JP5397031B2 - Manufacturing method for high performance insulation - Google Patents
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本発明は、高温で使用される高性能断熱材、特に、耐水性にも優れる高性能断熱材の製造方法に関する。 The present invention relates to a method for producing a high-performance heat insulating material used at a high temperature, particularly a high-performance heat insulating material having excellent water resistance.
有機材料が使用できないような高温（≧５００℃）で使用することができ、静止空気に近い低熱伝導率を示す断熱材としては、従来、ヒュームドシリカなどの微細粉末を主成分とする微細多孔質成形体（以下、これを「高性能断熱材」という）を用いたものがある（非特許文献１、特許文献１））。
As a heat insulating material that can be used at a high temperature (≧ 500 ° C.) where no organic material can be used and has a low thermal conductivity close to that of still air, a fine porous material mainly composed of fine powder such as fumed silica has been used. There is a material using a molded body (hereinafter referred to as “high performance heat insulating material”) (Non-patent
この文献に開示された高性能断熱材は、超微細固体粒子（数ｎｍ〜数１０nｍ）で構成されているため、熱伝導が微細粒子の点接触に依存すること、気孔率が高く（８０ｖｏｌ％以上）、その気孔も微細で気体の平均自由工程よりも小さい（１００ｎｍ以下）気孔を多く含み、かつ赤外線を反射する材料を含むために、低熱伝導率であることが特徴である。 Since the high-performance heat insulating material disclosed in this document is composed of ultrafine solid particles (several nm to several tens of nm), the heat conduction depends on the point contact of the fine particles, and the porosity is high (80 vol%). As described above, since the pores are fine and contain a large number of pores (100 nm or less) smaller than the mean free path of gas, and include a material that reflects infrared rays, they are characterized by low thermal conductivity.
前記超微細固体粒子としては、ヒュームド酸化物、例えば、ヒュームドシリカが代表的であり、ドイツのデグサ社製アエロジル（登録商標）などが知られている。かかるヒュームド酸化物は、金属酸化物を原料に火炎加水分解法（ＭＣｌｎ＋２ｍＨ２＋ｍＯ２、ここでＭ＝Ｓｉ、Ａｌ、Ｔｉ、Ｚｒなど；Ｓｉの場合１０００℃程度）によって得ることができる。このようにして得られるヒュームド酸化物、例えば、ヒュームドシリカは、ＢＥＴ比表面積５〜６００ｍ２/ｇ、１次粒子径５〜５０ｎｍ、密度２．２ｇ／ｃｃ、見掛比容積１０００〜２０００ｍｌ／１００ｇで、鎖状の集塊粒子からなるものが代表的なものである。 As the ultrafine solid particles, fumed oxides such as fumed silica are typical, and Aerosil (registered trademark) manufactured by Degussa of Germany is known. Such fumed oxide can be obtained by a flame hydrolysis method (MCln + 2 mH 2 + mO 2 , where M = Si, Al, Ti, Zr, etc .; in the case of Si, about 1000 ° C.) using a metal oxide as a raw material. The fumed oxide thus obtained, for example, fumed silica, has a BET specific surface area of 5 to 600 m 2 / g, a primary particle diameter of 5 to 50 nm, a density of 2.2 g / cc, and an apparent specific volume of 1000 to 2000 ml / 100 g. A typical example is a chain of agglomerated particles.
