JP7276812B2 - Heat-resistant clay raw materials and heat-resistant ceramics - Google Patents
Heat-resistant clay raw materials and heat-resistant ceramics Download PDFInfo
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- 239000004927 clay Substances 0.000 title claims description 103
- 239000002994 raw material Substances 0.000 title claims description 58
- 239000000919 ceramic Substances 0.000 title claims description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 49
- 239000000463 material Substances 0.000 claims description 48
- 239000005350 fused silica glass Substances 0.000 claims description 40
- 238000010304 firing Methods 0.000 claims description 39
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 claims description 36
- 229910052670 petalite Inorganic materials 0.000 claims description 36
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052878 cordierite Inorganic materials 0.000 claims description 18
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000010433 feldspar Substances 0.000 claims description 11
- -1 Rouseki Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000010459 dolomite Substances 0.000 claims description 5
- 229910000514 dolomite Inorganic materials 0.000 claims description 5
- 239000000454 talc Substances 0.000 claims description 5
- 229910052623 talc Inorganic materials 0.000 claims description 5
- 235000012222 talc Nutrition 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001553 barium compounds Chemical class 0.000 claims description 4
- 238000010411 cooking Methods 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 4
- 150000003438 strontium compounds Chemical class 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- 230000009467 reduction Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 235000012211 aluminium silicate Nutrition 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- 239000005995 Aluminium silicate Substances 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052571 earthenware Inorganic materials 0.000 description 3
- 239000003779 heat-resistant material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012771 household material Substances 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052604 silicate mineral Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 229910000174 eucryptite Inorganic materials 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910001760 lithium mineral Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011214 refractory ceramic Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- 229910052644 β-spodumene Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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- Cookers (AREA)
Description
本発明は、低熱膨張係数を持つ工業素材や家庭用素材などの原料として用いられる耐熱粘土原料に関するものである。特に、直火用などの食器または調理器として使用可能な耐熱陶磁器に用いられる耐熱粘土原料に関する。 TECHNICAL FIELD The present invention relates to a heat-resistant clay raw material having a low coefficient of thermal expansion, which is used as a raw material for industrial materials and household materials. In particular, it relates to a heat-resistant clay raw material used for heat-resistant ceramics that can be used as tableware or cooking utensils for direct fire.
コーディエライト（２ＭｇＯ・２Ａｌ2Ｏ3・５ＳｉＯ2）またはペタライトを用いた低膨張のセラミックス焼結体は、陶磁器製品や低膨張を特徴とするセラミックとして工業に利用されている。これらは、熱膨張係数が小さく、耐熱衝撃性に優れていることが知られている。 Low-expansion ceramic sintered bodies using cordierite ( 2MgO.2Al.sub.2 O.sub.3.5SiO.sub.2 ) or petalite are industrially used as ceramic products and low-expansion ceramics. These are known to have a small thermal expansion coefficient and excellent thermal shock resistance.
従来の直火用の耐熱素材は、土鍋のような耐熱陶器製食器に使用されてきた。他にも瓦やレンガなどの低膨張性能を必要としている製品にも含まれている。日本国内での直火用の耐熱素材は、主流は、ペタライトとコーディエライトであった。陶磁器などが熱衝撃により割れる理由は、加熱・冷却に伴う体積変化による破壊である。ペタライトやコーディエライトは低い熱膨張の素材であり、これを粘土と混合することにより、耐熱性能を向上させることができる。 Conventional heat-resistant materials for direct fire have been used for heat-resistant ceramic tableware such as clay pots. It is also included in other products that require low expansion performance, such as roof tiles and bricks. In Japan, the main heat-resistant materials for direct fire were petalite and cordierite. The reason why ceramics break due to thermal shock is destruction due to volume change accompanying heating and cooling. Petalite and cordierite are materials with low thermal expansion, and by mixing them with clay, heat resistance can be improved.
このように、低膨張原料であるペタライトは粘土と混合した混合粘土として利用され、この混合粘土を焼結したものは耐熱陶磁器として広く普及している。例えば、特許文献１では、粘土を２０～８０重量％、所定メッシュサイズのペタライトを８０～２０重量％の割合で混練した混錬体とし、これを炭素粒子と珪酸化合物の混練体と混練した後、所定の温度で焼成することを特徴とする耐熱材の製造方法が提案されている。 Thus, petalite, which is a low-expansion raw material, is used as mixed clay mixed with clay, and sintered mixed clay is widely used as heat-resistant ceramics. For example, in Patent Document 1, a kneaded body obtained by kneading 20 to 80% by weight of clay and 80 to 20% by weight of petalite having a predetermined mesh size is kneaded with a kneaded body of carbon particles and a silicic acid compound. , a method for producing a heat-resistant material characterized by firing at a predetermined temperature has been proposed.
また、特許文献２では、低膨張性セラミックス製容器本体の表面に釉薬を施釉し底面に薄膜導電層を被着形成してなる電磁誘導加熱調理器用容器であって、その容器本体の素地がペタライト７０％と粘土３０％とからなるものが提案されている。また、特許文献３では、タルク、長石、粘土鉱物、コーディエライト、および融剤からなる直火用磁器素地が提案されている。 Further, Patent Document 2 discloses a container for an electromagnetic induction heating cooker in which a glaze is applied to the surface of a container body made of low-expansion ceramics and a thin film conductive layer is adhered to the bottom surface, and the base material of the container body is petalite. A composition of 70% and 30% clay has been proposed. Further, Patent Document 3 proposes a porcelain body for open fire, which is composed of talc, feldspar, clay mineral, cordierite, and flux.
