200306964 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種適用來作為藉微波之照射而以 熱燒結陶-尤器材料或精密陶瓷材料等之被燒結物的爐壁二 之耐火絕熱材料及被覆材。 【先前技術】 以在’在被燒結物之燒結中’一般中使用電氣爐或瓦斯 爐等H以來自如此外部之加熱進行燒結^在被声 結物之表面與内部之間為免溫度差變大，必須使爐内温： 緩慢上昇。因此，有燒結時間很長之問題。 因此’為解決如此之問題，遂提出以微波燒結被燒結物 t方法（例如特開平6销63#)。此方法係具有燒結時間可 佰短或氣之控制性等優點，伴隨環境負荷之降低等要求 ’成為將來之燒結法而倍受矚目。 U波燒結軒，微波會被被燒結物吸收，被燒結物會自己 考X熱’故S被燒結4勿之表面與内部之間温度差會變小。因 此’可縮短燒結時間同時並可均—地燒結被燒結物。 又藉微波以本身發熱燒結被燒結物中，以具有與被燒 結物同等微波吸收特性之财火絕熱材包圍被燒結物，藉由 抑制被燒結物之輻射冷卻產生的溫度梯度，可使被燒結物 更進一步的燒結。 但，以具有與被燒結物同等微波吸收特性之耐火絕熱材 包圍被燒結物時，微波之能量亦會被包圍被燒結物的耐火 絕熱材消耗。因此，燒結所需之能量會增大。 82103 200306964 為減夕被耐火絕熱材料所消耗的微波能量，若減少 ^ 材料之厚度，藉輻射冷卻而從对火絕熱材料朝向 、、’失之熱里热法忽略，在被燒結物與耐火絕熱材料之 曰1冒產生溫度梯度的問題仍存在。 上述微波燒結法係就被燒結物之均—燒結及微波之能量 降低而言，已達相當高水準。 ::、以有限之微波能量為使更多之被燒結物燒結，當然 要尋、长牙重可適用於上述微波燒結法之更高性能的耐火絕 △、：料’亦即’耐火絕熱材料乃要求：①與被燒結物同樣 藉U波吸收而發熱’同時並擁有可更減少與藉輻射冷卻 Μ產生之被燒結物之間的溫度梯度之優異絕熱性；②全體 之微波吸收更小；③擁有對於所謂以短時間昇溫及冷卻之 使用環境優異的耐剝落性。 【發明内容】 登j月之說明 本發明之目的在於係提供一種適用來作為藉微波之照射 而以本身發熱燒結被燒結物之爐壁材的高性能耐火絕熱材 料及被覆材。 若例示本發明之較佳態樣，如以下般。 (1) 一種耐火絕熱材料，係藉微波之照射而以本身發熱 燒結被燒結物之微波燒結爐用耐火絕熱材料，其特徵在於 ••在基材之一面設置發熱層，並且基材係以無機纖維質材 料作為主成份，發熱層係以富鋁紅柱石（muuiteM+為主成 份。 82103 200306964 (2) 刖述之耐火絕熱材料，其中發熱層係除含有富鋁紅 柱石(mullite)以夕卜’尚含有微波吸收特性比富鋁紅柱石 (mullite)還大之物質。 (3) 刚述之耐火絕熱材料，其中發熱層係含有富鋁紅柱 石（muUite)與無機黏結材，或發熱層係含有富紹紅柱石 (mulhte)、具有微波吸收特性比富鋁紅柱石還大之 物質、及無機黏結材；而且，其無機黏結材係只使富鋁紅 柱石（mullne)、或使富鋁紅柱石（mulHte)與具有微波吸收特 性比萄鋁紅柱石（nuilhte)還大之物質呈皮膜狀連續被覆著。 (4) 别述之耐火絕熱材料，其中具有微波吸收特性比富 紹紅柱石（mullite)還大之物質為調整發熱層之發熱量者。 (5) 前述耐火絕熱材料，其中發熱層為含有無機纖維。 (6) 前述耐火絕熱材料，其中無機纖維為富鋁紅柱石 (mullite)纖維。 (7) 前述耐火絕熱材料，其中發熱層係設置而接觸於基 材之一面。 (8) —種被覆材，係用以構成發熱層，其特徵在於：在 富紹紅柱石（mullite)系水泥中，添加氧化鐵、氧化鎭、氧 化錯及碳化矽等之具有微波吸收特性比富鋁紅柱石 (mullite)還大之物質一種以上、及富鋁紅柱石㈤以出㊁）纖 維。 本發明人等經專心研究，結果在微波燒結中藉基材與發 熱層形成一用以包圍被燒結物之耐火絕熱材料。在本說明 書中所謂燒結係包含燒結。 82103 200306964 首先，說明有關發熱層，發熱層宜以富鋁紅柱石（mulHte) 作為主成分來形成。照射微波時，若考慮使被燒結物與發 熱層之表面溫度實質上相同，發熱層可適宜為與被燒結物 相同的材質。但，當被燒結物為陶瓷器材料時，陶瓷器材 料在1 000°C附近會軟化收縮，故無法使發熱層形成與被燒 結物相同的陶瓷器材質。另外，富鋁紅柱石（mullite)因具 有在陶竞裔材料之燒結溫度以上的溫度區域之耐熱性，同 時具有最接近於陶瓷器之微波吸收特性，故宜可使用來作 為發熱層之構成成分。 又，發熱層其構成成分宜含有微波吸收比富鋁紅柱石 (mullite)遂大之物質。將被燒結物即陶瓷器以具有最接近 於其之微波吸收特性的富鋁紅柱石（mulme)之發熱層而照 射破波，前述被燒結物與發熱層之表面溫度應為相等。但 貝卩不上車乂發熱層文微波得到之熱量，從發熱層朝外部消 =的煞里為無法忽略的大小。因此，只使發熱層之構成成 為田銘紅柱石（mullite)時，發熱層之溫度會受輻射冷卻 而IV低，故在被燒結物與發熱層之間會產生溫度梯度。從 以上之理由，宜藉由於發熱層中除富鋁紅柱石（mullite)以 卜之構成成分尚含有微波吸收比富鋁紅柱石（mulHte)還大 的物貝，而補償發熱層表面與被燒結物之溫度的差分。如 迟 U波吸收比画鋁紅柱石（muiiite)還大的物質可舉例 氧化鐵、氧化鎂、氧化錯、碳化矽等。 、t熱層係無機黏結材宜為只使富鋁紅柱石（muiHte) 或具有萄鋁紅柱石（muUite)與微波吸收特比富鋁紅柱石 82103 200306964 (mullite)還大之铷拼 σ ^冬 貝’主皮膜狀連續地被覆著之構造。 可知即使發埶芦 …、曰之構成成分為相同，若其構造相里，於 發熱層亦會產生差別。甘 ^ 门 /、 、 J其一例，圖1中係表示發熱非常充分 之發熱層的微小構iiL、0义 冓化與叙熱不充分之發熱層的微 的掃描型電子顯微鏡照片，圖2中係表示微小構造差^; 型圖。發熱為非常充分之發熱層的微小構造係如圖⑷之: 所不般’然機黏結材1乃使富鋁紅柱石(mullite)2盥且有忾 =收特性比富紹紅柱石㈣㈣還大的物f(㈣微 壬皮膜狀連續性被覆著。 當使用擁有此構造之發熱層時，發熱層及被燒結物之表 =附近的溫度乃從周波數2 · 4 5 G H z之微波照射開始約_ 分後達到1300。(：。 然而，發熱為不充分之發熱層的微小構造，如圖i及圖2 之b所示般，無機黏結材！之皮膜發展乃看不出來，而以盈 ，黏結材所得到之富lg紅柱石（muUite)2與具有微波吸: 寸性比富紹紅柱石（mullite)還大之物質（亦即微粉3)的結合 為部分的。使用此發熱層時，發熱層及被燒結物之表㈣ 近的溫度只昇溫至900。〇，而益法掉社姑陡 、 料。 m结被燒結物即陶瓷器材 上述之結果’係表示發熱層之發熱非常依存於以I機黏 ，皮膜發展的粒子彼此間結合之程度的一例。如、此例 表不般，構成發熱層之粒子與粒子之結合會很少，若粒子 彼此間為離散的狀態很明顯，發熱層之發熱會不充分〃，益 法燒結被燒結物。 刃 ^ 82103 -10- 200306964 又，為於發熱層顯現耐剝落特性 施^ /ώ,,,.,,,, 補強材且含有無機纖 、.隹。在mu，為以短時間進行昇溫、冷卻， 可承受熱剝落。使用無機纖維作為補強而 剝落特性。 巧虿政顯現耐 前述之無機黏結材i乃呈皮膜狀只被覆富銘紅柱石 (mulllte)2、或富銘紅柱石（mulUte)2與微粉3之組合的構造 係當含有無機纖維時，乃更重要。