前記ヒュームド酸化物の成形材料は、断熱材として有望視されているが、この成形材料は液体（水分）と接触したとき収縮するという問題があった。これは、断熱材の場合で云えば、このような収縮が起きると、厚みの減少による熱抵抗の低下を招くと同時に、厚みと垂直方向に収縮して断熱材間に隙間を生じる結果、その隙間より熱が漏れるという致命的な問題が生じる。例えば、このような断熱材を冶金炉などの断熱ライニングとして使用する場合、熱遮蔽域に隙間を生じて熱流路を形成したり、ライニングが縮んで弛みが出るという問題が生じる。そのため、従来は、かかるヒュームドシリカなどを主原料とする高性能断熱材については、アルミ蒸着フイルムなどの耐水性材料で被覆包装したり、撥水性材料による処理をして使用するということで対応していた。しかし、耐水性包装および撥水処理剤等は、耐熱性が５００℃程度以下であるため、高温用用途に使用する場合において、一度、高温で使用すると、耐水性を失うという問題があった。 The fumed oxide molding material is considered promising as a heat insulating material, but there is a problem that the molding material shrinks when it comes into contact with a liquid (moisture). In the case of a heat insulating material, if such shrinkage occurs, it causes a decrease in thermal resistance due to a decrease in thickness, and at the same time, shrinks in a direction perpendicular to the thickness and creates a gap between the heat insulating materials. A fatal problem of heat leaking from the gap occurs. For example, when such a heat insulating material is used as a heat insulating lining for a metallurgical furnace or the like, there arises a problem that a gap is formed in the heat shielding area to form a heat flow path, or the lining contracts and loosens. Therefore, in the past, high-performance heat insulating materials mainly made of such fumed silica were covered by using water-resistant materials such as aluminum vapor deposited film or treated with water-repellent materials. Was. However, since the heat resistance packaging and the water repellent agent have a heat resistance of about 500 ° C. or less, there is a problem that when used at a high temperature, the water resistance is lost once used at a high temperature.
以上説明したように、従来、高温域で使用するための耐水性の良好な高性能断熱材は、有効なものがないのが実情であった。 As described above, conventionally, there is no effective high-performance heat insulating material with good water resistance for use in a high temperature range.
本発明の目的は、使用に当たって水分を吸収したような場合であっても、そして後で乾燥されるようなことがあっても収縮の起こらない高性能断熱材を製造する方法を提案することにある。 An object of the present invention is to propose a method for producing a high-performance heat insulating material which does not cause shrinkage even when it absorbs moisture during use and may be dried later. is there.
発明者らは、従来技術が抱えている上述した問題点のない高性能断熱材、とくに、施工後に水分吸収と乾燥という条件に曝されても収縮の起こらない高性能断熱材の構成について、鋭意検討した結果、本発明に係る下記の高性能断熱材の製造方法の開発に成功した。 The inventors diligently devised a configuration of a high-performance heat insulating material that does not have the above-mentioned problems in the prior art, particularly a high-performance heat insulating material that does not shrink even if exposed to moisture absorption and drying conditions after construction. As a result of the examination, the inventors have succeeded in developing a method for producing the following high-performance heat insulating material according to the present invention .
本発明は、ヒュームドシリカを主原料として含み、その他にＳｉＣ超微粉、セラミックファイバーのいずれか少なくとも一種を含み、細孔径分布のグラフ上において、細孔径の大きさが０．０１〜０．１μｍ、１０〜１０００μｍおよび０．１〜１０μｍの範囲内にそれぞれ、山形のピークが存在する細孔分布をもつ粒子からなる原料を圧縮成形し、得られた成形体を予め水中に浸漬して吸湿させ、次いで、乾燥することにより、該細孔径分布のグラフ上において、細孔径の大きさが０．１〜１０μｍの範囲内に山形のピークをもつ細孔を消滅させることを特徴とする高性能断熱材の製造方法を提案する。 The present invention includes a heat Yumudo silica as main components Other SiC ultrafine, see contains at least one one of ceramic fibers, on the graph of the pore size distribution, the size of the pore diameter from 0.01 to 0. A raw material consisting of particles having a pore distribution with a peak in the range of 1 μm , 10 to 1000 μm and 0.1 to 10 μm , respectively, is compression molded, and the resulting molded body is dipped in water in advance to absorb moisture. It is followed by drying, in the graph of the pore size distribution, high, wherein Rukoto quenched pores size of pore diameter has a chevron peak in the range of 0.1~10μm We propose a method for manufacturing performance insulation.
前記のように構成された本発明によれば、５００℃以上というような高温雰囲気で使用されるものが、水分（湿分）と接触したような場合でも収縮が起こらない高性能断熱材を製造することができる。従って、この断熱材を施工した場合、断熱材の収縮に起因して隙間を生じさせて熱流が洩れたり、該断熱材からなるライニング自体が縮んで弛みを生じたりすることがなく、また、厚み減少による断熱性の低下も生じないものが得られる。とくに、冶金炉などの溶湯容器や熱交換器などの高温雰囲気で使われる断熱材料として好適なものを製造することができる。 According to the onset bright configured as described above, those used in a high temperature atmosphere such as 500 ° C. or higher, the moisture performance insulation shrinkage even when (moisture) and as contact does not occur a Can be manufactured. Therefore, when this heat insulating material is applied, the heat flow does not leak due to the shrinkage of the heat insulating material, the lining made of the heat insulating material itself does not shrink and loosen, and the thickness The thing which does not produce the heat insulation fall by reduction is obtained. In particular, Ru can be produced suitable as a heat insulating material used in a high temperature atmosphere, such as molten metal vessel and heat exchangers, such as metallurgical furnaces.