耐熱陶磁器は、土鍋やご飯炊きの様に一般家庭に広く普及している。主要な構成原料は粘土と低膨張材であり、これに添加材を配合することで焼成した製品に特長を持たせている。従来の良質な日本製土鍋などの陶磁器製品では、低膨張材としてペタライトが多く利用されている。これは、コーディエライトでは十分な精度が得られず、より低膨張のペタライトが好まれるためである。 Heat-resistant ceramics are widely used in general households, such as clay pots and rice cookers. The main constituent raw materials are clay and low-expansion materials, and by adding additives to them, the characteristics of fired products are given. Petalite is often used as a low-expansion material in conventional ceramic products such as earthenware pots made in Japan. This is because cordierite does not provide sufficient accuracy and petalite with lower expansion is preferred.
ここで、ペタライトは、原産国がブラジルとジンバブエ共和国に限定されている。ブラジルの鉱山は廃坑となっており、現状、国内ではジンバブエ共和国のみから輸入している。また、ジンバブエ共和国は、近年のクーデターと外貨の喪失、ハイパーインフレで、経済が不安定であり、荷物の滞りが起きている。このペタライトの希少性の高さと納入リスクの高さから価格も上昇しており、陶磁器製品の生産コストを増加させる要因となっている。このため、納入の安定性の向上と生産コストの低減が可能な代替原料の開発が求められている。 Here, for petalite, the country of origin is limited to Brazil and the Republic of Zimbabwe. Brazil's mines have been abandoned, and currently, we import only from the Republic of Zimbabwe. In addition, the Republic of Zimbabwe is experiencing economic instability due to the recent coup d'état, loss of foreign currency, and hyperinflation, causing delays in cargo. Due to the high rarity of petalite and the high delivery risk, the price is also rising, which is a factor in increasing the production cost of ceramic products. Therefore, there is a demand for the development of alternative raw materials that can improve the stability of delivery and reduce production costs.
その他、陶磁器の焼成には、酸化焼成と還元焼成があり、特に還元焼成では発色のよい陶磁器が得られる。しかしながら、通常、粘土はこの焼成条件の違いにより熱膨張係数が異なり、十分な低膨張性（耐熱性）が得られない場合がある。このため、焼成条件の如何（酸化・還元）に関わらず、低い熱膨張係数を実現できる耐熱粘土原料の開発も求められている。 In addition, firing of ceramics includes oxidation firing and reduction firing, and particularly reduction firing yields ceramics with good coloring. However, clay usually has a different coefficient of thermal expansion due to the difference in firing conditions, and it may not be possible to obtain sufficiently low expansion (heat resistance). Therefore, there is a demand for the development of a heat-resistant clay raw material that can achieve a low coefficient of thermal expansion regardless of the firing conditions (oxidation or reduction).
本発明はこのような背景に鑑みてなされたものであり、従来の高価なペタライトに大きく依存することなく低コストで製造可能であり、かつ、焼成条件に関わらず低膨張で高い耐熱性を備える耐熱陶磁器の原料となる耐熱粘土原料、および、この耐熱粘土原料の焼成体として得られる耐熱陶磁器を提供することを目的とする。 The present invention has been made in view of this background, and can be manufactured at low cost without relying heavily on conventional expensive petalite, and has low expansion and high heat resistance regardless of firing conditions. It is an object of the present invention to provide a heat-resistant clay raw material which is a raw material for heat-resistant ceramics, and a heat-resistant ceramics obtained as a sintered body of the heat-resistant clay raw material.
本発明の耐熱粘土原料は、粘土および低膨張材を主成分とする耐熱粘土原料であって、上記低膨張材は、（１）溶融石英のみ、（２）溶融石英とペタライト、（３）溶融石英とコーディエライト、（４）溶融石英とペタライトとコーディエライト、のいずれかの組み合わせで構成され、上記記主成分である上記粘土と上記低膨張材との合計１００質量部において、上記粘土が１０～７０質量部であり、残部が上記低膨張材であることを特徴とする。 The heat-resistant clay raw material of the present invention is a heat-resistant clay raw material containing clay and a low-expansion material as main components. In a total of 100 parts by mass of the clay as the main component and the low-expansion material, the clay is 10 to 70 parts by mass, and the balance is the low-expansion material.
上記耐熱粘土原料の酸化焼成による焼成体および還元焼成による焼成体は、室温から７００℃における熱膨張係数が０．１～４．０×１０-6／Ｋであることを特徴とする。 The sintered body obtained by oxidizing and reducing heat-resistant clay raw material is characterized by having a thermal expansion coefficient of 0.1 to 4.0×10 -6 /K at room temperature to 700°C.
なお、本発明における「熱膨張係数」は、室温（２５℃）から７００℃までの温度領域において、熱機械分析装置を用いて測定した平均線膨張係数であり、試料の初期長さに対する試料長さの変化量を温度差で除した値である。 In addition, the "thermal expansion coefficient" in the present invention is an average linear expansion coefficient measured using a thermomechanical analyzer in a temperature range from room temperature (25 ° C.) to 700 ° C., and the sample length with respect to the initial length of the sample. It is the value obtained by dividing the amount of change in thickness by the temperature difference.
上記耐熱粘土原料は、酸化鉄、蝋石、長石、シャモット、ドロマイト、石灰、タルク、マグネサイト、アルミナ、バリウム化合物、およびストロンチウム化合物から選ばれる少なくとも１つの添加材を、上記主成分１００質量部に対して０．１～３０質量部含むことを特徴とする。 The heat-resistant clay raw material contains at least one additive selected from iron oxide, Rouseki, feldspar, chamotte, dolomite, lime, talc, magnesite, alumina, barium compounds, and strontium compounds, per 100 parts by mass of the main component. It is characterized by containing 0.1 to 30 parts by mass.
本発明の耐熱陶磁器は、耐熱粘土原料の焼成体であり、上記耐熱粘土原料が本発明の耐熱粘土原料であることを特徴とする。特に、この耐熱陶磁器は、食器または調理器であることを特徴とする。 The heat-resistant ceramics of the present invention is a fired body of a heat-resistant clay raw material, and the heat-resistant clay raw material is the heat-resistant clay raw material of the present invention. In particular, the heat-resistant ceramics are characterized as tableware or cooking utensils.