其理由係若含有纖维， 密度會降低而發熱效率降低，皮職構造可彌補200306964 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to a refractory and adiabatic insulation of a furnace wall 2 which is suitable for sintering a ceramic material such as a ceramic material or a ceramic material or a precision ceramic material by microwave irradiation. Materials and coatings. [Prior art] In general, "sintering of the sintered object" uses an electric furnace or a gas furnace, etc. H. Sintering with such external heating ^ avoids the temperature difference between the surface and the inside of the object to be sintered Large, the furnace temperature must be increased slowly: Therefore, there is a problem that the sintering time is very long. Therefore, in order to solve such a problem, a method for sintering a sintered object by microwave (for example, JP 6 Pin 63 #) is proposed. This method has the advantages that the sintering time can be shortened or the gas can be controlled. With the reduction of environmental load and other requirements, it will become a sintering method in the future and attracts much attention. For U-wave sintering, microwaves will be absorbed by the sintered object, and the sintered object will test X heat by itself, so the temperature difference between the surface and the inside of S will be reduced. Therefore, it is possible to shorten the sintering time and sinter the object to be sintered uniformly. In addition, the sintered object is sintered by heating by itself, and the sintered object is surrounded by a fire and heat insulation material having the same microwave absorption characteristics as the sintered object. By suppressing the temperature gradient generated by the radiated cooling of the sintered object, the sintered object can be sintered. The material is further sintered. However, when a sintered object is surrounded by a refractory and heat-insulating material having the same microwave absorption characteristics as the sintered object, the energy of the microwave is also consumed by the refractory and heat-insulating material surrounding the sintered object. Therefore, the energy required for sintering will increase. 82103 200306964 In order to reduce the microwave energy consumed by refractory insulation materials, if the thickness of the material is reduced, radiant cooling is used to ignore the thermal insulation method from the direction of the fire insulation materials, and the heat loss is ignored. The problem of material temperature gradients still exists. The above-mentioned microwave sintering method has reached a relatively high level in terms of the homogeneity of the sintered object-the sintering and the reduction of microwave energy. :: 、 With limited microwave energy for sintering more objects to be sintered, of course, it is necessary to find out that the long teeth can be applied to the above-mentioned microwave sintering method for higher performance fire-resistant insulation △ ,: material, that is, fire-resistant insulation The requirements are: ① the same as the object to be sintered to generate heat by U-wave absorption 'and at the same time have excellent thermal insulation that can reduce the temperature gradient between the object to be