JP2016104682A - Heat insulator - Google Patents
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- JP2016104682A JP2016104682A JP2014249484A JP2014249484A JP2016104682A JP 2016104682 A JP2016104682 A JP 2016104682A JP 2014249484 A JP2014249484 A JP 2014249484A JP 2014249484 A JP2014249484 A JP 2014249484A JP 2016104682 A JP2016104682 A JP 2016104682A
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- 239000012212 insulator Substances 0.000 title abstract description 4
- 239000011148 porous material Substances 0.000 claims abstract description 111
- 239000000835 fiber Substances 0.000 claims abstract description 50
- 239000000919 ceramic Substances 0.000 claims abstract description 23
- 230000005484 gravity Effects 0.000 claims abstract description 22
- 239000011810 insulating material Substances 0.000 claims description 42
- 229910020068 MgAl Inorganic materials 0.000 claims description 17
- 230000000694 effects Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 238000009413 insulation Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 229910052596 spinel Inorganic materials 0.000 description 7
- 239000011029 spinel Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000011449 brick Substances 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 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
- 239000010419 fine particle Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
Description
本発明は、ＭｇＡｌ２Ｏ４の多孔質焼結体からなり、１０００℃以上の温度域での断熱性に優れた断熱材に関する。 The present invention relates to a heat insulating material comprising a porous sintered body of MgAl 2 O 4 and having excellent heat insulating properties in a temperature range of 1000 ° C. or higher.
特許文献１または２に、所定の気孔径分布を有するスピネル質セラミックス多孔体は、伝導伝熱及び輻射伝熱を抑制できること、それにより１０００℃以上の高温での耐熱性にも優れた断熱材として使用できること、が開示されている。
上記の特許文献１，２に記載されたスピネル質セラミックス多孔体は、従来よりも高温の１０００℃以上での低い熱伝導性と良好な耐熱性を有する一方で、高い気孔率のため、強度が十分とは言えなかった。
The spinel ceramic porous bodies described in the
ところで、強度を向上させるには、気孔率を下げ、かさ比重を高くする手法が一般的である。しかし、特許文献１，２に記載の断熱材で単に気孔率を下げるだけでは、熱伝導率が上昇し、かつ、かさ比重も高くなるので、低い熱伝導率でありながら軽くて扱いやすい断熱材、という要望には、充分応えられるものではなかった。
By the way, in order to improve the strength, a method of decreasing the porosity and increasing the bulk specific gravity is common. However, simply reducing the porosity with the heat insulating materials described in
本発明は、上記技術的課題に鑑み、１０００℃以上の高温でも熱伝導率の増加が抑制されるという優れた断熱性を維持しつつ、軽量性にも優れた断熱材の提供を目的とする。 In view of the above technical problem, the present invention aims to provide a heat insulating material that is excellent in lightness while maintaining excellent heat insulating properties such that an increase in thermal conductivity is suppressed even at a high temperature of 1000 ° C. or higher. .
本発明の一の態様に係る断熱材は、ＭｇＡｌ２Ｏ４中にセラミックス繊維を含み気孔率が８５ｖｏｌ％以上９１ｖｏｌ％未満の多孔質焼結体からなり、孔径０．８μｍ以上１０μｍ未満の気孔が全気孔容積のうち１０ｖｏｌ％以上４０ｖｏｌ％以下を占め、かつ、孔径０．０１μｍ以上０．８μｍ未満の気孔が全気孔容積のうちの５ｖｏｌ％以上１０ｖｏｌ％以下を占め、かさ比重が０．６以下であることを特徴とする。 The heat insulating material according to one aspect of the present invention is made of a porous sintered body containing ceramic fibers in MgAl 2 O 4 and having a porosity of 85 vol% or more and less than 91 vol%, and has pores having a pore diameter of 0.8 μm or more and less than 10 μm. The total pore volume occupies 10 vol% or more and 40 vol% or less, and the pore diameter of 0.01 μm or more and less than 0.8 μm occupies 5 vol% or more and 10 vol% or less of the total pore volume, and the bulk specific gravity is 0.6 or less. It is characterized by being.
かかる構成を有することで、低い熱伝導率を維持しつつ、軽量な断熱材の提供を可能とする。 By having such a configuration, it is possible to provide a lightweight heat insulating material while maintaining a low thermal conductivity.
前記断熱材は、１０００℃以上１５００℃以下における熱伝導率が０．４０Ｗ／（ｍ・Ｋ）以下であると好ましい。 The heat insulating material preferably has a thermal conductivity of not less than 1000 ° C. and not more than 1500 ° C. of 0.40 W / (m · K) or less.
また、高温での熱伝導率の増加が抑制されているほど、高温域においても優れた断熱効果が得られることから、１０００℃以上１５００℃以下における熱伝導率は、２０℃以上１０００℃以下における熱伝導率の１．５倍を超えないことが好ましい。 Moreover, since the heat insulation effect which was excellent also in the high temperature range is acquired, so that the increase in the heat conductivity at high temperature is suppressed, the heat conductivity in 1000 to 1500 degreeC is 20 to 1000 degreeC. It is preferable not to exceed 1.5 times the thermal conductivity.