本発明の耐熱粘土原料は、主成分として、粘土と、少なくとも溶融石英を含む低膨張材とを、所定割合で含む原料であるので、従来の高価なペタライトやコーディエライトのみに頼ることなく低コストで製造可能であり、かつ、焼成条件に関わらず低膨張で高い耐熱性を備える耐熱陶磁器の原料として好適となる。低膨張は、具体的には、室温から７００℃における熱膨張係数が４．０×１０-6／Ｋ以下の低い値となる。 The heat-resistant clay raw material of the present invention is a raw material containing clay and a low-expansion material containing at least fused quartz in a predetermined ratio as main components. It can be manufactured at a low cost, and is suitable as a raw material for heat-resistant ceramics having low expansion and high heat resistance regardless of firing conditions. Low expansion specifically means that the coefficient of thermal expansion from room temperature to 700° C. is a low value of 4.0×10 −6 /K or less.
耐熱粘土原料は、酸化鉄、蝋石、長石、シャモット、ドロマイト、石灰、タルク、マグネサイト、アルミナ、バリウム化合物、およびストロンチウム化合物から選ばれる少なくとも１つの添加材を、主成分１００質量部に対して０．１～３０質量部含むので、製品に種々の特長を付与できる。特に、蝋石や長石を配合することで、吸水率が減ると共に、焼き締まり効果で強度が増し、それらに比例して、耐熱性が向上する。 The heat-resistant clay raw material contains at least one additive selected from iron oxide, Rouseki, feldspar, chamotte, dolomite, lime, talc, magnesite, alumina, barium compounds, and strontium compounds in an amount of 0 per 100 parts by mass of the main component. Since it contains 1 to 30 parts by mass, various features can be imparted to the product. In particular, by blending Rouseki and feldspar, the water absorption rate is reduced, and the hardening effect increases the strength, and the heat resistance is improved in proportion to these.
本発明の耐熱陶磁器は、上述の本発明の耐熱粘土原料の焼成体であるので、従来の高価なペタライトに大きく依存することなく低コストで製造可能であり、かつ、焼成条件に関わらず低膨張で高い耐熱性を備える。このため、例えば、直火用などの食器または調理器として好適に利用できる。 Since the heat-resistant ceramic of the present invention is a fired body of the heat-resistant clay raw material of the present invention, it can be manufactured at low cost without relying heavily on conventional expensive petalite, and has low expansion regardless of firing conditions. with high heat resistance. Therefore, for example, it can be suitably used as tableware or cooker for open fire.
本発明の耐熱粘土原料は、粘土および低膨張材を主成分とし、陶磁器などの素地原料となるものである。この耐熱粘土原料では、低膨張材として少なくとも溶融石英を配合することを特徴としている。低膨張材の組み合わせは、（１）溶融石英のみ、（２）溶融石英とペタライト、（３）溶融石英とコーディエライト、（４）溶融石英とペタライトとコーディエライト、のいずれかである。これらの組み合わせは、従来のペタライトの全部または一部を溶融石英を含む他の低膨張材に置換するものであり、いずれの組み合わせにおいてもペタライト配合量の低減が図れる。 The heat-resistant clay material of the present invention contains clay and a low-expansion material as main components, and is used as a base material for ceramics and the like. This heat-resistant clay raw material is characterized by containing at least fused quartz as a low-expansion material. Combinations of low-expansion materials are any of (1) fused silica only, (2) fused silica and petalite, (3) fused silica and cordierite, and (4) fused silica, petalite and cordierite. These combinations replace all or part of the conventional petalite with another low-expansion material containing fused silica, and any combination can reduce the amount of petalite blended.
主成分である粘土と低膨張材の合計の耐熱粘土原料全体に対する含有割合は、５０質量％以上であり、好ましくは６０質量％以上であり、より好ましくは８０質量％以上であり、さらに好ましくは９０質量％以上である。また、耐熱粘土原料全体に対する各成分の含有割合としては、例えば、溶融石英が２０質量％以上７０質量％未満、粘土が３０質量％以上８０質量％未満、添加材が数質量％から４０質量％程度である。 The total content of the main component clay and low-expansion material in the total heat-resistant clay raw material is 50% by mass or more, preferably 60% by mass or more, more preferably 80% by mass or more, and still more preferably It is 90% by mass or more. The content of each component in the entire heat-resistant clay raw material is, for example, 20% by mass or more and less than 70% by mass of fused silica, 30% by mass or more and less than 80% by mass of clay, and several to 40% by mass of additives. degree.
母材となる粘土としては、カオリン鉱物群を含む粘土類（蛙目粘土、木節粘土、カオリナイト、ディッカイト、ナクライト、ハロイサイト、ニュージランドカオリン、朝鮮カオリン、河東カオリンなどのカオリン）、セリサイト、ベントナイトなどが挙げられる。 Clays used as base materials include clays containing kaolin mineral groups (kaolins such as Gairome clay, Kibushi clay, kaolinite, dickite, nacrite, halloysite, New Zealand kaolin, Korean kaolin, and Kawato kaolin), sericite, and bentonite. etc.
粘土は、主成分である粘土と低膨張材との合計１００質量部に占める割合が１０～７０質量部である。好ましくは３０～７０質量部であり、より好ましくは４０～６０質量部であり、さらに好ましくは４５～５５質量部である。主成分における粘土が、１０質量部未満であると製品形状への成形が困難となるおそれがあり、７０質量部をこえると、粘土の高い熱膨張係数により十分な耐熱性が得られなくなるおそれがある。 The clay accounts for 10 to 70 parts by mass of the total 100 parts by mass of the main component clay and the low-expansion material. It is preferably 30 to 70 parts by mass, more preferably 40 to 60 parts by mass, still more preferably 45 to 55 parts by mass. If the clay in the main component is less than 10 parts by mass, molding into a product shape may be difficult, and if it exceeds 70 parts by mass, sufficient heat resistance may not be obtained due to the high coefficient of thermal expansion of the clay. be.