sintered by radiation cooling M; ② the overall microwave absorption is smaller; ③ It has excellent resistance to spalling in a so-called temperature rising and cooling environment. [Summary of the Invention] The description of the present invention aims to provide a high-performance refractory and heat-insulating material and a covering material suitable for use as a furnace wall material for sintering an object to be sintered by heating itself by microwave irradiation. The preferred aspects of the present invention are as follows. (1) A refractory and heat-insulating material is a refractory and heat-insulating material for a microwave sintering furnace that sinters a to-be-sintered object with its own heat by the irradiation of microwaves, which is characterized in that a heat-generating layer is provided on one side of the substrate The fibrous material is the main component, and the heating layer is made of mullite (muuiteM + as the main component. 82103 200306964 (2) The refractory and heat-insulating material described herein, in which the heating layer contains mullite in addition to mullite) It still contains substances with microwave absorption properties greater than mullite. (3) The refractory and heat-insulating material just mentioned, in which the heating layer contains muUite and inorganic bonding material, or the heating layer contains Fushao andalusite (mulhte), substances with larger microwave absorption properties than mullite, and inorganic bonding materials; moreover, the inorganic bonding material is only mullite or mullite (MulHte) and a substance having a microwave absorption characteristic larger than that of mullite (mulilte) are continuously covered in a film form. (4) A refractory and heat-insulating material of another kind, which has a microwave absorption characteristic richer than Andalusite (mullite) is a large substance that adjusts the heat generation of the heating layer. (5) The aforementioned refractory insulation material, wherein the heating layer contains inorganic fibers. (6) The aforementioned refractory insulation material, wherein the inorganic fiber is mullite (mullite) fiber. (7) The aforementioned refractory and heat-insulating material, wherein the heat-generating layer is provided in contact with one side of the substrate. (8) A coating material is used to form the heat-generating layer, which is characterized in: (Mullite) series of cement, adding iron oxide, hafnium oxide, oxidized oxide, and silicon carbide, etc., have more than one substance having a microwave absorption characteristic larger than mullite, and mullite is used to produce ㊁ fiber. The inventors have conducted intensive studies and found that in microwave sintering, a base material and a heating layer are used to form a refractory and heat-insulating material for surrounding the sintered object. The sintering system in this specification includes sintering. 