また、本発明の別の態様にかかる断熱材は、ＭｇＡｌ２Ｏ４中にセラミックス繊維を含む気孔率７０ｖｏｌ％以上８５ｖｏｌ％未満の多孔質焼結体からなり、孔径０．８μｍ以上１０μｍ未満の気孔が全気孔容積のうちの４０ｖｏｌ％以上７０ｖｏｌ％未満を占め、かつ、孔径０．０１μｍ以上０．８μｍ未満の気孔が全気孔容積のうちの１０ｖｏｌ％以上３０ｖｏｌ％未満を占め、１０００℃以上１５００℃以下における熱伝導率が、２０℃以上１０００℃未満における熱伝導率の１．５倍を超えないことを特徴とする。
Further, the heat insulating material according to another aspect of the present invention is a porous sintered body having a porosity of 70 vol% or more and less than 85 vol% containing ceramic fibers in MgAl 2 O 4 , and has a pore diameter of 0.8 μm or more and less than 10 μm.
かかる構成を有することで、軽量でありながら、高温度域での熱伝導率の上昇がより抑制された断熱材の提供を可能とする。 By having such a configuration, it is possible to provide a heat insulating material that is light in weight and further suppresses an increase in thermal conductivity in a high temperature range.
前記断熱材は、高温での熱伝導率が小さいほど、優れた断熱効果が得られることから、１０００℃以上１５００℃以下における熱伝導率が０．４０Ｗ／（ｍ・Ｋ）以下であることが好ましく、より好ましくは、０．３５Ｗ／（ｍ・Ｋ）以下である。 The heat insulating material has an excellent heat insulating effect as the thermal conductivity at a high temperature is small. Therefore, the thermal conductivity at 1000 ° C. or higher and 1500 ° C. or lower is 0.40 W / (m · K) or lower. Preferably, it is 0.35 W / (m · K) or less.
また、高温での熱伝導率の増加が抑制されているほど、高温域においても優れた断熱効果が得られることから、１０００℃以上１５００℃以下における熱伝導率は、２０℃以上１０００℃以下における熱伝導率の１．２倍を超えないことが、より好ましい。 Moreover, since the heat insulation effect which was excellent also in the high temperature range is acquired, so that the increase in the heat conductivity at high temperature is suppressed, the heat conductivity in 1000 to 1500 degreeC is 20 to 1000 degreeC. More preferably, it does not exceed 1.2 times the thermal conductivity.
本発明に係る断熱材は、１０００℃以上の高温でも熱伝導率の増加が抑制されて優れた断熱性が保持されつつ、軽くて扱いやすいものである。さらに、孔径の異なる気孔容積を適切に制御することで、用途により熱伝導率と軽量性を最適化でき、より好適である。 The heat insulating material according to the present invention is light and easy to handle while maintaining an excellent heat insulating property while suppressing an increase in thermal conductivity even at a high temperature of 1000 ° C. or higher. Furthermore, by appropriately controlling the pore volumes having different pore diameters, the thermal conductivity and light weight can be optimized depending on the application, which is more preferable.
以下、本発明を詳細に説明する。本発明の一の態様に係る断熱材は、ＭｇＡｌ２Ｏ４中にセラミックス繊維を含み気孔率が８５ｖｏｌ％以上９１ｖｏｌ％未満の多孔質焼結体からなり、孔径０．８μｍ以上１０μｍ未満の気孔が全気孔容積のうち１０ｖｏｌ％以上４０ｖｏｌ％以下を占め、かつ、孔径０．０１μｍ以上０．８μｍ未満の気孔が全気孔容積のうちの５ｖｏｌ％以上１０ｖｏｌ％以下を占め、かさ比重が０．６以下である。 Hereinafter, the present invention will be described in detail. The heat insulating material according to one aspect of the present invention is made of a porous sintered body containing ceramic fibers in MgAl 2 O 4 and having a porosity of 85 vol% or more and less than 91 vol%, and has pores having a pore diameter of 0.8 μm or more and less than 10 μm. The total pore volume occupies 10 vol% or more and 40 vol% or less, and the pore diameter of 0.01 μm or more and less than 0.8 μm occupies 5 vol% or more and 10 vol% or less of the total pore volume, and the bulk specific gravity is 0.6 or less. It is.
本発明に係る多孔質焼結体の材質は、スピネル質のＭｇＡｌ２Ｏ４（マグネシアスピネル）である。スピネル質の多孔質焼結体は、高温での粒成長や粒界の結合によって生じる気孔の形状や大きさの変動が小さく、熱伝導率の変動を抑制する効果を長期間維持できる。 The material of the porous sintered body according to the present invention is spinel MgAl 2 O 4 (magnesia spinel). The spinel porous sintered body has a small variation in pore shape and size caused by grain growth at high temperature and grain boundary bonding, and can maintain the effect of suppressing variation in thermal conductivity for a long period of time.
特にＭｇＡｌ２Ｏ４は、１０００℃以上の高温域での構造安定性が高く、等方的な結晶構造を有するため、高温に曝された場合でも、特異な粒成長や収縮がほとんど起こらない。 In particular, MgAl 2 O 4 has a high structural stability at a high temperature range of 1000 ° C. or higher and has an isotropic crystal structure, so that even when exposed to high temperatures, the specific grain growth and shrinkage hardly occur.
このため、ＭｇＡｌ２Ｏ４は、本発明の特徴である特定の気孔構成を維持することができるので、高温で使用される断熱材として好適である。なお、前記化学組成及びスピネル質の構造は、例えば、粉末Ｘ線回折法により測定及び同定することができる。 For this reason, MgAl 2 O 4 can maintain the specific pore structure that is a feature of the present invention, and therefore is suitable as a heat insulating material used at high temperatures. The chemical composition and the spinel structure can be measured and identified by, for example, a powder X-ray diffraction method.
