion microcrystal is a eucryptite-based crystal and / or a silica-O-based crystal. That is, the low expansion microcrystals are generated after the crystal structure of petalite is once collapsed. In addition, even at the location of the glaze slurry, a low expansion microcrystal is crystallized by the action of Li element in petalite, using zircon contained in the glaze as a crystal forming nucleus. This low expansion microcrystal is a eucryptite-based crystal and / or a silica-O-based crystal.

Thereby, the intermediate layer 30 and the glaze layer 20 are formed.
Since it is possible to prevent the expansion of the material, it is possible to appropriately match the base layer 10 and the glaze layer 20. In particular, even when Li-based glaze is applied, vitrification of the intermediate layer 30 can be suppressed and high expansion can be prevented, so that the base layer 10 and the glaze layer 20 can be appropriately matched. Become.

In the state of the ceramics sintered body A,
The glass layer is present in the base layer 10 and the glaze layer 20, but this is due to feldspar.

In the above description, petalite is used, but spodumene may be used instead of petalite. In other words, Spodumene is used in place of petalite in the base material,
Spodumene may be used instead of petalite in the glaze raw material. It is also possible to use petalite and spodumene together.

In the above description, talc is used, but instead of talc, magnesite (MgCO ₃ ), dolomite (MgCO ₃ .CaC).
O ₃ ) may be used. Moreover, you may use the substance which has a MgO component more than them. It is also possible to use those materials together. For example, it is possible to use talc and magnesite together instead of one talc.

Next, the test results of the above embodiment will be described. First, the test in the case of no glaze will be described.

Five kinds of glaze-free test bodies are manufactured by mixing the raw materials in the base raw materials as shown in Table 4.

[0089]

[Table 4]

That is, the compounding ratio of B-1 type, that is, 45% by weight of kaolin and 2% of synthetic cordierite.
5% by weight, 5% by weight talc, 3% by weight alumina, 12% by weight feldspar, 5% by weight petalite, 5% zircon
Each raw material is mixed as a weight% to produce a base material, the base material is molded into a predetermined shape, dried and then 1270 ° C.
The one that is fired at is manufactured. In other words, it should be baked without glaze. This is a non-glaze B-1 type test body.

Also, the compounding ratio of B-2 type, that is,
50% by weight of kaolin, 10% by weight of synthetic cordierite, 15% by weight of talc, 6% by weight of alumina, 15% by weight of feldspar, 8% by weight of petalite, 8% by weight of zircon, and the respective raw materials were mixed. To produce a base material, and the base material is molded into a predetermined shape, dried and then fired at 1250 ° C. In other words, it should be baked without glaze. This is a non-glaze B-2 type test body.

Also, the mixing ratio of B-3 type, that is,
50% by weight of kaolin, 15% by weight of synthetic cordierite, 10% by weight of talc, 4% by weight of alumina, 8% by weight of feldspar, 7% by weight of petalite, and 6% by weight of zircon were mixed together. To produce a base material, which is shaped into a predetermined shape, dried and then fired at 1300 ° C. In other words, it should be baked without glaze. This is a non-glaze B-3 type test body.

The B-4 type compounding ratio, that is,
40% by weight of kaolin, 22% by weight of synthetic cordierite, 10% by weight of talc, 5% by weight of alumina, 9% by weight of feldspar, 7% by weight of petalite, 7% by weight of zircon, and the respective raw materials were mixed. To produce a base material, and the base material is molded into a predetermined shape, dried and then fired at 1250 ° C. In other words, it should be baked without glaze. This is a non-glaze B-4 type test body.

The blending ratio of B-5 type, that is,
35% by weight of kaolin, 30% by weight of synthetic cordierite, 5% by weight of talc, 6% by weight of alumina, 4% by weight of feldspar, 10% by weight of petalite, 10% by weight of zircon, and the respective raw materials were mixed. To produce a base material, and the base material is shaped into a predetermined shape, dried and then fired at 1350 ° C. In other words, it should be baked without glaze. This is a non-glaze B-5 type test body.

Then, the expansion coefficient (specifically, the expansion coefficient at 800 ° C.), the water absorption rate, and the bend value of each of the test specimens were measured, and the results are shown in Table 5.