82103 200306964 First, the heat generating layer will be described. The heat generating layer should be formed with mullite as the main component. When the microwave is irradiated, if the surface temperature of the object to be sintered and the heat-generating layer are considered to be substantially the same, the heat-generating layer may suitably be made of the same material as the object to be sintered. However, when the object to be sintered is a ceramic material, the ceramic material will soften and shrink near 1 000 ° C, so the heating layer cannot be made of the same ceramic material as the object to be sintered. In addition, mullite has heat resistance in the temperature range above the sintering temperature of the ceramic material and has microwave absorption characteristics closest to that of ceramics. Therefore, it can be used as a component of the heating layer. In addition, the constituent components of the heat-generating layer should preferably contain a substance whose microwave absorption is larger than that of mullite. The sintered object, ie, the ceramic, is irradiated with a heat-generating layer of mullite having the microwave absorption characteristics closest to it, and the surface temperature of the sintered object and the heat-generating layer should be equal. However, the heat obtained from the microwave of the heating layer of the car can't get on the car. The heat dissipation from the heating layer to the outside is the size that cannot be ignored. Therefore, when only the structure of the heat-generating layer is mullite, the temperature of the heat-generating layer is cooled by radiation and the IV is low, so a temperature gradient occurs between the sintered object and the heat-generating layer. For the above reasons, it is desirable to compensate the surface of the heating layer and the sintered layer by excluding the mullite-rich mullite in the heat-generating layer as a component that contains microwave absorption greater than that of the mullite. The difference in temperature of things. For example, substances whose absorption of the late U wave is larger than that of muiiite can be exemplified by iron oxide, magnesium oxide, oxidized oxide, and silicon carbide. The thermal bonding layer inorganic bonding material should be made of only mullite (muiHte) or with mullite (muUite) and microwave absorption, which is much larger than mullite 82103 200306964 (mullite). Shell's main skin is continuously covered with a membrane. It can be seen that even if the constituents of the hairpin are the same, if the structural phase is in the same, there will be a difference in the heating layer. As an example, the gate /, and J are shown in FIG. 1, which are microstructures of a heating layer with sufficient heat generation, iiL, 0, and a thermal scanning layer with insufficient heating, and a scanning electron microscope photograph in FIG. 2. Department represents a slight structural difference ^; The microstructure of the heating layer with very sufficient heat generation is shown in Figure :: The difference is that the mechanical bonding material 1 is made of mullite 2 and has 忾 = the characteristics are larger than that of Fushao andalusite.