そして、本発明に係る多孔質焼結体はセラミックス繊維を含む。セラミックス繊維がＭｇＡｌ２Ｏ４中に含まれると、多孔質焼結体全体の気孔率を高くでき、かさ比重が下がるので、軽量化が図れる。また、繊維を入れずに単に気孔率のみ高くする場合に比べて、強度の向上も図ることが可能である。 And the porous sintered compact which concerns on this invention contains ceramic fiber. When the ceramic fiber is contained in MgAl 2 O 4 , the porosity of the entire porous sintered body can be increased and the bulk specific gravity is lowered, so that weight reduction can be achieved. In addition, it is possible to improve the strength as compared with the case where only the porosity is increased without adding fibers.
セラミックス繊維には、断熱材に用いられる周知の材料を広く適用でき、一例として、アルミナ、ジルコニア、ムライト、等が挙げられる。ただし、高温大気中で酸化分解し、使用できない材料、例えば炭化ケイ素は、あまり好ましいものとは言えない。 Known materials used for heat insulating materials can be widely applied to ceramic fibers, and examples thereof include alumina, zirconia, mullite, and the like. However, materials that cannot be used due to oxidative decomposition in high-temperature air, such as silicon carbide, are not very preferable.
セラミックス繊維の形状も格別制限はない。例えば、平均径３〜１０μｍ、平均長０．２〜１００ｍｍの短繊維、前記短繊維を数百〜数千本束にした繊維束、あるいは連続した長繊維が含まれていてもよい。しかしながら、気孔率を本発明の範囲内に維持する、という観点からは、前記の短繊維を分散させる形態が好ましい。 The shape of the ceramic fiber is not particularly limited. For example, short fibers having an average diameter of 3 to 10 μm and an average length of 0.2 to 100 mm, a fiber bundle in which the short fibers are bundled in hundreds to thousands, or continuous long fibers may be included. However, from the viewpoint of maintaining the porosity within the range of the present invention, the above-described form in which the short fibers are dispersed is preferable.
セラミックス繊維の添加率は、特に限定されるものではないが、少なすぎるとかさ比重低減の効果がほとんど得られない恐れがある。また、多すぎると孔径０．０１μｍ以上０．８μｍ未満の気孔、および、孔径０．８μｍ以上１０μｍ未満の気孔が全体に占める割合の低下により、後述する熱伝導率増加の抑制効果が十分に得られない、という懸念が生じる。 The addition rate of the ceramic fiber is not particularly limited, but if it is too small, the effect of reducing bulk specific gravity may hardly be obtained. On the other hand, if the amount is too large, the pores having a pore diameter of 0.01 μm or more and less than 0.8 μm and the ratio of pores having a pore diameter of 0.8 μm or more and less than 10 μm occupying the whole decrease sufficiently to obtain the effect of suppressing the increase in thermal conductivity described later. There is a concern that it will not be possible.
なお、本発明の一の態様において、孔径０．８μｍ以上１０μｍ未満の気孔が全気孔容積のうち１０ｖｏｌ％以上４０ｖｏｌ％以下を占め、かつ、孔径０．０１μｍ以上０．８μｍ未満の気孔が全気孔容積のうちの５ｖｏｌ％以上１０ｖｏｌ％以下を占めておれば、１０００μｍ以上の気孔を含んでいてもかまわない。 In one embodiment of the present invention, pores having a pore diameter of 0.8 μm or more and less than 10 μm occupy 10 vol% or more and 40 vol% or less of the total pore volume, and pores having a pore diameter of 0.01 μm or more and less than 0.8 μm are all pores. As long as it occupies 5 vol% or more and 10 vol% or less of the volume, it may contain pores of 1000 μm or more.
好ましいセラミックス繊維の添加率は、多孔質焼結体に対して、０．０５ｖｏｌ％以上３５ｖｏｌ％以下、より好ましくは０．１ｖｏｌ％以上３０ｖｏｌ％以下である。 A preferable addition rate of the ceramic fiber is 0.05 vol% or more and 35 vol% or less, more preferably 0.1 vol% or more and 30 vol% or less with respect to the porous sintered body.
なお、セラミックス繊維の含有率は、セラミックス繊維とセラミックス繊維以外の固形分の重量比で調整する。添加量で換算すれば、０．５ｗｔ％以上７５ｗｔ％以下であり、より好ましくは、５ｗｔ％以上６０ｗｔ％以下となる。 In addition, the content rate of ceramic fiber is adjusted with the weight ratio of solid content other than ceramic fiber and ceramic fiber. In terms of the amount added, it is 0.5 wt% or more and 75 wt% or less, and more preferably 5 wt% or more and 60 wt% or less.
また、セラミックス繊維のＭｇＡｌ２Ｏ４中での分布についても、設計される断熱材の要求仕様に応じて適時調整できる。一例として、繊維の密度を、表層は大きく中心部は低くすると、表層が高強度のため型崩れしにくい断熱材とすることができる。 Also, the distribution of ceramic fibers in MgAl 2 O 4 can be adjusted in a timely manner according to the required specifications of the heat insulating material to be designed. As an example, if the density of the fiber is large in the surface layer and low in the central portion, the heat insulating material that does not easily lose shape due to the high strength of the surface layer can be obtained.
また、本発明の一の態様における多孔質焼結体の気孔率は、８５ｖｏｌ％以上９１ｖｏｌ％未満とする。前記気孔率が８５ｖｏｌ％未満では、前記多孔質焼結体中においてＭｇＡｌ２Ｏ４からなる基材部の占める割合が高く、伝導伝熱が増加し、熱伝導率を十分小さくすることが困難となる。一方で、前記気孔率が９１ｖｏｌ％以上では、前記多孔質焼結体中においてＭｇＡｌ２Ｏ４からなる基材部の占める割合が絶対的に低くなるため、極めて脆弱となり、十分な耐熱性が得られない。 Further, the porosity of the porous sintered body in one embodiment of the present invention is set to 85 vol% or more and less than 91 vol%. When the porosity is less than 85 vol%, the proportion of the base material portion made of MgAl 2 O 4 is high in the porous sintered body, the conduction heat transfer increases, and it is difficult to sufficiently reduce the thermal conductivity. Become. On the other hand, when the porosity is 91 vol% or more, the proportion of the base material portion made of MgAl 2 O 4 in the porous sintered body is absolutely low, so that it becomes extremely brittle and sufficient heat resistance is obtained. I can't.