本発明の製造方法の適用によって得られる高性能断熱材は、水銀圧入法で測定した細孔径分布のグラフ上において、細孔径の大きさが０．０１〜０．１μｍ範囲および１０〜１０００μｍの範囲にそれぞれ、山形のピーク（極大値）が存在する細孔分布を示すものの、該細孔径分布のグラフにおいて、細孔径の大きさが０．１〜１０μｍの範囲内には、そのピークがない細孔分布をもつ粒子構造を有することが特徴的な構成である。 High-performance insulation material that is obtained by applying the production method of the present invention, in the graph of the pore size distribution measured by mercury porosimetry, the pore diameter size is 0.01~0.1μm range and 10~1000μm of Each of the ranges shows a pore distribution in which a mountain-shaped peak (maximum value) exists, but in the pore diameter distribution graph, there is no peak in the range of the pore diameter of 0.1 to 10 μm. It has a characteristic structure having a particle structure having a pore distribution.
水銀圧入法では、大気圧から徐々に圧力を上げて試料に水銀を浸入させ、各圧力における水銀の浸入量から試料の細孔径分布を測定する方法である。水銀は物質を濡らすことはないが、加圧することにより物質の細孔に浸入する性質がある。このとき、圧力を上げるに従い、大きな孔から順に小さな孔へ水銀が浸入するので、圧力を上げながら累積浸入量を順次に、測定し、その圧力値を細孔径に換算することで、一定の径以上の累積細孔体積を求めることができる。通常、細孔径分布は、ある細孔径より大きい（または小さい）細孔の単位試料重量当たり体積を細孔径に対してプロットして表す場合（積分型）と、ある微小細孔径範囲に属する細孔の単位試料重量当たり体積を細孔径に対してプロットしヒストグラムとして表す場合（微分型）とがある。いずれの場合も、細孔径は対数で表される。 In the mercury intrusion method, the pressure is gradually increased from the atmospheric pressure, mercury is infiltrated into the sample, and the pore diameter distribution of the sample is measured from the amount of mercury intrusion at each pressure. Mercury does not wet the substance, but has the property of entering the pores of the substance when pressurized. At this time, as the pressure is increased, mercury enters from the larger holes to the smaller holes in order, so the cumulative amount of intrusion is measured sequentially while the pressure is increased, and the pressure value is converted to the pore diameter, so that a constant diameter is obtained. The above cumulative pore volume can be determined. Normally, the pore size distribution is expressed by plotting the volume per unit sample weight of pores larger (or smaller) than a certain pore size against the pore size (integrated type) and pores belonging to a certain micropore size range. In some cases, the volume per unit sample weight is plotted against the pore diameter and expressed as a histogram (differential type). In either case, the pore diameter is expressed as a logarithm.
本発明で言うピークとは、微分型で表した細孔径分布のグラフ上に山形に見られるところ、極大値である。通常、横軸の細孔径を１桁当たり３〜１０程度に分割したヒストグラムで表わすので、その極大値の有無は容易に判別できる。 The peak referred to in the present invention is a maximum value as seen in a mountain shape on a graph of the pore size distribution expressed in a differential form. Usually, since the horizontal axis is represented by a histogram in which the pore diameter is divided into about 3 to 10 per digit, the presence or absence of the maximum value can be easily discriminated.