溶融石英は、結晶質の石英と異なり、ＳｉＯ2の純度が高く、アモルファス状態の石英である。本発明で使用できる溶融石英（石英ガラス）としては、水晶、石英を酸水素炎や電気により高温で溶融したものを急冷固化し、これを粉砕した粉末や、化学気相蒸着法、ゾル－ゲル法により得られたものなどが挙げられる。 Unlike crystalline quartz, fused quartz has a high purity of SiO 2 and is amorphous quartz. Fused quartz (quartz glass) that can be used in the present invention includes powders obtained by melting crystal or quartz at a high temperature with an oxyhydrogen flame or electricity, then rapidly solidifying and pulverizing them, chemical vapor deposition, sol-gel. Examples include those obtained by law.
石英は、長石原料などに含まれており、陶磁器原料として広く使用されている。しかし、陶磁器に使用される石英は多くが結晶質のものである。粘土や釉に石英を混ぜる理由としては、焼成後の陶磁器強度の向上や光沢のために添加されることが多いが、熱膨張係数が増加する。耐熱陶磁器は、焼成温度を調整（１３００℃以下）することで、陶磁器中のＳｉＯ2を完全に溶融させずに焼結させることができる。これにより、ペタライトの様な低膨張の結晶の性能を維持したままの陶磁器を生産できる。溶融石英は非晶質であり、熱膨張係数の低い原料である。自然界にある石英は、ほとんどが結晶質であり、通常、耐熱陶磁器粘土にペタライトとコーディエライトを除く長石類を混ぜることはない。本発明では、ペタライトの全部または一部を溶融石英に置換した耐熱粘土原料とし、溶融石英を完全に溶融させずに焼結させることなどにより、低膨張で高い耐熱性を備えた耐熱陶磁器を実現している。 Quartz is contained in raw materials such as feldspar, and is widely used as a raw material for ceramics. However, most of the quartz used in ceramics is crystalline. The reason why quartz is mixed with clay or glaze is that it is often added to improve the strength and luster of ceramics after firing, but it increases the coefficient of thermal expansion. Heat-resistant ceramics can be sintered without completely melting SiO 2 in the ceramics by adjusting the firing temperature (1300° C. or lower). As a result, ceramics can be produced while maintaining the performance of low-expansion crystals such as petalite. Fused silica is amorphous and a raw material with a low coefficient of thermal expansion. Quartz in nature is mostly crystalline, and feldspars other than petalite and cordierite are usually not mixed with refractory ceramic clay. In the present invention, heat resistant ceramics with low expansion and high heat resistance are realized by using a heat resistant clay raw material in which all or part of the petalite is replaced with fused silica, and by sintering the fused silica without completely melting it. are doing.
溶融石英は、化学合成によって製造されるため、安定した入手が可能である。この結果、本発明の耐熱粘土原料と耐熱陶磁器の安定供給が可能となる。また、低膨張材として溶融石英を主に用いることで、原料調達がペタライトに大きくは依存せず、ジンバブエ共和国からの荷物の供給の不安定さや価格の高騰に悩まされることがなくなる。 Since fused silica is produced by chemical synthesis, it is readily available. As a result, it is possible to stably supply the heat-resistant clay raw material and the heat-resistant ceramics of the present invention. In addition, by using fused silica as the main low-expansion material, the procurement of raw materials does not depend heavily on petalite, and there is no need to worry about the unstable supply of goods from the Republic of Zimbabwe or the price hike.
溶融石英以外の低膨張材として、上記のとおりペタライトとコーディエライトを用いる。ペタライトは、リチウム含有のケイ酸塩鉱物である。コーディエライト（２ＭｇＯ・２Ａｌ2Ｏ3・５ＳｉＯ2）は、マグネシウム含有のケイ酸塩鉱物である。 Petalite and cordierite are used as low-expansion materials other than fused silica, as described above. Petalite is a lithium-containing silicate mineral. Cordierite (2MgO.2Al 2 O 3 .5SiO 2 ) is a magnesium-containing silicate mineral.
低膨張材は、主成分である粘土と低膨張材との合計１００質量部に占める割合が３０～９０質量部である。この低膨張材は、主成分における粘土を除いた残部であるので、主成分に占める割合は、上述の粘土の範囲から決定できる。
また、低膨張材の組み合わせとして、溶融石英以外を併用するケースである（２）溶融石英とペタライト、（３）溶融石英とコーディエライト、（４）溶融石英とペタライトとコーディエライトの場合は、いずれの場合も、低膨張材の全量に対して溶融石英を半量以上とすることが好ましい。低膨張材の含有割合としては、（溶融石英：それ以外）＝（４：１）～（１：１）とすることが好ましい。
The low-expansion material accounts for 30 to 90 parts by mass with respect to 100 parts by mass in total of the main component clay and the low-expansion material. Since this low-expansion material is the remainder of the main component excluding clay, the ratio of the low-expansion material to the main component can be determined from the above range of clay.
In addition, as a combination of low-expansion materials, there are cases in which materials other than fused silica are used in combination. In either case, it is preferable that the amount of fused quartz is half or more of the total amount of the low-expansion material. The content ratio of the low-expansion material is preferably (fused silica:other)=(4:1) to (1:1).