[0096]

[Table 5]

That is, the unglaze B-1 type test body had an expansion coefficient of 3.5 × 10 ^-6 , a water absorption rate of 0%, and a bend value of 1.9 mm. Further, the unglaze B-2 type test body had an expansion coefficient of 3.3 × 10 ⁻⁶ , a water absorption rate of 0%, and a bend value of 2.1 mm. Further, in the above-mentioned non-glaze B-3 type test body, the expansion coefficient is 2.8 × 1.
The water absorption rate was 0 ^-6 , the water absorption rate was 0%, and the bend value was 1.4 mm.
Further, in the unglaze B-4 type test body, the expansion coefficient was 2.4 × 10 ⁻⁶ , the water absorption rate was 0%, and the bend value was 1.6 m.
It became m. Furthermore, the unglaze B-5 type test body had an expansion coefficient of 2.5 × 10 ⁻⁶ , a water absorption rate of 0%, and a bend value of 1.7 mm. As described above, good values were obtained in all cases.

Regarding the above test results, similar results were obtained even when spodumene was used instead of the above petalite.

Next, the test in the case of glaze will be described. That is, the composition of each raw material in the base material is set as shown in Table 6, and any one of the three types of glazes shown in Table 6 is glazed to produce five types of glaze test bodies.

[0100]

[Table 6]

That is, the compounding ratio of the B-1 type was 45% by weight of kaolin and 2% of synthetic cordierite.
5% by weight, 5% by weight talc, 3% by weight alumina, 12% by weight feldspar, 5% by weight petalite, 5% zircon
The raw materials are manufactured by mixing each raw material in a weight percentage, and the raw materials are molded into a predetermined shape, dried, and then bisqued. On the other hand, a glaze having a G-2 type compounding ratio in Table 6 is manufactured. That is, 75% by weight of petalite, 4% by weight of feldspar, 3% by weight of dolomite, 3% by weight of talc,
A glaze is produced with kaolin at 5% by weight and zircon at 10% by weight. Then, the above-mentioned unglazed body is glazed with this glaze and then baked at 1270 ° C. to manufacture a test body. This test piece is a glazed B-1 type test piece. This glazed B-1 type test body is B-1 for the base material.
Type (see Table 4) and the glaze is G-2 type (see Table 6).

The B-2 type compounding ratio, that is,
50% by weight of kaolin, 10% by weight of synthetic cordierite, 15% by weight of talc, 6% by weight of alumina, 15% by weight of feldspar, 8% by weight of petalite, 8% by weight of zircon, and the respective raw materials were mixed. To produce a base material, shape the base material into a predetermined shape, dry it, and then perform bisque firing. On the other hand, the glaze having the compounding ratio of G-1 type in Table 4 is manufactured. That is, 70% by weight of petalite, 5% by weight of feldspar, 3% by weight of dolomite, 3% by weight of talc,
A glaze is produced with kaolin at 5% by weight and zircon at 14% by weight. Then, the glaze is glazeed on the unglazed body and then fired at 1250 ° C. to manufacture a test body. This test piece is a glazed B-2 type test piece. This glazed B-2 type test body is B-2 for the base material.
Type (see Table 4) and the glaze is G-1 type (see Table 6).

The B-3 type compounding ratio, that is,
50% by weight of kaolin, 15% by weight of synthetic cordierite, 10% by weight of talc, 4% by weight of alumina, 8% by weight of feldspar, 7% by weight of petalite, and 6% by weight of zircon were mixed together. To produce a base material, shape the base material into a predetermined shape, dry it, and then perform bisque firing.
On the other hand, a glaze having a G-3 type compounding ratio in Table 6 is manufactured. That is, a glaze is produced with 80% by weight of petalite, 0% by weight of feldspar, 5% by weight of dolomite, 3% by weight of talc, 5% by weight of kaolin and 7% by weight of zircon. Then, after the glaze is applied to the unglazed body, firing is performed at 1300 ° C. to manufacture a test body. This test piece is a glazed B-3 type test piece. This glazed B-3 type test body is a B-3 type (see Table 4) for the base material and a G-3 type (see Table 6) for the glaze.

The B-4 type compounding ratio, that is,
40% by weight of kaolin, 22% by weight of synthetic cordierite, 10% by weight of talc, 5% by weight of alumina, 9% by weight of feldspar, 7% by weight of petalite, 7% by weight of zircon, and the respective raw materials were mixed. To produce a base material, shape the base material into a predetermined shape, dry it, and then perform bisque firing.
On the other hand, a glaze having a G-2 type compounding ratio in Table 6 is manufactured. Then, the glaze is glazeed on the unglazed body and then fired at 1250 ° C. to manufacture a test body.
This test body is a glazed B-4 type test body. This glazed B-4 type test body is B-4 type (see Table 4) for the base material and G-2 type (see Table 6) for the glaze.