この点、従来の高性能断熱材は、細孔径の大きさが０．０１〜０．１μｍ、０．１〜１０μｍおよび１０〜１０００μｍ範囲内の３つの領域に分かれて、それぞれの範囲内に細孔分布の前記ピークの位置が存在するような細孔分布を示す粒子構造をもつもので構成されている。即ち、高性能断熱材において、細孔径が０．０１〜０．１μｍの範囲内にピークをもつ細孔というのは、原料となるヒュームド酸化物からなる１次粒子が凝集し２次粒子を構成している１次粒子間に生じている空隙に相当し、原料粒子固有の形状を反映している。また、このピークは非常にシャープな山形を示し、この山形は細孔径でおおよそ０.５桁程度の範囲に収まる。 In this regard, the conventional high-performance heat insulating material is divided into three regions in which the pore diameter is 0.01 to 0.1 μm, 0.1 to 10 μm, and 10 to 1000 μm, and each fine region is fine. It has a particle structure showing a pore distribution such that the position of the peak of the pore distribution exists. That is, in the high-performance heat insulating material, the pore having a peak in the range of 0.01 to 0.1 μm means that the primary particles made of the fumed oxide as a raw material aggregate to form secondary particles. This corresponds to voids generated between the primary particles, and reflects the shape unique to the raw material particles. Moreover, this peak shows a very sharp chevron, and this chevron falls within a range of about 0.5 digits in pore diameter.
一方、細孔径が０．１〜１０μｍの範囲内の位置にピークが存在する細孔というのは、前述の２次粒子間の隙間に相当するものであり、２次粒子の充填状態を反映しているものである。これは上記小径側のピークに比較して、ブロードでやや低い山形を示し、山形の裾に相当する２つ谷の部分（極小値）の幅は１〜３桁程度と広いものとなる。具体的には、「細孔径の大きさが０．１〜１０μｍの範囲内には山形のピークがない細孔分布」とは、細孔径が０．１μｍでの浸入量と１０μｍでの浸入量の高い方の値に対して、細孔径の大きさが０．１μｍ〜１０μｍの範囲内での浸入量の値がそれ以下である場合を言う。 On the other hand, a pore having a peak at a position in the range of 0.1 to 10 μm corresponds to the gap between the secondary particles described above and reflects the filling state of the secondary particles. It is what. Compared with the peak on the small diameter side, this shows a slightly lower mountain shape, and the width of the two valley portions (minimum value) corresponding to the hem of the mountain shape is as wide as about 1 to 3 digits. Specifically, “a pore distribution having no peak in the range of 0.1 to 10 μm in pore size” means that the penetration amount is 0.1 μm and the penetration amount is 10 μm. When the pore size is within the range of 0.1 μm to 10 μm, the infiltration amount is less than the higher value.
そして、細孔径が１０〜１０００μｍの範囲内の位置にピークをもつ細孔というのは、マクロな亀裂や、欠陥に相当する空隙と考えられており、最も低い山形を示す。
以上のことから、本発明の高性能断熱材というのは、粒子相互の間に生じている空隙がないということであり、そうした粒子構造をもつものと云うことができる。
A pore having a peak at a position in the range of 10 to 1000 μm is considered to be a macro crack or a void corresponding to a defect, and shows the lowest mountain shape.
From the above, the high-performance heat insulating material of the present invention means that there are no voids formed between particles, and it can be said that it has such a particle structure.
ところで、発明者らの研究によると、従来の高性能断熱材については、この断熱材にまず水分を吸収させ、その後に乾燥を行うと、該断熱材は一定の収縮を起こし、とりわけ細孔径の大きさが０．１〜１０μｍの範囲内にピークが存在するような細孔が消失することを発見した。しかし、細孔径の大きさが０．０１〜０．１μｍの範囲内のピークを持つ細孔にはほとんど変化が無く、１０〜１０００μｍの範囲内にピークが存在する細孔はわずかに増加し、いずれも消失しないことも判った。 By the way, according to the researches of the inventors, with respect to the conventional high-performance heat insulating material, when this heat insulating material first absorbs moisture and then dried, the heat insulating material causes a certain shrinkage, and in particular, has a pore diameter. It was discovered that pores with a peak in the range of 0.1 to 10 μm disappeared. However, there is almost no change in the pores having a peak in the range of 0.01 to 0.1 μm, and the number of pores having a peak in the range of 10 to 1000 μm is slightly increased. It was also found that none of them disappeared.
またこうした高性能断熱材というのは、これを乾燥すると、上述のような収縮を起こして、外形の変化を招くが、熱伝導率はわずかに増加するものの影響は小さいことも判った。ただし、こうした断熱材は厚みが減ることで、厚みに比例する熱抵抗も小さくなっていく現象が見られる。 It was also found that such a high-performance heat insulating material, when dried, causes the above-described shrinkage and causes a change in outer shape, but the effect is small although the thermal conductivity is slightly increased. However, there is a phenomenon in which the heat resistance proportional to the thickness decreases as the thickness of such a heat insulating material decreases.