本発明では、これらの低膨張材以外に、添加材として他の低膨張な原料を含有してもよい。例えば、β－スポジュメン（Ｌｉ2Ｏ・Ａｌ2Ｏ3・４ＳｉＯ2）、β－ユークリプタイト（Ｌｉ2Ｏ・Ａｌ2Ｏ3・２ＳｉＯ2）などのリチウム系鉱物、ムライト（３Ａｌ2Ｏ3・２ＳｉＯ2）、ジルコン（ＺｒＯ2・ＳｉＯ2）、ホウケイ酸ガラス（Ｎａ2Ｏ－Ｂ2Ｏ3－ＳｉＯ2）などが挙げられる。 In the present invention, in addition to these low-expansion materials, other low-expansion raw materials may be contained as additives. For example, lithium minerals such as β-spodumene (Li 2 O.Al 2 O 3.4SiO 2 ), β-eucryptite (Li 2 O.Al 2 O 3.2SiO 2 ), mullite (3Al 2 O 3 . 2SiO.sub.2 ) , zircon ( ZrO.sub.2.SiO.sub.2 ), borosilicate glass ( Na.sub.2O -- B.sub.2O.sub.3 -- SiO.sub.2 ), and the like.
耐熱粘土原料には、一般の耐熱陶磁器原料において公知の添加材を添加してもよい。添加材としては、例えば、酸化鉄、蝋石、長石、シャモット、カオリン、ドロマイト、石灰、タルク、マグネサイト、アルミナ、バリウム化合物、ストロンチウム化合物などが挙げられる。これらは単独でも２種以上を併用してもよい。これらの中でも、酸化鉄、蝋石、長石、シャモットを添加することが好ましい。酸化鉄（酸化第二鉄）は色付けなどに使用され、蝋石は滑材として使用され、長石は光沢出しなどに使用され、シャモットは焼き締まり時のクッション材などに使用される。 Additives known in the general heat-resistant ceramic raw material may be added to the heat-resistant clay raw material. Additives include, for example, iron oxide, Rouseki, feldspar, chamotte, kaolin, dolomite, lime, talc, magnesite, alumina, barium compounds, and strontium compounds. These may be used alone or in combination of two or more. Among these, it is preferable to add iron oxide, Rouseki, feldspar, and chamotte. Iron oxide (ferric oxide) is used for coloring, Rouseki is used as a lubricant, feldspar is used for lustering, and chamotte is used as a cushioning material during baking.
添加材は、主成分１００質量部に対して、例えば合計で０．１～３０質量部配合できる。好ましくは０．１～１０質量部であり、より好ましくは０．１～５質量部である。 Additives can be blended, for example, in a total amount of 0.1 to 30 parts by mass with respect to 100 parts by mass of the main component. It is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass.
本発明の耐熱陶磁器は、本発明の耐熱粘土原料の焼成体である。耐熱陶磁器は、大きく分けて（Ａ）耐熱粘土原料からなる陶土を成形する、（Ｂ）必要に応じて陶土の成形体の表面に施釉する、（Ｃ）焼成炉にて焼成し、その後炉冷する、の工程により製造される。 The heat-resistant ceramics of the present invention are fired bodies of the heat-resistant clay raw material of the present invention. Heat-resistant ceramics can be broadly divided into (A) molding pottery clay made from heat-resistant clay raw materials, (B) applying a glaze to the surface of a molded body of pottery clay as necessary, and (C) firing in a firing furnace and then cooling in the furnace. Manufactured by the process of
（Ａ）の成形工程では、耐熱粘土原料を構成する各鉱物などを所定量混合する。この混合は公知の湿式または乾式法いずれの方法であっても使用できる。湿式法で混合した場合は混合物（泥漿）を脱水、ケーキ化して成形用の陶土とする。材料は、混練後に成形される。成形方法としては、ローラーマシーン成形、プレス成形、圧力鋳込（圧搾）成形、鋳込成形、水コテ成形などを利用でき、土鍋など所定の形状に成形される。 In the forming step (A), predetermined amounts of each mineral constituting the heat-resistant clay raw material are mixed. Any known wet or dry method can be used for this mixing. When mixed by a wet method, the mixture (sludge) is dehydrated and turned into a cake to obtain pottery clay for molding. The material is shaped after kneading. As a molding method, roller machine molding, press molding, pressure casting (squeezing) molding, cast molding, water iron molding, etc. can be used, and it is molded into a predetermined shape such as an earthenware pot.
（Ｂ）の施釉工程は、必要に応じて実施される。この工程では、（Ａ）の工程で成形された成形体の表面に施釉する。釉薬は、ガラス質の釉層を形成できるものであれば使用できる。施釉の方法としては、ディッピング、スプレー掛けなどを利用でき、成形体の表面に施釉される。 The glazing step (B) is carried out as necessary. In this step, the surface of the compact formed in step (A) is glazed. Any glaze can be used as long as it can form a vitreous glaze layer. Dipping, spraying, or the like can be used as the glaze method, and the glaze is applied to the surface of the compact.
（Ｃ）の焼成工程では、上記で得られた成形体をガス窯や電気窯内に入れ、これを１１５０～１３００℃の温度、好ましくは１１５０～１２５０℃の温度で焼成する。焼成時間は８～１２時間程度である。１３００℃以下で焼成することで、上述のように溶融石英を完全に溶融させずに焼結できる。ここで、焼成条件として、酸化焼成と還元焼成とがあり、いずれの条件としてもよい。酸化焼成は、窯内に多量の空気（酸素）を供給し、十分に酸素が存在する条件化で焼成する方法である。還元焼成は、例えば窯内に木や石炭、ガスなどを不完全燃焼を起こす程度に投入して焼成する方法である。 In the firing step (C), the compact obtained above is placed in a gas kiln or an electric kiln and fired at a temperature of 1150 to 1300°C, preferably 1150 to 1250°C. The firing time is about 8 to 12 hours. By firing at 1300° C. or less, fused quartz can be sintered without being completely melted as described above. Here, firing conditions include oxidative firing and reduction firing, and either of them may be used. Oxidation firing is a method in which a large amount of air (oxygen) is supplied into the kiln and firing is performed under conditions in which sufficient oxygen exists. Reduction firing is, for example, a firing method in which wood, coal, gas, or the like is put into a kiln to the extent that it causes incomplete combustion.