The blending ratio of B-5 type, that is,
35% by weight of kaolin, 30% by weight of synthetic cordierite, 5% by weight of talc, 6% by weight of alumina, 4% by weight of feldspar, 10% by weight of petalite, 10% by weight of zircon, and the respective raw materials were mixed. To produce a base material, shape the base material into a predetermined shape, dry it, and then perform bisque firing. On the other hand, a glaze having a G-3 type compounding ratio in Table 6 is manufactured. Then, the above-mentioned unglazed body is glazed with this glaze and then baked at 1350 ° C. to manufacture a test body. This test body is a glazed B-5 type test body. This glazed B-5 type specimen is B-5 for the base material.
Type (see Table 4) and the glaze is G-3 type (see Table 6).

And, the above-mentioned glazed B-1 type test body,
For each of the glazed B-2 type test body, the glazed B-3 type test body, the glazed B-4 type test body, and the glazed B-5 type test body, the water absorption rate and the expansion coefficient (specifically, The expansion coefficient at 800 ° C.) and the bend value were measured. Then, the water absorption rate becomes 0% and the expansion coefficient is 2.5.
~ 3.5 × 10 ^-6 , bend value 1.5 ~ 2.5m
It became m. Moreover, the bending strength was 90 MPa and the thermal shock resistance was 300 ° C. or higher. That is, good values were obtained in all cases.

Further, the above G-1 type glaze and G-2
The expansion coefficient (specifically, the expansion coefficient at 800 ° C.) was measured for the Glazed type glaze and the G-3 type glaze. That is, although the glaze was baked and solidified, the expansion coefficient was measured. And the expansion coefficient is 1.0 to
It was 1.5 × 10 ⁻⁷ , and the result of low expansion could be obtained.

As described above, since the ceramics sintered body A in this example is a porcelain product having a low expansion and an excellent thermal shock resistance, it can be used as it is in a freezer, oven, electronic It can be used for both range and IH cookers. So, for example,
After cooking, the dish placed on the ceramics sintered body A can be stored in a freezer as it is, and heated in an oven, a microwave oven or an IH cooker before a meal, and can be used as it is on a dining table. Further, it is also possible to serve with a meal while heating with an IH heat insulation cooker for a table. Furthermore, after the meal, the ceramics sintered body A can be washed with an automatic washing machine and dried with a hot air dryer.

Although the above-mentioned ceramics sintered body A has been described as dish-shaped tableware, it may be any dish other than dish-shaped, and may be something other than tableware.

[0110]

According to the ceramics sintered body of the present invention, since the crystal body of cordierite is filled between the crystal grains of synthetic cordierite, vitrification of the base layer is suppressed, Since the entire base layer is in a low expansion state, it is possible to obtain a ceramic sintered body having a low expansion and a high thermal shock resistance. Furthermore, since the intermediate layer made of a low-expansion crystal is formed between the base layer and the glaze layer, vitrification of the joint portion between the base layer and the glaze layer is suppressed, and the base and glaze layers are suppressed. Appropriate conformance of is possible.
As a result, the ceramic sintered body can be made to have low expansion and high thermal shock resistance as a whole.

Further, according to the glaze of the present invention, since the lithium element-containing material is contained, a predetermined crystal is formed by the action of the lithium element in the lithium element-containing material during firing after glaze of the glaze. The low expansion crystals are formed around the nucleus. Therefore, it is possible to suppress the high expansion of the intermediate layer between the base material and the glaze layer, and improve the compatibility between the base material and the glaze.

Further, according to the method for manufacturing a ceramics sintered body of the present invention, a material (for example, talc, etc.) for generating cordierite in the gap between the synthetic cordierites.
Kaolin, etc.) is mixed with the base material, so in the firing step, in the gaps between the crystal grains of the synthetic cordierite,
Since the cordierite microcrystals are filled in a matrix form, it is possible to suppress vitrification of the base material, reduce the expansion, and at the same time reduce deformation during firing.

Further, according to the method for producing a ceramics sintered body of the present invention, the material for forming cordierite in the gap between the synthetic cordierite is mixed with the base material, so that the first firing step is performed. In the above, since the crystallites of cordierite are filled in the gaps between the crystal grains of the synthetic cordierite in a matrix, vitrification of the matrix can be suppressed. Further, a lithium element-containing material that is a material having a lithium element (for example, petalite,
Spodumene) and a material for crystal formation nuclei (for example, zircon), which is a material that becomes a crystal formation nucleus when a low expansion crystal is generated by the action of the lithium element, are mixed with the base material and the glaze, respectively. Therefore, in the second firing step, at the joint between the base layer and the glaze layer, the function of the lithium element causes the low-expansion microcrystalline body to crystallize using the crystal-forming nucleus material as the crystal-forming nucleus. be able to. In this way, it is possible to manufacture a ceramic sintered body having a low expansion and a high thermal shock resistance as a whole.