前記気孔率は、ＪＩＳ Ｒ ２６１４「耐火断熱れんがの比重及び真気孔率の測定方法」にて算出される。 The porosity is calculated according to JIS R 2614 “Measurement method of specific gravity and true porosity of refractory heat insulating brick”.
前記多孔質焼結体の気孔構成は、孔径０．８μｍ以上１０μｍ未満の気孔が全気孔容積のうち１０ｖｏｌ％以上４０ｖｏｌ％以下を占めている。 As for the pore structure of the porous sintered body, pores having a pore diameter of 0.8 μm or more and less than 10 μm occupy 10 vol% or more and 40 vol% or less of the total pore volume.
前記多孔質焼結体の気孔は、そのほとんどが孔径１０μｍ未満の小気孔である。孔径１０μｍ以上の気孔が多く存在する場合は、赤外線散乱効果が十分でなくなる。そのため、孔径０．８μｍ以上１０μｍ未満の範囲内に少なくとも１つの気孔径分布ピークを有すると好ましいものである。 Most of the pores of the porous sintered body are small pores having a pore diameter of less than 10 μm. When there are many pores having a pore diameter of 10 μm or more, the infrared scattering effect is not sufficient. Therefore, it is preferable to have at least one pore size distribution peak in the range of 0.8 μm or more and less than 10 μm.
そして、前記孔径０．８μｍ以上１０μｍ未満の気孔が全気孔容積に占める割合が、１０ｖｏｌ％未満であると赤外線散乱効果が十分でなくなる。一方、４０ｖｏｌ％超では８５ｖｏｌ％以上の気孔率を得ることが困難となる。 When the ratio of the pores having a pore diameter of 0.8 μm or more and less than 10 μm to the total pore volume is less than 10 vol%, the infrared scattering effect is not sufficient. On the other hand, if it exceeds 40 vol%, it becomes difficult to obtain a porosity of 85 vol% or more.
そして、前記多孔質焼結体の気孔のうち、孔径０．０１μｍ以上０．８μｍ未満の気孔（微小気孔）が全気孔容積のうちの５ｖｏｌ％以上１０ｖｏｌ％以下を占める。 Of the pores of the porous sintered body, pores (micropores) having a pore diameter of 0.01 μm or more and less than 0.8 μm occupy 5 vol% or more and 10 vol% or less of the total pore volume.
このような微小気孔が上記のような割合で存在していることにより、単位体積当たりの気孔数を多くすることができ、粒界におけるフォノン散乱量が増加し、伝導伝熱を抑制する効果がある。 The presence of such micropores in the above proportion can increase the number of pores per unit volume, increase the amount of phonon scattering at the grain boundaries, and have the effect of suppressing conduction heat transfer. is there.
前記微小気孔が全気孔容積に占める割合が５ｖｏｌ％未満であると、単位体積当たりの気孔数が少なく、伝導伝熱を抑制する効果が十分でなくなる。一方、１０ｖｏｌ％超では８５ｖｏｌ％以上の気孔率を得ることが困難となる。 When the proportion of the micropores in the total pore volume is less than 5 vol%, the number of pores per unit volume is small, and the effect of suppressing conduction heat transfer becomes insufficient. On the other hand, if it exceeds 10 vol%, it is difficult to obtain a porosity of 85 vol% or more.
前記多孔質焼結体は、孔径１０μｍ超の範囲内に気孔径分布ピークを有していても差し支えない。しかしながら、粗大な気孔は輻射伝熱により断熱性の低下を招くため、一例として、孔径１０００μｍ超の気孔の存在は好ましくない。 The porous sintered body may have a pore size distribution peak in the range of the pore size exceeding 10 μm. However, since coarse pores cause a decrease in heat insulation due to radiant heat transfer, as an example, the presence of pores having a pore diameter of more than 1000 μm is not preferable.
前記多孔質焼結体中の気孔径分布は、ＪＩＳ Ｒ １６５５「ファインセラミックスの水銀圧入法による成形体気孔径分布試験方法」により測定される。 The pore size distribution in the porous sintered body is measured by JIS R 1655 “Method for testing pore size distribution of molded ceramics by mercury porosimetry”.
さらに、本発明の一の態様に係る断熱材は、かさ比重が０．６以下である。ここで、かさ比重は、ＪＩＳ Ｒ ２６１４「耐火断熱れんがの比重及び真気孔率測定方法」にて計測される。 Furthermore, the heat insulating material according to one embodiment of the present invention has a bulk specific gravity of 0.6 or less. Here, the bulk specific gravity is measured according to JIS R 2614 “Method for measuring specific gravity and true porosity of refractory heat-insulating brick”.