さらに、発明者らが知見したところによると、前述の粒子構造（０．１〜１０μｍの範囲内にピークをもたないもの）を有する高性能断熱材については、これに水分の吸収と乾燥の処理を繰り返し施した場合でも、その後は、吸温、加熱の履歴には関係なく上記の細孔径分布にほとんど変化がなく、さらなる収縮は起こらないことを究明した。即ち、成形体（断熱材）を水分吸収や乾燥した場合に消失する細孔は、細孔径の大きさが０．１〜１０μｍの範囲内に細孔分布のピークが存在する細孔のみであって、細孔径の大きさが０．０１〜０．１μｍおよび１０〜１０００μｍの範囲内に細孔分布のピークが存在するような細孔については消失するようなことはないことが判ったのである。 Furthermore, according to the findings of the inventors, the high-performance heat insulating material having the above-described particle structure (having no peak in the range of 0.1 to 10 μm) is absorbed into water and dried. It was found that even when the treatment was repeated, the pore diameter distribution was hardly changed and no further shrinkage occurred regardless of the history of temperature absorption and heating. That is, the pores that disappear when the molded body (heat insulating material) absorbs moisture or is dried are only pores having a pore distribution peak within a pore diameter range of 0.1 to 10 μm. Thus, it has been found that pores having pore distribution peaks in the range of 0.01 to 0.1 μm and 10 to 1000 μm do not disappear. .
多孔質体中に浸透した液体を乾燥除去しようとする場合、細孔径の逆数に比例する浸透圧相当の力が、細孔を収縮させる方向に働く。したがって、小さい細孔ほど収縮しやすく、大きい細孔ほど収縮しづらくなる。一方、細孔の強度が収縮に抗する力となるため、強度のある細孔は収縮せず、強度のない細孔は収縮する。 When the liquid that has penetrated into the porous body is to be removed by drying, a force equivalent to the osmotic pressure proportional to the inverse of the pore diameter acts in the direction of contracting the pores. Therefore, the smaller the pores, the easier it is to shrink, and the larger the pores, the more difficult it is to shrink. On the other hand, since the strength of the pores is a force against the shrinkage, the strong pores do not shrink, and the pores without strength shrink.
すなわち、高性能断熱材については、前述の通り、０．０１〜０．１μｍの範囲内にピークをもつ細孔というのは、原料粒子固有の形状を反映する隙間に相当し、浸透圧が原料粒子を壊すほど大きくないため、収縮することはない。一方、０．１〜１０μｍの範囲内の位置にピークが存在する細孔というのは、原料粒子の充填状態を反映しており、浸透圧によって充填状態が密になり、結果として消失する。さらに、１０〜１０００μｍの範囲内の位置にピークをもつ細孔というのは、マクロな亀裂や、欠陥に相当する空隙と考えられ、収縮力が最も小さい。そのため、より強力な原料粒子の充填状態の緻密化が完全に均質化しない結果として、マクロな亀裂がむしろ増加するようになるため、１０〜１０００μｍの範囲内の位置にピークをもつ細孔量は増加すると考えられる。 That is, for the high-performance heat insulating material, as described above, the pore having a peak in the range of 0.01 to 0.1 μm corresponds to a gap reflecting the shape unique to the raw material particles, and the osmotic pressure is the raw material. It does not shrink as it is not large enough to break the particles. On the other hand, pores having a peak at a position in the range of 0.1 to 10 μm reflect the packed state of the raw material particles, and the packed state becomes dense due to osmotic pressure and disappears as a result. Furthermore, pores having a peak at a position within the range of 10 to 1000 μm are considered to be macro cracks and voids corresponding to defects, and have the smallest contraction force. Therefore, as a result of the densification of the packing state of the stronger raw material particles not being completely homogenized, macro cracks rather increase, so the amount of pores having a peak at a position in the range of 10 to 1000 μm is It is thought to increase.