In particular, when the base material contains zircon, it is possible to stabilize the crystal of cordierite at the time of sintering or heating at the time of production, and to have a low expansion and a high thermal shock resistance. It is possible to maintain the high state in a good condition. Further, this zircon serves as a crystal formation nucleus when a low-expansion microcrystal is crystallized.

[Brief description of drawings]

FIG. 1 is a diagram showing a ceramics sintered body according to an embodiment of the present invention, (a) is a perspective view showing an example of its appearance, (b) is a sectional view thereof, and (c) is a sectional view thereof. It is an enlarged view of a sectional view.

FIG. 2 is an explanatory view showing a method for manufacturing a ceramics sintered body according to an example of the present invention.

[Explanation of symbols]

A ceramics sintered body 10 foundation layers 20 Glaze layer 30 Middle class

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toru Suzuki             210-1 Koza, Inazu-cho, Mizunami-shi, Gifu Marusa             Ceramics Co., Ltd. F-term (reference) 4G030 AA02 AA03 AA04 AA07 AA08                       AA17 AA36 AA37 BA18 BA24                       CA01 CA05 GA04 GA09 GA15                       GA20 GA27 GA35 HA05 HA07                       HA08 HA10 HA15 HA16 HA17                       HA18

Claims (31)

[Claims] 1. A ceramic sintered body having a base layer and a glaze layer, wherein the base layer has crystal grains of synthetic cordierite and cordierite present between crystal grains of the synthetic cordierite. A ceramic sintered body characterized by comprising a light crystallite and an intermediate layer made of a low expansion crystallite between the base layer and the glaze layer. 2. The ceramic sintered body according to claim 1, wherein the green body layer further contains zircon. 3. The cordierite crystals existing between the crystal grains of the synthetic cordierite are produced by the reaction of talc, kaolin and alumina, which have been blended as a raw material for the base layer. Claim 1 characterized by the above.
Alternatively, the ceramic sintered body according to item 2. 4. The low expansion crystalline body in the intermediate layer comprises:
A ceramic sintered body according to claim 1 or 2 or 3, which is a euryptite-based crystal and / or a silica-O-based crystal. 5. A lithium element-containing material, which is a raw material having a lithium element, is blended as a raw material for the base layer and / or a raw material for the glaze layer, and a predetermined amount is obtained by the action of the lithium element in the lithium element-containing material. The ceramic sintered body according to claim 1, 2 or 3 or 4, wherein the low-expansion crystal body is formed around a crystal-forming nucleus. 6. The ceramic sintered body according to claim 5, wherein the crystal formation nucleus is zircon. 7. The ceramic sintered body according to claim 5, wherein the lithium element-containing material is at least one of petalite and spodumene. 8. The expansion coefficient of the low-expansion crystalline material in the intermediate layer is 3.5 × 10 ⁻⁶ or less, according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7. The ceramics sintered body described. 9. A glaze, which is a material containing a lithium element, which is a material having a lithium element, and a crystal formation nucleus which is a material serving as a crystal formation nucleus when a low expansion crystal is formed by the action of the lithium element. Materials and
A glaze characterized by having. 10. The glaze according to claim 9, wherein the lithium element-containing material is at least one of petalite and spodumene. 11. The glaze according to claim 9, wherein the crystal-forming nucleus material is zircon. 12. The mixing ratio in the glaze is 50 to 85% by weight for the lithium element-containing material, and 5 to 15% by weight for the crystal-forming nucleus material. Or the glaze according to 11. 13. A glaze, comprising at least one of petalite and spodumene, and zircon, wherein the mixing ratio in the glaze is at least 50 to 85% by weight of at least one of petalite and spodumene, and A glaze characterized by containing 5 to 15% by weight of zircon. 14. The glaze further comprises dolomite,
10. Talc and kaolin are included.
Or the glaze according to 10 or 11 or 12 or 13. 15. The mixing ratio in the glaze is 2 to 10% by weight for dolomite and 2 to 10% by weight for talc.