上記に示したように、ＭｇＡｌ２Ｏ４中にセラミックス繊維を含み気孔率が８５ｖｏｌ％以上９１ｖｏｌ％未満、孔径０．８μｍ以上１０μｍ未満の気孔が全気孔容積のうち１０ｖｏｌ％以上４０ｖｏｌ％以下、孔径０．０１μｍ以上０．８μｍ未満の気孔が全気孔容積のうちの５ｖｏｌ％以上１０ｖｏｌ％以下、という気孔形態において、セラミックス繊維が含まれることにより、強度を低減させることなく軽量化される、すなわち、かさ比重が低減される。 As shown above, the pores having ceramic fibers in MgAl 2 O 4 and having a porosity of 85 vol% or more and less than 91 vol% and a pore diameter of 0.8 μm or more and less than 10 μm are 10 vol% or more and 40 vol% or less of the total pore volume, In the pore form in which the pores of 0.01 μm or more and less than 0.8 μm are 5 vol% or more and 10 vol% or less of the total pore volume, the ceramic fiber is contained, thereby reducing the weight without reducing the strength. Bulk specific gravity is reduced.
そして、前記断熱材の熱伝導率は、具体的には、１０００℃以上１５００℃以下における熱伝導率が、２０℃以上１０００℃未満における熱伝導率の１．５倍を超えないものとものとする。 And the thermal conductivity of the said heat insulating material is specifically, the thermal conductivity in 1000 degreeC or more and 1500 degrees C or less does not exceed 1.5 times the thermal conductivity in 20 degreeC or more and less than 1000 degreeC. To do.
このように高温域における熱伝導率の増加が抑制された断熱材は、１０００℃以上の高温域においても、１０００℃未満の低温域の場合と同等の断熱効果が保持される。 Thus, the heat insulating material in which the increase in the thermal conductivity in the high temperature region is suppressed maintains the same heat insulating effect even in the high temperature region of 1000 ° C. or higher as in the low temperature region of less than 1000 ° C.
前記断熱材は、１０００℃以上１５００℃以下の高温域における熱伝導率が０．４５Ｗ／（ｍ・Ｋ）以下であると好ましく、０．４０Ｗ／（ｍ・Ｋ）以下であるとより好ましい。このような１０００℃以上の高温域でも熱伝導率が増加することなく抑制されている断熱材は、高温域での使用においても断熱効果の変動が少ない。 The heat insulating material preferably has a thermal conductivity of 0.45 W / (m · K) or less, more preferably 0.40 W / (m · K) or less, in a high temperature range of 1000 ° C. or more and 1500 ° C. or less. Such a heat insulating material that is suppressed without increasing the thermal conductivity even in a high temperature region of 1000 ° C. or more has little variation in the heat insulating effect even when used in a high temperature region.
ここで、かさ比重が０．６以下という範囲は、多孔質焼結体としては必ずしも軽量の部類ではないが、上記に示す本発明の熱伝導率の増加抑制効果を併せ持つ断熱材としては十分に軽く、かつ、かさ比重が適度にあることで強度が担保され、壊れにくいため扱いやすい、という点で優位といえる。かさ比重の下限は特に限定されないが、実用上断熱材として使用できる範囲であればよく、一例として０．３以上であればよい。 Here, the range where the bulk specific gravity is 0.6 or less is not necessarily a lightweight category as a porous sintered body, but is sufficient as a heat insulating material having the above-described effect of suppressing the increase in thermal conductivity of the present invention. It is advantageous in that it is light and has an appropriate bulk specific gravity, which ensures strength and is easy to handle because it is difficult to break. Although the minimum of bulk specific gravity is not specifically limited, What is necessary is just the range which can be used as a heat insulating material practically, and should just be 0.3 or more as an example.
次に、本発明の他の一態様に係る断熱材について説明する。本発明の他の一態様に係る断熱材は、ＭｇＡｌ２Ｏ４中にセラミックス繊維を含む気孔率７０ｖｏｌ％以上８５ｖｏｌ％未満の多孔質焼結体からなり、孔径０．８μｍ以上１０μｍ未満の気孔が全気孔容積のうちの４０ｖｏｌ％以上７０ｖｏｌ％未満を占め、かつ、孔径０．０１μｍ以上０．８μｍ未満の気孔が全気孔容積のうちの１０ｖｏｌ％以上３０ｖｏｌ％未満を占め、１０００℃以上１５００℃以下における熱伝導率が、２０℃以上１０００℃未満における熱伝導率の１．５倍を超えないものである。 Next, a heat insulating material according to another embodiment of the present invention will be described. The heat insulating material according to another aspect of the present invention is composed of a porous sintered body having a porosity of 70 vol% or more and less than 85 vol%, which contains ceramic fibers in MgAl 2 O 4 , and has pores having a pore diameter of 0.8 μm or more and less than 10 μm. The total pore volume occupies 40 vol% or more and less than 70 vol%, and the pore diameter of 0.01 μm or more and less than 0.8 μm occupies 10 vol% or more and less than 30 vol% of the total pore volume, 1000 ° C or more and 1500 ° C or less The thermal conductivity at is not more than 1.5 times the thermal conductivity at 20 ° C. or more and less than 1000 ° C.
本発明の一の態様に係る断熱材との違いは、気孔率、孔径０．８μｍ以上１０μｍ未満の気孔、孔径０．０１μｍ以上０．８μｍ未満の気孔、の全気孔に占める容積の割合である。これにより、本発明の一の態様に係る断熱材と比べて気孔率が低いので、かさ比重はやや増加するが、熱伝導率をより低く抑えることが可能となる。 The difference from the heat insulating material according to one embodiment of the present invention is the ratio of the volume to the total pores of the porosity, the pores having a pore diameter of 0.8 μm or more and less than 10 μm, and the pores having a pore diameter of 0.01 μm or more and less than 0.8 μm. . Accordingly, since the porosity is lower than that of the heat insulating material according to one aspect of the present invention, the bulk specific gravity is slightly increased, but the thermal conductivity can be further suppressed.