以上の知見に基づき、ヒュームド酸化物を主原料として含む高性能断熱材用圧縮成形体については、まずこれに水分吸収を行わせ、その後、引続き乾燥する処理を予め行うことによって、細孔径の大きさが０．１〜１０μｍの範囲内に細孔分布のピークがくるような細孔を、予め消滅させておくことによって、この断熱材が再び水分を吸収し、あるいはさらに乾燥されるようなことがあっても、再び収縮するようなことのない高性能断熱材にすることが有効であると考えられる。 Based on the above knowledge, the compression molded body for high-performance heat insulating material containing fumed oxide as the main raw material is first subjected to moisture absorption, and then subjected to subsequent drying in advance to increase the pore diameter. By eliminating the pores whose pore distribution peaks within a range of 0.1 to 10 μm in advance, this heat insulating material absorbs moisture again or is further dried. Even if there is, it is considered effective to make a high-performance heat insulating material that does not shrink again.
以上の説明から明らかなように、本発明の製造方法の適用によって得られる高性能断熱材とは、ヒュームド酸化物を主原料として含み、その他にセラミック超微粉やセラミックファイバーなどのいずれか少なくとも一種を含む原料を圧縮成形したものであって、細孔径の大きさが０．０１〜０．１μｍ、１０〜１０００μｍおよび０．１〜１０μｍの範囲内にはそれぞれ細孔分布のピーク位置がくるような細孔構造をもつものについて、その圧縮成形体を、まず水中に浸漬し、次いでこれを乾燥する処理を予め行うことによって、細孔径の大きさが０．１〜１０μｍの範囲内にピーク位置が来るような細孔を消滅させてなる断熱材であると云うことができる。 As apparent from the above description, the resulting that performance insulation material by application of the production method of the present invention, it comprises a fumed oxide as main components, at least one one of a ceramic ultrafine powder or ceramic fiber and other In which the pore size is in the range of 0.01 to 0.1 μm, 10 to 1000 μm, and 0.1 to 10 μm, so that the peak positions of the pore distribution are respectively present. For those having a fine pore structure, the compression molded body is first immersed in water and then dried, so that the peak position is within the range of 0.1 to 10 μm. It can be said that it is a heat insulating material formed by eliminating pores such as.
本発明の高性能断熱材を得るための吸湿ならびに乾燥の処理は、処理前の圧縮成形体の厚さにもよるが、数時間から数日間、水中に静置して吸湿させた後、１１０〜２００℃の温度域に数時間〜数日間保持して乾燥する方法が好適である。なお、この処理に当たっては、処理すべき圧縮成形体が水中で膨らむことがあるので、ガラスクロス入りの高性能断熱材などを使用することが推奨される。 The moisture absorption and drying treatment for obtaining the high-performance heat insulating material of the present invention depends on the thickness of the compression-molded body before the treatment, but after standing still in water for several hours to several days, the moisture is then absorbed. A method of drying in a temperature range of ˜200 ° C. for several hours to several days is preferable. In this treatment, it is recommended to use a high-performance heat insulating material containing glass cloth because the compression molded body to be treated may swell in water.
なお、本発明において、主原料として用いられるヒュームド酸化物の例としては、シリカやアルミナやチタニア、ジルコニアなどであり、その他の補助成分として含むセラミック超微粉の例はＳｉＣが好ましく、そしてセラミックファイバーの例としては、アルミナやシリカなどが好ましい。 Incidentally, Oite this onset bright, as an example of fumed oxides used as the main raw material, and the like silica, alumina or titania, zirconia, examples of the ceramic ultrafine powder is SiC is preferably included as other auxiliary components, and As an example of the ceramic fiber, alumina or silica is preferable.
上記の原料を、例えば、ヒュームドシリカを６０〜９５ｍａｓｓ％、ＳｉＣを５〜４０ｍａｓｓ％係る混合粉をガラスクロスなどに充填したり、成形枠内に充填し、油圧もしくは圧空などの圧縮成形機を使って、比重：０．１５〜０．５程度になるように圧縮成形して成形体とする。例えば、混合粉の配合としては、
（１）ヒュームドジルコニアを１０〜４０ｍａｓｓ％、ヒュームドアルミナを１０〜４０ｍａｓｓ％、残部をヒュームドシリカとした配合、
（２）ヒュームドチタニアを１０〜５０ｍａｓｓ％、ヒュームドアルミナを５〜２０ｍａｓｓ％、残部をヒュームドシリカとした配合、
（３）ヒュームドシリカを１〜１０ｍａｓｓ％、ヒュームドジルコニアを１０〜５０ｍａｓｓ％、残部をヒュームドアルミナとした、
配合例が好ましい。
For example, 60 to 95 mass% of fumed silica and 5 to 40 mass% of mixed powder of SiC are filled into a glass cloth or the like, and a compression molding machine such as hydraulic pressure or pneumatic pressure is filled. Use and compression molding to a specific gravity of about 0.15 to 0.5 to obtain a molded body. For example, as a blend of mixed powder,
(1) 10 to 40 mass% of fumed zirconia, 10 to 40 mass% of fumed alumina, and the balance of fumed silica as the balance,
(2) 10 to 50 mass% of fumed titania, 5 to 20 mass% of fumed alumina, and a blend containing fumed silica as the balance,
(3) 1-10 mass% of fumed silica, 10-50 mass% of fumed zirconia, and the remainder fumed alumina.