And kaolin is 3 to 10% by weight, the glaze according to 9 or 10 or 11 or 12 or 13 or 14. 16. A method for producing a ceramics sintered body, comprising mixing synthetic cordierite as a raw material and a material for producing cordierite in a gap between the synthetic cordierites. A base material manufacturing step of manufacturing the base material, a forming step of forming the base material manufactured in the base material manufacturing step into a predetermined shape, and a firing step of firing the base material formed in the forming step. A method for manufacturing a ceramics sintered body, comprising: 17. A method for producing a ceramics sintered body, which comprises, as a raw material, synthetic cordierite, a material for producing cordierite in a gap between the synthetic cordierite, and a lithium element. A base material for producing a base material by mixing a lithium element-containing material, which is a material, and a crystal formation nucleus material, which is a material that becomes a crystal formation nucleus when a low expansion crystal is generated by the action of the lithium element A raw material manufacturing step, a molding step of molding the raw material manufactured in the raw material manufacturing step into a predetermined shape, a first firing step of firing the raw material molded in the molding step to produce a green body, A lithium element-containing material, which is a material having a lithium element, with respect to the base body manufactured in the first firing step;
A material for a crystal formation nucleus, which is a material that serves as a crystal formation nucleus when a low expansion crystal is generated by the action of the lithium element,
A method of manufacturing a ceramic sintered body, comprising: a glaze step of applying a glaze having: and a second firing step of firing the base material glazed by the glaze step. 18. The method for producing a ceramic sintered body according to claim 17, wherein the lithium element-containing material is at least one of petalite and spodumene. 19. The method for producing a ceramic sintered body according to claim 17, wherein the material for crystal formation nuclei is zircon. 20. The mixing ratio of the base material is 10 to 30% by weight of synthetic cordierite, and
The lithium element-containing material is 2 to 10% by weight, and
20. The method for producing a ceramic sintered body according to claim 17, 18 or 19, wherein the material for crystal formation nuclei is 5 to 10% by weight. 21. The mixing ratio in the glaze is 50 to 85% by weight for the lithium element-containing material, and 5 to 15% by weight for the crystal-forming nucleus material. Alternatively, the method for producing a ceramics sintered body according to 19 or 20. 22. The glaze further comprises dolomite,
2. Talc and kaolin are included.
A method for manufacturing a ceramics sintered body according to 7 or 18 or 19 or 20 or 21. 23. The mixing ratio in the glaze is 2 to 10% by weight for dolomite and 2 to 10% by weight for talc.
The method for manufacturing a ceramics sintered body according to claim 22, wherein kaolin is 3 to 10% by weight. 24. The ceramic sintered body according to claim 16, wherein the base material is further mixed with zircon in the step of producing the base material. Production method. 25. The material for generating cordierite in the gap between the synthetic cordierites is talc,
Kaolin and alumina.
6 or 17 or 18 or 19 or 20 or 21 or 22
Alternatively, the method for producing a ceramics sintered body according to 23 or 24. 26. The material for generating cordierite in the gap between the synthetic cordierites is talc,
It is kaolin, The manufacturing method of the ceramics sintered compact of Claim 16 or 17 or 18 or 19 or 20 or 21 or 22 or 23 or 24. 27. A method for producing a ceramics sintered body, comprising at least one of petalite and spodumene, zircon, and synthetic cordierite as a base material.
A base material manufacturing process of manufacturing a base material by mixing talc and kaolin, a molding process of molding the base material manufactured in the base material manufacturing process into a predetermined shape, and a molding process of the molding process. A first firing step for producing a green body by firing a base material, and a glaze step for applying a glaze having at least one of petalite and spodumene and zircon to the base produced in the first firing step. And a second firing step of firing the base material glazed in the glaze step. 28. The mixing ratio in the base material is 10 to 30% by weight for the synthetic cordierite, 5 to 15% by weight for the talc, and 35 for the kaolin.
To 50% by weight, at least one of the petalite and spodumene is 5 to 10% by weight, the zircon is 5 to 10% by weight, and the mixing ratio in the glaze is at least the above petalite and spodumene. Either is 70 to 80% by weight, and zircon is 5 to 5%.
28. The method for producing a ceramics sintered body according to claim 27, which is 15% by weight. 29. The method for producing a ceramics sintered body according to claim 27, wherein the base material further contains alumina. 30. The mixing ratio of the base material is such that talc is 5 to 15% by weight and kaolin is 35 to 35% by weight.
30% by weight, and 6% by weight or less of alumina, 25 or 26 or 27 or 28.
29. The method for manufacturing a ceramics sintered body according to 29. 31. The base material according to claim 16, further comprising feldspar.
9 or 20 or 21 or 22 or 23 or 24 or 25
Alternatively, the method for producing a ceramic sintered body according to 26, 27, 28, 29 or 30.