これは、特に、孔径０．０１μｍ以上０．８μｍ未満の気孔、および孔径０．８μｍ以上１０μｍ未満の気孔の割合を、本発明の一の態様と比べて増やしたことによる効果であるといえる。 This can be said to be an effect obtained by increasing the ratio of pores having a pore diameter of 0.01 μm or more and less than 0.8 μm and pores having a pore diameter of 0.8 μm or more and less than 10 μm as compared with one embodiment of the present invention.
なお、１０００℃以上１５００℃以下における熱伝導率が０．４０Ｗ／（ｍ・Ｋ）以下であると好ましく、熱伝導率が０．３５Ｗ／（ｍ・Ｋ）以下であると、より好ましい。あるいは、１０００℃以上１５００℃以下における熱伝導率が、２０℃以上１０００℃未満における熱伝導率の１．２倍を超えないと、さらに好ましいものである。 The thermal conductivity at 1000 ° C. or higher and 1500 ° C. or lower is preferably 0.40 W / (m · K) or lower, and the thermal conductivity is more preferably 0.35 W / (m · K) or lower. Alternatively, it is more preferable that the thermal conductivity at 1000 ° C. or higher and 1500 ° C. or lower does not exceed 1.2 times the thermal conductivity at 20 ° C. or higher and lower than 1000 ° C.
以上の通り、本発明に係る断熱材は、ＭｇＡｌ２Ｏ４中にセラミックス繊維を添加し、さらに、気孔率や所定の範囲の気孔孔径の比率を適切に制御することで、熱伝導率増加抑制効果と軽量化を、任意のバランスで両立させることを可能にしたものである。 As described above, the heat insulating material according to the present invention suppresses an increase in thermal conductivity by adding ceramic fibers in MgAl 2 O 4 and appropriately controlling the porosity and the ratio of pore diameters within a predetermined range. It is possible to achieve both effects and weight reduction in an arbitrary balance.
従って、従来のＭｇＡｌ２Ｏ４単体で構成される断熱材と比べても、所定の特性向上を目的とした材料設計が可能であり、より幅広い要求に応えられるものである。 Therefore, even when compared with a conventional heat insulating material composed of MgAl 2 O 4 , material design for the purpose of improving predetermined characteristics is possible, and it can meet a wider range of requirements.
なお、上記のような本発明に係る断熱材の製造方法は、特に限定されるものではなく、公知の多孔質焼結体の製造方法を適用できる。例えば、気孔構造の形成・調整は、造孔材や起泡剤の添加等により行うことができる。 In addition, the manufacturing method of the heat insulating material which concerns on the above this invention is not specifically limited, The manufacturing method of a well-known porous sintered compact can be applied. For example, the pore structure can be formed and adjusted by adding a pore former or a foaming agent.
また、本発明に係る断熱材は、断熱特性を著しく劣化させる、等の悪影響がない限りにおいて、様々な変形例が可能である。例えば、複数の材料から成る繊維が添加されていてもよい。また、微小粒子がさらに添加されていてもよい。あるいは、繊維のない領域を部分的に設けてもよい。さらには、本発明に係る断熱材の表層に、各種の膜を付与し、より耐熱性を向上させることもできる。 In addition, the heat insulating material according to the present invention can be variously modified as long as there is no adverse effect such as remarkably deteriorating the heat insulating characteristics. For example, fibers made of a plurality of materials may be added. Further, fine particles may be further added. Or you may provide the area | region without a fiber partially. Furthermore, various films can be provided on the surface layer of the heat insulating material according to the present invention to further improve the heat resistance.
以下、本発明を実施例に基づき具体的に説明するが、本発明は下記に示す実施例により制限されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not restrict | limited by the Example shown below.
（実施例１〜３、比較例１）
水硬性アルミナ粉末（ＢＫ−１１２；住友化学株式会社製）１１ｍｏｌに対して、酸化マグネシウム粉末（ＭＧＯ１１ＰＢ；株式会社高純度化学研究所製）９ｍｏｌの割合で混合し、これに水硬性アルミナと酸化マグネシウムの合計重量に対して等倍の重量の純水を加え、均一に分散させてスラリーを調製した。そして、平均径３〜５μｍ、平均長１００ｍｍ以下のバルク繊維のアルミナ繊維、造孔材として直径５〜１０μｍの粒状のアクリル樹脂をそれぞれ準備し、アルミナ繊維の添加率、造孔材の径及び添加量、焼成温度及び焼成時間を適宜変更し、下記表１の実施例１〜３、比較例１にそれぞれ示すような気孔構成を有する多孔質焼結体を作製した。なお、造孔剤は前記スラリーに対して４０〜７０ｖｏｌ％の範囲で、アルミナ繊維は５０ｗｔ％を加えて混合、成形し、６０ｍｍ×７０ｍｍ×２０ｍｍの成形体を得たのちに、これらを、大気中、１５００℃〜１６００℃で３〜４時間の範囲で変更して焼成し、多孔質焼結体を作製した。
(Examples 1 to 3, Comparative Example 1)
11 mol of hydraulic alumina powder (BK-112; manufactured by Sumitomo Chemical Co., Ltd.) is mixed at a ratio of 9 mol of magnesium oxide powder (MGO11PB; manufactured by Kojundo Chemical Laboratory Co., Ltd.), and this is mixed with hydraulic alumina and magnesium oxide. A slurry was prepared by adding equal weight of pure water to the total weight of and uniformly dispersing pure water. Then, an alumina fiber of bulk fiber having an average diameter of 3 to 5 μm and an average length of 100 mm or less, and a granular acrylic resin having a diameter of 5 to 10 μm as a pore former are prepared, respectively, and the addition rate of the alumina fiber, the diameter of the pore former and the addition The porous sintered body having pore structures as shown in Examples 1 to 3 and Comparative Example 1 in Table 1 below was prepared by appropriately changing the amount, firing temperature and firing time. The pore former is in the range of 40 to 70 vol% with respect to the slurry, and the alumina fiber is mixed and molded by adding 50 wt% to obtain a molded body of 60 mm x 70 mm x 20 mm. Inside, it changed at 1500-1600 degreeC in the range for 3 to 4 hours, and baked, and produced the porous sintered compact.