Formulation examples are preferred.
なお、従来の高性能断熱材の粒子構造は、未使用の状態で、細孔径の大きさが０．０１〜０．２μｍの範囲内のものが０．３〜１．０ｍｌ／ｇ、細孔径の大きさが０．１〜１０μｍの範囲内のものが０．７〜３．０ｍｌ／ｇ、細孔径の大きさが１０〜１０００μｍの範囲内のものが０．６〜１ｍｌ／ｇ程度の細孔が存在する細孔径分布となっている。 In addition, the particle structure of the conventional high-performance heat insulating material is 0.3 to 1.0 ml / g when the pore size is in the range of 0.01 to 0.2 μm and the pore size is unused. In the range of 0.1 to 10 μm, the pore size is 0.7 to 3.0 ml / g, and in the pore size range of 10 to 1000 μm is about 0.6 to 1 ml / g. It has a pore size distribution in which pores exist.
これに対し、本発明の高性能断熱材は、細孔径の大きさが０．０１〜０．１μｍの範囲内のものおよび１０〜１０００μｍの範囲内にある細孔の量は従来のものと大差がないが、細孔径の大きさが０．１〜１０μｍの範囲内にある細孔については、０．５ｍｌ／ｇ以下、好ましくは０．３ｍｌ／ｇ以下である。その結果、本発明の高性能断熱材は、成形体の吸水、乾燥の処理時に消失する０．１〜１０μｍの範囲内にピークのある細孔分布を示す細孔の量が少ないため、寸法安定性も高く、熱抵抗が劣化するようなことがない。 On the other hand, the high-performance heat insulating material of the present invention is greatly different from the conventional one in that the pore size is in the range of 0.01 to 0.1 μm and the amount of pores in the range of 10 to 1000 μm. However, for pores having a pore size in the range of 0.1 to 10 μm, it is 0.5 ml / g or less, preferably 0.3 ml / g or less. As a result, the high-performance heat-insulating material of the present invention is dimensionally stable because the amount of pores exhibiting a pore distribution with a peak in the range of 0.1 to 10 μm that disappears during the water absorption and drying treatment of the molded body is small. The heat resistance is not deteriorated.
２種の高性能断熱材を用意し、これらを常温の水中に６時間浸漬した後、１１０℃で１８時間乾燥して発明例１、２の高性能断熱材とした。その発明例１、２に係る高性能断熱材および従来の高性能断熱材（比較例１、２）を、再び常温の水中に６時間浸漬した後、１１０℃で１８時間乾燥する試験を両者に対して行った（水中浸漬と乾燥を２回繰り返した）。この試験の結果について、熱伝導率を表１に、そして、細孔径分布を図１、図２に示した。なお、熱伝導率についてはホットディスク法（京都電子工業製）、細孔径分布は水銀ポロシメータにて測定した。 Two types of high-performance heat insulating materials were prepared, and these were immersed in water at room temperature for 6 hours, and then dried at 110 ° C. for 18 hours to obtain high-performance heat insulating materials of Invention Examples 1 and 2. A test in which the high-performance heat insulating material according to Invention Examples 1 and 2 and the conventional high-performance heat insulating material (Comparative Examples 1 and 2) are dipped again in normal temperature water for 6 hours and then dried at 110 ° C. for 18 hours is used for both. (Immersion in water and drying were repeated twice). Regarding the results of this test, the thermal conductivity is shown in Table 1, and the pore size distribution is shown in FIGS. The thermal conductivity was measured with a hot disk method (manufactured by Kyoto Electronics Co., Ltd.), and the pore size distribution was measured with a mercury porosimeter.