本発明の耐熱陶磁器は、直火に掛けた場合、経済産業省認定工場のための工業標準化法に基づいたＪＩＳ Ｓ ２４００で規定されている温度差３５０℃以上の基準を満たすものである。また、粘土と溶融石英のみの調合だけではなく、添加材（溶融鉱物）として蝋石やカオリン、ドロマイト、長石などを添加することで、より焼き締り、低膨張のまま高強度が得られる。溶融石英の使用により、従来の高価なペタライトやコーディエライトを使用しない、または、使用量を低減しつつ、低膨張かつ直火に強い耐熱陶磁器が製造できる。 The heat-resistant ceramic of the present invention satisfies the standard of temperature difference of 350°C or more specified in JIS S 2400 based on the Industrial Standardization Law for Ministry of Economy, Trade and Industry certified factories when exposed to an open flame. In addition to mixing only clay and fused quartz, adding Rouseki, kaolin, dolomite, feldspar, etc. as additives (fused minerals) makes it possible to harden and obtain high strength with low expansion. By using fused silica, it is possible to produce heat-resistant ceramics with low expansion and resistance to direct fire without using conventional expensive petalite or cordierite, or with a reduced amount of use.
陶磁器が熱衝撃により割れる理由は、加熱・冷却に伴う体積変化による破壊である。ペタライトやコーディエライトは低い熱膨張の素材であり、従来は、これを粘土と混合することにより、耐熱陶磁器用の原料の生産を行っている。溶融石英も低い熱膨張を持つ素材であり、本発明ではこれを採用することで新たな耐熱陶磁器用の粘土材料を得ている。 The reason why ceramics crack due to thermal shock is destruction due to volume change accompanying heating and cooling. Petalite and cordierite are materials with low thermal expansion, and conventionally, raw materials for heat-resistant ceramics are produced by mixing them with clay. Fused quartz is also a material with low thermal expansion, and by adopting this in the present invention, a new clay material for heat-resistant ceramics is obtained.
このように、溶融石英は低膨張であるため、粘土など膨張係数の高い鉱物と混ぜ合わせることにより、低膨張の耐熱粘土原料が実現できると考えた。しかし、粘土とペタライトを使用する場合と比較すれば、粘土と溶融石英のみでは焼き締まりが劣る。このため、上述のように蝋石などの溶融鉱物を使用することで、焼き締まった低膨張を実現できる。 Since fused silica has a low expansion coefficient in this way, we thought that it would be possible to realize a low-expansion heat-resistant clay raw material by mixing it with minerals with a high expansion coefficient such as clay. However, compared with the case of using clay and petalite, using only clay and fused quartz results in poor densification. Therefore, by using a molten mineral such as Rouseki as described above, a hardened low expansion can be achieved.
耐熱粘土原料の酸化焼成による焼成体および還元焼成による焼成体は、室温から７００℃における熱膨張係数が０．１～４．０×１０-6／Ｋであることが好ましい。より好ましくは０．１～３．０×１０-6／Ｋであり、さらに好ましくは０．１～２．５×１０-6／Ｋである。熱膨張係数が４．０×１０-6／Ｋをこえる場合、用途によっては十分な耐熱性が得られないおそれがある。 It is preferable that the calcined body obtained by oxidizing and reducing the heat-resistant clay raw material has a thermal expansion coefficient of 0.1 to 4.0×10 -6 /K at room temperature to 700°C. It is more preferably 0.1 to 3.0×10 -6 /K, still more preferably 0.1 to 2.5×10 -6 /K. If the coefficient of thermal expansion exceeds 4.0×10 −6 /K, there is a possibility that sufficient heat resistance cannot be obtained depending on the application.
また、還元焼成と酸化焼成の場合における同温度条件で測定した熱膨張係数の差が、－１．０～１．０×１０-6／Ｋであることが好ましい。より好ましくは－０．８～０．８×１０-6／Ｋであり、さらに好ましくは－０．５～０．５×１０-6／Ｋである。熱膨張係数の差が、±１．０×１０-6／Ｋ範囲内とすることで、焼成条件に関わらず、十分な低膨張性（耐熱性）が得られる。 Also, the difference in thermal expansion coefficient measured under the same temperature conditions in the case of reduction firing and oxidation firing is preferably -1.0 to 1.0×10 -6 /K. It is more preferably −0.8 to 0.8×10 −6 /K, still more preferably −0.5 to 0.5×10 −6 /K. By setting the difference in thermal expansion coefficient within the range of ±1.0×10 −6 /K, sufficiently low expansion (heat resistance) can be obtained regardless of the firing conditions.
本発明の耐熱陶磁器は、後述の実施例に示すように、耐熱粘土原料の組成によっては、ペタライト製の直火用耐熱食器の熱膨張係数の標準値であった熱膨張係数２．０×１０-6／Ｋ以下の低膨張性（耐熱性）をも実現できる。 Depending on the composition of the heat-resistant clay raw material, the heat-resistant ceramics of the present invention have a coefficient of thermal expansion of 2.0×10, which is the standard value of the heat-resistant tableware made of Petalite for direct fire, as shown in the examples below. A low expansibility (heat resistance) of -6 /K or less can also be achieved.