上記において得られた多孔質焼結体について、Ｘ線回折（Ｘ線源：ＣｕＫα、電圧：４０ｋＶ、電流：０．３Ａ、走査速度：０．０６°／ｓ）にて結晶相を同定したところ、マグネシアスピネル相が観察された。 About the porous sintered body obtained above, the crystal phase was identified by X-ray diffraction (X-ray source: CuKα, voltage: 40 kV, current: 0.3 A, scanning speed: 0.06 ° / s) A magnesia spinel phase was observed.
（参考例１）
市販の繊維断熱材（耐熱温度１６００℃）を、参考例１とした。
(Reference Example 1)
A commercially available fiber heat insulating material (heat-resistant temperature 1600 ° C.) was used as Reference Example 1.
上記実施例１〜３、比較例１、参考例１について、水銀ポロシメータを用いて気孔容積を測定した。図３に、その気孔径分布を示す。ＪＩＳ Ｒ ２６１４「耐火断熱れんがの比重及び真気孔率の測定方法」を参考にして、かさ比重を測定した。また、上記実施例及び比較例の各多孔質焼結体又は断熱レンガについて、ＪＩＳ Ｒ ２６１６を参考にして熱伝導率の測定を行った。焼成体繊維含有率（ｖｏｌ％）は、各多孔質焼結体の任意の一断面を劈開後、顕微鏡観察を行い、観察視野内で繊維の占める面積にて算出した。破壊エネルギー値の測定は、荷重点変位速度一定の条件で試料を安定破壊させ、荷重−変位曲線が変位軸と囲む面積に相当する仕事量を、万能投影機などで測定した投影破断面積Ａの二倍で除すことで算出した。これら各種評価結果を、図１及び下記表１にまとめて示す。 About the said Examples 1-3, the comparative example 1, and the reference example 1, the pore volume was measured using the mercury porosimeter. FIG. 3 shows the pore size distribution. The bulk specific gravity was measured with reference to JIS R 2614 "Measurement method of specific gravity and true porosity of fireproof insulating brick". Moreover, about each porous sintered compact or heat insulation brick of the said Example and comparative example, the heat conductivity was measured with reference to JISR2616. The fired body fiber content (vol%) was calculated from the area occupied by the fibers within the observation field by performing microscopic observation after cleaving an arbitrary cross section of each porous sintered body. The measurement of the fracture energy value is performed by stably breaking the sample under the condition that the load point displacement speed is constant, and calculating the work amount corresponding to the area surrounded by the load-displacement curve with the displacement axis of the projected fracture area A measured by a universal projector or the like. Calculated by dividing by 2. These various evaluation results are summarized in FIG. 1 and Table 1 below.
表１に示した評価結果から、繊維を添加し、気孔容積の割合が本発明の一の態様に係る実施範囲にある実施例１〜３は、１０００℃から１５００℃における熱伝導率は０．４０Ｗ／（ｍ・Ｋ）を下回り、かつ、かさ比重も、０．６を下回っていることがわかる。 From the evaluation results shown in Table 1, in Examples 1 to 3, in which fibers are added and the ratio of the pore volume is in the implementation range according to one embodiment of the present invention, the thermal conductivity at 1000 ° C. to 1500 ° C. is 0.00. It can be seen that it is below 40 W / (m · K) and the bulk specific gravity is below 0.6.
これに対して、繊維を含まない比較例１は、かさ比重が０．６を上回っていた。 On the other hand, the comparative example 1 which does not contain a fiber had a bulk specific gravity exceeding 0.6.
（実施例４〜７、比較例２）
アルミナ繊維の添加率、造孔材の径及び添加量、焼成温度及び焼成時間を適宜変更し、それ以外は実施例１〜３と同様にして、下記表１の実施例４〜７、比較例２にそれぞれ示すような気孔構成を有する多孔質焼結体を作製、評価した。
(Examples 4-7, Comparative Example 2)
The addition rate of the alumina fiber, the diameter and addition amount of the pore former, the firing temperature and the firing time were appropriately changed, and the others were the same as in Examples 1 to 3, and Examples 4 to 7 in Table 1 below, Comparative Example A porous sintered body having a pore structure as shown in Fig. 2 was prepared and evaluated.
図２及び表２に示した評価結果から、繊維を添加し、気孔率、気孔容積の割合が本発明の他の態様に係る実施範囲にある実施例４〜７は、１０００℃から１５００℃における熱伝導率は十分低いものであることがわかる。 From the evaluation results shown in FIG. 2 and Table 2, Examples 4 to 7 in which fibers are added and the ratio of porosity and pore volume are in the implementation range according to another aspect of the present invention are from 1000 ° C. to 1500 ° C. It can be seen that the thermal conductivity is sufficiently low.
さらに、実施例６〜７は、１０００℃から１５００℃における熱伝導率は、さらに低いものであり、より好適である。 Further, Examples 6 to 7 are more preferable because the thermal conductivity at 1000 ° C. to 1500 ° C. is even lower.