上記の試験において、断熱材に水分を吸収させた後に乾燥する処理を行ったもの（発明例１、２）は、細孔分布のグラフ上において、細孔径の大きさが０．１〜１０μｍの範囲内にピーク位置がくる細孔については消失していたが、細孔径の大きさが０．０１〜０、１μｍおよび１０〜１０００μｍの範囲内にピークが存在する細孔については消失していなかった。即ち、本発明の高性能断熱材は、細孔径の大きさが０．０１〜０．１μｍおよび１０〜１０００μｍの範囲内にそれぞれピーク位置が存在する細孔のみを含み、圧縮成形体の収縮の原因となる０．１〜１０μｍの範囲内に細孔径分布のピークがくるような細孔が消失しており、それ故に、たとえその後に、再び水分吸収や乾燥を行っても、もはや細孔径分布が変化するようなことがなくなることがわかった。 In the above test, the heat treatment material that was dried after absorbing moisture (Invention Examples 1 and 2) had a pore size of 0.1 to 10 μm on the pore distribution graph. The pores whose peak positions were within the range disappeared, but the pores whose pore sizes were within the range of 0.01 to 0, 1 μm and 10 to 1000 μm did not disappear. It was. That is, the high-performance heat insulating material of the present invention includes only pores having peak positions in the range of 0.01 to 0.1 μm and 10 to 1000 μm, respectively, and the shrinkage of the compression molded body is reduced. The pores whose pore size distribution peaks within the range of 0.1 to 10 μm which is the cause have disappeared. Therefore, even if water absorption or drying is performed again thereafter, the pore size distribution is no longer present. It turns out that there is no such thing as changing.
ただし、水分吸収−乾燥による収縮の結果、厚みが小さくなることで、厚みに比例する熱抵抗が少し小さくなる。 However, as a result of shrinkage due to moisture absorption-drying, the thermal resistance proportional to the thickness is slightly reduced by reducing the thickness.
これに対し、従来の高性能断熱材は、厚さで２０％、厚さと垂直方向の長さで６％の収縮があった。一方、本発明の高性能断熱材の収縮は、厚さおよび長さともに１％未満（測定誤差の範囲内）であった。従来の高性能断熱材シートは、これを隙間なく貼り付け、水分と接触させたのち乾燥すると、収縮の結果として面積は８８％になり、面積の１２％の部分が高性能断熱材で覆われなくなってしまい、加えて、厚みが減少する結果として熱抵抗が２０％も低下した。一方、本発明の高性能断熱材については、収縮はなく、高性能断熱材間に隙間ができることもなく、熱抵抗も劣化することはなかった。 In contrast, the conventional high-performance heat insulating material contracted by 20% in thickness and 6% in length in the direction perpendicular to the thickness. On the other hand, the shrinkage of the high performance heat insulating material of the present invention was less than 1% in both thickness and length (within the measurement error range). The conventional high performance heat insulating material sheet is pasted without any gaps, and after drying after contacting with moisture, the area becomes 88% as a result of shrinkage, and 12% of the area is covered with high performance heat insulating material. In addition, as a result of the decrease in thickness, the thermal resistance decreased by 20%. On the other hand, the high performance heat insulating material of the present invention was not contracted, no gap was formed between the high performance heat insulating materials, and the thermal resistance was not deteriorated.
本発明の製造方法の適用によって製造された高性能断熱材は、５００℃以上で使用した後も、また、水分と接触させた後、乾燥が起こっても収縮することがないので、施工後の使用中に、収縮によって熱流がもれたり、隙間が開いてライニング層が弛んだりすることもなく、厚み減少による断熱性の劣化もない。 The high-performance heat insulating material manufactured by the application of the manufacturing method of the present invention does not shrink even after being used after being used at 500 ° C. or more, or after being brought into contact with moisture. During use, there is no leakage of heat due to shrinkage, no gaps are formed and the lining layer is not loosened, and there is no deterioration in heat insulation due to thickness reduction.
本発明は、冶金炉や取鍋などの溶湯容器のライニングの他、熱交換器等の各種熱機器の断熱材料の製造方法として応用できるものである。
This onset Ming, other lining of the molten metal container, such as a metallurgical furnace or a ladle, a shall be applied as a manufacturing method of the heat insulating material of various thermal equipment such as a heat exchanger.
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