実施例１～実施例１７
表１に示す組成の耐熱粘土原料を調整し、これを用いて所定の試験片を成形し、同表に示す各雰囲気において１２００℃で８時間焼成して、試験片を制作した。粘土は、蛙目粘土を用いた。この試験片の熱膨張係数を、熱機械分析装置を用い、昇温速度を７℃／分として室温（２５℃）から７００℃まで加熱して測定した。結果を表１に示す。なお、実施例１６と実施例１７については、粘土分が少ないため試験片に脆さがあった。
Examples 1 to 17
A heat-resistant clay raw material having the composition shown in Table 1 was prepared, a predetermined test piece was molded using this, and fired at 1200° C. for 8 hours in each atmosphere shown in the same table to produce a test piece. Gairome clay was used as the clay. The coefficient of thermal expansion of this test piece was measured by heating from room temperature (25° C.) to 700° C. at a heating rate of 7° C./min using a thermomechanical analyzer. Table 1 shows the results. In Examples 16 and 17, the test pieces were brittle due to the low clay content.
比較例１、比較例２
表２に示す組成の粘土原料を調整し、これを用いて所定の試験片を成形し、同表に示す各雰囲気において１２００℃で８時間焼成して、試験片を制作した。粘土は、蛙目粘土を用いた。この試験片の熱膨張係数を、実施例１と同様に測定した。結果を表２に示す。
Comparative Example 1, Comparative Example 2
A clay raw material having the composition shown in Table 2 was prepared, a predetermined test piece was molded using this, and fired at 1200° C. for 8 hours in each atmosphere shown in the same table to produce a test piece. Gairome clay was used as the clay. The thermal expansion coefficient of this test piece was measured in the same manner as in Example 1. Table 2 shows the results.
参考例１、参考例２
低膨張材にペタライトのみを用いた場合の例として、表３に示す組成の耐熱粘土原料を調整し、これを用いて所定の試験片を成形し、同表に示す各雰囲気において１２００℃で８時間焼成して、試験片を制作した。粘土は、蛙目粘土を用いた。この試験片の熱膨張係数を、実施例１と同様に測定した。結果を表３に示す。
Reference Example 1, Reference Example 2
As an example of using only petalite as a low-expansion material, a heat-resistant clay raw material having the composition shown in Table 3 was prepared, a predetermined test piece was molded using this, and the test piece was heated at 1200 ° C. in each atmosphere shown in the same table. It was baked for a period of time to produce a test piece. Gairome clay was used as the clay. The thermal expansion coefficient of this test piece was measured in the same manner as in Example 1. Table 3 shows the results.
実施例１と実施例２に示すように、溶融石英と粘土の単味の調合では、酸化焼成１．９３４×１０-6／Ｋであり、還元焼成２．５１６×１０-6／Ｋであり、還元焼成の焼き締まりの結果、還元雰囲気で焼成した方が３０％ほど高くなった。
一方、実施例３と実施例４に示すように、溶融石英とペタライトと粘土の混合の調合では、酸化焼成２．１８２×１０-6／Ｋであり、還元焼成２．１７８×１０-6／Ｋであり、ほぼ変わらない結果であった。これは、ガラス化したペタライトに溶融石英が付着したためと推察される。
As shown in Examples 1 and 2, the simple blend of fused quartz and clay had an oxidative firing rate of 1.934×10 −6 /K and a reduction firing rate of 2.516×10 −6 /K. As a result of reduction firing, firing in a reducing atmosphere was about 30% higher.
On the other hand, as shown in Examples 3 and 4, in the blend of fused quartz, petalite and clay, the oxidation firing rate was 2.182×10 −6 /K and the reduction firing rate was 2.178×10 −6 /K. K, and the result was almost the same. It is presumed that this is because fused quartz adheres to the vitrified petalite.
実施例１１は、粘土５０質量部に対し、溶融石英とペタライトを２５質量部ずつ２等分に割った上、土鍋などの水漏れ防止の焼結材としてＮＡＴ酸化鉄（酸化第二鉄）を３質量部混ぜてある。
この実施例１１を実施例３と比較した場合、ＮＡＴ酸化鉄が混ざると、それに準じて本来、熱膨張係数は悪くなる（大きくなる）が、溶融石英の焼き締まりが緩やかであるため、その分、熱膨張係数は７．９％ほど低くなった。また、実施例１２に示すように、同調合で還元焼成の場合、熱膨張係数は３．８％ほど高くなった。これは、還元焼成による鉄の焼き締りが大きいためである。
なお、実施例１２は、２．２６１×１０-6／Ｋという結果であり、これは土鍋や耐熱食器では十分通用する値である。また、ＪＩＳ Ｓ ２４００陶磁器製耐熱食器の耐熱検査３５０℃以上に耐えうるものである。
In Example 11, 50 parts by mass of clay and 25 parts by mass of fused quartz and petalite were divided into two equal parts, and NAT iron oxide (ferric oxide) was added as a sintering material to prevent water leakage in clay pots. 3 parts by mass are mixed.
When this Example 11 is compared with Example 3, when NAT iron oxide is mixed, the coefficient of thermal expansion is originally deteriorated (increased) accordingly, but since the densification of fused silica is moderate, , the coefficient of thermal expansion was lowered by 7.9%. In addition, as shown in Example 12, the thermal expansion coefficient increased by about 3.8% in the case of reduction firing with the same blending. This is because iron is strongly densified by reduction firing.
The result of Example 12 is 2.261×10 −6 /K, which is a value that is sufficiently acceptable for earthenware pots and heat-resistant tableware. In addition, it can withstand JIS S 2400 ceramic heat resistant tableware heat resistance test of 350°C or higher.
実施例１５は、粘土５０質量部に対し、溶融石英とコーディエライトを２５質量部ずつ２等分に割った上、土鍋などの水漏れ防止の焼結材としてＮＡＴ酸化鉄（酸化第二鉄）を３質量部混ぜてある。
この実施例１５を実施例５と比較した場合、上記のとおり、ＮＡＴ酸化鉄が混ざると、それに準じて本来、熱膨張係数は悪くなる（大きくなる）ものであり、この比較でも極端に悪化していた。これは、コーディエライトが、質が悪く、石英分との結合が特に悪化していることを表している。
In Example 15, 50 parts by mass of clay and 25 parts by mass of fused quartz and cordierite were divided into two equal parts, and NAT iron oxide (ferric oxide) was used as a sintering material for preventing water leakage in clay pots. ) is mixed with 3 parts by mass.