これに対して、気孔率、気孔容積の割合が本発明の他の態様に係る実施範囲外にある比較例２は、１０００℃から１５００℃における熱伝導率がやや高めであった。 On the other hand, in Comparative Example 2 in which the ratio of the porosity and the volume of the pores was out of the implementation range according to another aspect of the present invention, the thermal conductivity at 1000 ° C. to 1500 ° C. was slightly higher.
なお、参考例１は、繊維のみで構成された断熱材である。これは、本発明品と比較すると、かさ比重はずっと低い値である。しかしながら、実施例は１０００℃から１５００℃における熱伝導率は０．５１Ｗ／（ｍ・Ｋ）である。 Reference Example 1 is a heat insulating material composed only of fibers. This is a much lower bulk specific gravity than the product of the present invention. However, in the examples, the thermal conductivity at 1000 ° C. to 1500 ° C. is 0.51 W / (m · K).
このことから、本発明に係る断熱材は、特に高温域での低い熱伝導率、および熱伝導率の上昇が抑制されるという特性を重視する用途に、より好適であるといえる。 From this, it can be said that the heat insulating material which concerns on this invention is more suitable for the use which attaches importance to the characteristic that low heat conductivity in a high temperature range and the raise of heat conductivity are suppressed especially.
さらに、実施例１〜７、比較例１，２について、破壊エネルギーの値を測定して比較を行った。破壊エネルギー値の測定は、荷重点変位速度一定の条件で試料を安定破壊させ、荷重−変位曲線が変位軸と囲む面積に相当する仕事量を、万能投影機などで測定した投影破断面積Ａの二倍で除すことで算出した。 Furthermore, about Examples 1-7 and Comparative Examples 1 and 2, the value of fracture energy was measured and compared. The measurement of the fracture energy value is performed by stably breaking the sample under the condition that the load point displacement speed is constant, and calculating the work amount corresponding to the area surrounded by the load-displacement curve with the displacement axis of the projected fracture area A measured by a universal projector or the like. Calculated by dividing by 2.
その結果、実施例１は８．８Ｎ／ｍ、実施例２は１０．５Ｎ／ｍ、実施例３は１７．３Ｎ／ｍ、実施例４は４．７Ｎ／ｍ、実施例５は５．２Ｎ／ｍ、実施例６は１．７Ｎ／ｍ、実施例７は４．３Ｎ／ｍ、となった。これに対して、比較例１は０．５Ｎ／ｍ、比較例２は８．７Ｎ／ｍであった。 As a result, Example 1 was 8.8 N / m, Example 2 was 10.5 N / m, Example 3 was 17.3 N / m, Example 4 was 4.7 N / m, and Example 5 was 5.2 N. / M, Example 6 was 1.7 N / m, and Example 7 was 4.3 N / m. On the other hand, the comparative example 1 was 0.5 N / m and the comparative example 2 was 8.7 N / m.
上記結果より、本発明に係る繊維が添加された実施例１〜７は、繊維を添加しない比較例１と比べて、破壊エネルギー値は高いものであった。なお、本発明の他の態様に係る多孔質焼結体の実施範囲である気孔率８５ｖｏｌ％を超える比較例２は、１０００〜１５００℃での熱伝導率の上昇が、実施例４〜７と比べて高く、高温での優れた断熱性が得られるという本発明の効果が、充分に得られていないものと言える。 From the above results, Examples 1 to 7 to which the fibers according to the present invention were added had higher fracture energy values than Comparative Example 1 in which no fibers were added. In Comparative Example 2, which exceeds the porosity of 85 vol%, which is the implementation range of the porous sintered body according to another aspect of the present invention, the increase in the thermal conductivity at 1000-1500 ° C is that of Examples 4-7. It can be said that the effect of the present invention, which is higher than that of the present invention and provides excellent heat insulation at high temperatures, has not been sufficiently obtained.
なお、上記実施例において添加する繊維として、アルミナ繊維を例示したが、本発明に用いる繊維中にシリカが含まれていると、多孔質焼結体全体の耐熱性・断熱性を低下させる。アルミナ繊維に限らず、他の種類の繊維を用いる場合であっても、繊維中のシリカ含有量は５ｗｔ％以下にすることが好ましい。そうすることにより、多孔質焼結体を作製する時のみならず、高温で使用する過程で収縮が抑えられ、狙い通りの気孔径分布を維持することできる。すなわち、シリカ含有量が５ｗｔ％以下の繊維を用いることにより、耐熱性・断熱性に優れた多孔質焼結体にすることができる。 In addition, although the alumina fiber was illustrated as a fiber added in the said Example, when the silica used is contained in the fiber used for this invention, the heat resistance and heat insulation of the whole porous sintered compact will be reduced. Even if other types of fibers are used, not only alumina fibers, the silica content in the fibers is preferably 5 wt% or less. By doing so, shrinkage is suppressed not only when producing a porous sintered body but also during the process of use at a high temperature, and the targeted pore size distribution can be maintained. That is, by using a fiber having a silica content of 5 wt% or less, a porous sintered body excellent in heat resistance and heat insulation can be obtained.
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| DE102015212290.5A DE102015212290B4 (en) | 2014-07-02 | 2015-07-01 | thermal insulation |
| CN201510380277.6A CN105236951A (en) | 2014-07-02 | 2015-07-02 | Heat insulator |
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| JPH05186280A (en) * | 1992-01-14 | 1993-07-27 | Toshiba Ceramics Co Ltd | Production of ceramic porous body |
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| JP7282870B2 (en) | 2018-08-01 | 2023-05-29 | サン－ゴバン サントル ド レシェルシュ エ デテュド ユーロペアン | Glass furnace with optical fiber |
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