When this Example 15 is compared with Example 5, as described above, when NAT iron oxide is mixed, the coefficient of thermal expansion is originally deteriorated (increased) accordingly, and even in this comparison, it is extremely deteriorated. was This indicates that the cordierite is of poor quality and is particularly badly bonded to the quartz content.
次に、本発明の耐熱陶磁器の物性測定を行った。
表４に示す組成の耐熱粘土原料を調整し、これを用いて同表に示す寸法の試験片を成形し、酸化焼成雰囲気において１２００℃で８時間焼成して、試験片を制作した。この試験片について、ＪＩＳ Ａ １５０９－４ 陶磁器タイル試験方法を準用して、曲げ強度を測定した。また、この試験片の熱膨張係数を、熱機械分析装置を用い、昇温速度を７℃／分として室温（２５℃）から７００℃まで加熱して測定した。これらの結果を表４に示す。
Next, physical properties of the heat-resistant ceramics of the present invention were measured.
A heat-resistant clay raw material having the composition shown in Table 4 was prepared, a test piece having the dimensions shown in the same table was molded, and fired at 1200° C. for 8 hours in an oxidizing firing atmosphere to produce a test piece. The flexural strength of this test piece was measured according to JIS A 1509-4 ceramic tile test method. Also, the coefficient of thermal expansion of this test piece was measured by heating from room temperature (25° C.) to 700° C. at a heating rate of 7° C./min using a thermomechanical analyzer. These results are shown in Table 4.
本発明の耐熱粘土原料は、高価で供給地が偏重しているペタライトに大きく依存することなく低コストで製造可能であり、かつ、焼成条件に関わらず低膨張で高い耐熱性を備える耐熱陶磁器の原料となるので、低熱膨張係数が要求される工業素材や家庭用素材などの原料として広く利用できる。特に、直火用などの食器または調理器である耐熱陶磁器として好適に利用できる。また、従来のペタライトは、自然鉱物であるため、リチウムの含有量が不安定であった。それに比較して、溶融石英は、安定性がある。また、供給が安定しており、安定生産による消費者保護に貢献できる。 The heat-resistant clay raw material of the present invention can be manufactured at low cost without relying heavily on petalite, which is expensive and has a biased supply source, and is a heat-resistant ceramic with low expansion and high heat resistance regardless of firing conditions. Since it can be used as a raw material, it can be widely used as a raw material for industrial materials and household materials that require a low coefficient of thermal expansion. In particular, it can be suitably used as heat-resistant ceramics such as tableware or cooking utensils for direct fire. In addition, since conventional petalite is a natural mineral, its lithium content is unstable. Fused silica, by comparison, is more stable. In addition, the supply is stable and can contribute to consumer protection through stable production.
Claims (5)
前記低膨張材は、（１）溶融石英のみ、（２）溶融石英とペタライト、（３）溶融石英とコーディエライト、（４）溶融石英とペタライトとコーディエライト、のいずれかの組み合わせで構成され、
前記主成分である前記粘土と前記低膨張材の合計の前記耐熱粘土原料全体に対する含有割合が９０質量％以上であり、
前記主成分である前記粘土と前記低膨張材との合計１００質量部において、前記粘土が４０～６０質量部であり、残部が前記低膨張材であり、
前記耐熱粘土原料の酸化焼成による焼成体および還元焼成による焼成体は、室温から７００℃における熱膨張係数が０．１～４．０×１０-6／Ｋであることを特徴とする耐熱粘土原料。 A heat-resistant clay raw material mainly composed of clay and a low-expansion material,
The low-expansion material is a combination of (1) fused silica only, (2) fused silica and petalite, (3) fused silica and cordierite, or (4) fused silica, petalite, and cordierite. is,
The total content of the clay, which is the main component, and the low-expansion material, with respect to the entire heat-resistant clay raw material is 90% by mass or more,
In a total of 100 parts by mass of the clay that is the main component and the low-expansion material, the clay is 40 to 60 parts by mass, and the balance is the low-expansion material,
The heat-resistant clay raw material, wherein the fired body obtained by oxidizing and firing the heat-resistant clay raw material and the fired body obtained by reducing firing have a thermal expansion coefficient of 0.1 to 4.0×10 −6 /K at room temperature to 700° C. .
前記耐熱粘土原料が、請求項１または請求項２記載の耐熱粘土原料であることを特徴とする耐熱陶磁器。 A heat-resistant ceramic that is a fired body of heat-resistant clay raw material,
A heat-resistant ceramic, wherein the heat-resistant clay material is the heat-resistant clay material according to claim 1 or claim 2 .
前記耐熱粘土原料が、粘土および低膨張材を主成分とし、
前記低膨張材は、（１）溶融石英のみ、（２）溶融石英とペタライト、（３）溶融石英とコーディエライト、（４）溶融石英とペタライトとコーディエライト、のいずれかの組み合わせで構成され、
前記主成分である前記粘土と前記低膨張材との合計１００質量部において、前記粘土が１０～７０質量部であり、残部が前記低膨張材であることを特徴とする耐熱陶磁器。 A heat-resistant ceramic that is a fired body of heat-resistant clay raw material and is a tableware or cooker,
The heat-resistant clay raw material contains clay and a low-expansion material as main components,
The low-expansion material is a combination of (1) fused silica only, (2) fused silica and petalite, (3) fused silica and cordierite, or (4) fused silica, petalite, and cordierite. is,
A heat-resistant ceramic ware characterized by comprising 10 to 70 parts by mass of said clay and the balance being said low-expansion material, in a total of 100 parts by mass of said clay as said main component and said low-expansion material.
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