的 物 f (㈣ 微 皮 skin film continuous coating. When using a heating layer with this structure, the surface of the heating layer and the object to be sintered = near the temperature is from the microwave irradiation of the cycle number 2 · 4 5 GH z After about _ minutes, it reaches 1300. (:. However, the heating is a microstructure of insufficient heating layer, as shown in Figure i and Figure 2b, the development of the inorganic bonding material! The combination of lg-rich andalusite 2 (muUite) 2 obtained with the bonding material and a substance having a microwave absorption: larger than that of mullite (ie, fine powder 3) is part. When using this heating layer The surface temperature of the heating layer and the object to be sintered only increased to 900 °, and the benefits of the company were sharp. The result of the above-mentioned result of the sintered object, ie, ceramic equipment, indicates that the heating of the heating layer is very dependent. An example of the degree to which the particles developed by the film are bound to each other by the I machine. This example is not normal, and the particles and particles constituting the heating layer will have very little combination. If the particles are in a discrete state, the heating of the heating layer will be insufficient, and the sintered object will be sintered. -10- 200306964 In order to show the spalling resistance of the heating layer ^ / FREE ,,,. ,,,, Reinforcing material and contains inorganic fibers,. 隹. In mu, it can withstand heating and cooling in a short time, which can withstand Thermal exfoliation. The use of inorganic fibers as reinforcement and peeling characteristics. Qiao Zhengzheng shows resistance to the aforementioned inorganic bonding material i is film-like and only covered with mulllte 2 or mulUte 2 and fine powder 3 The combined structure is more important when it contains inorganic fibers. The reason is that if it contains fibers, the density will decrease and the heating efficiency will decrease. The leather structure can make up for
降低。 奴…、W 細強材角色之無機纖維例如宜為氧化銘氧化石夕纖維 、乳化！呂纖維、富結紅柱石（臟出te)纖維。尤宜可使用含 鋁紅柱石(mumte)纖維。富鋁紅柱石(muUite)因呈有最接： 陶兗器材料之微波吸收特性’故使用來作為補強材： 、截維亦尤宜為富紹紅柱石（mullite)材質。 ’ 其次，說明有關基材。 基材係宜可使用可透過微波且具有高絕熱性之材料。若 微波被基材吸收，能量被消耗’結果，燒結被燒結物所： 的能量會明顯增大。又，為防止輕射冷卻所造成之發心 的溫度降低，基材宜具有高絕熱性。進一牛， 曰 A v &材宜具有 向的财剝落特性。 滿足如此特性之基材可舉例如：以氧化紹氧化石夕纖維為 主^分之陶曼纖維板。陶⑽維板係宜可使用能透過微波 同時亚具有優異的絕熱性及耐火性、與高耐剝落性。 82103 -11 - 200306964 【實施方式】 實施例之 雖說明本發明之實施例，但，此僅為例示而非限制本發 明。 首先，於萄銘紅柱石（mullite)系水泥中添加少量氧化鐵 及富铭紅柱石（mullite)纖維而混合以形成被覆材。 其次’將此被覆材以2 mm之厚度塗布於厚40 mm之陶竟 纖維板（東芝Monoflux株式會社製FMX-17SR)。其後，再以 i〇〇°c使之乾燥3小時，在100(rc下燒結i小時，而得到本發 明之耐火絕熱材料。 再者，使用此耐火絕熱材料，而使發熱層作為内側，製 作300 X 600 X 300 mm之密閉空間。 然後，準備具有外徑85 mm、内徑75 mm、高度85 mm之 尺寸的咖啡杯形狀陶土製容器作為被燒結物。將此陶土製 谷為放置於鈾述之密閉空間内，照射周波數2·45 gHz的微 波。 此4 ’發熱層及被燒結物之表面附近的溫度實質上係相 同，隨微波之照射時間略比例上昇，得到如圖1所示之昇溫 4寸性。亦即’至l30(rC之昇溫時間約l〇〇分鐘，可以短時間 什溫 〇 所妝射之微波係透過基材即陶瓷纖維板，主要到達發熱 層及被燒結物即陶土製容器而被吸收，進行發熱。接觸發 熱層之陶究纖維板，係可降低從發熱層以輻射冷卻及熱傳 導朝外部逃離之熱量，同時，發熱層中存在之氧化鐵（微波 82103 -12- 200306964 吸收比富鋁紅柱石（mulHte)還 .^ ^ 補仏發熱以輻射冷彻艿 尤、傳v所造成之溫度下降而在# 危、，、 隹毛熱層表面與被燒結物之⑽ J…因此’陶土製容器與發熱層表面之溫度實質上： 結果’不會產生受到熱衝擊所產生的龜裂，可以 燒結陶土製容器。 守a 若依本發明’包圍被燒結物之耐火絕熱材料所 波能量會降低，同日夺’被燒結物與發熱層之表面溫係實； 上相同’可均一地燒結被燒結物。 、、 【圖式簡單說明】 圖1 (a)係表示發熱非常充分之發熱層的微小構造之掃扩 型電子顯微鏡照片。 $田 圖1 (b)係表示發熱不充分之發熱層的微小構造之掃打 電子顯微鏡照片。 田里 圖2(a)係表示發熱非常充分之發熱層的微小構 圖。 圖2(b)係表示發熱不充分之發熱層的微小構造之模型图 圖3係表示有關本發明之一個實施例的昇溫特 圖。 之曲線 【圖式代表符號說明】 無機黏結材 '富銘紅柱石（mullite) 1 微粉 82103 -13-reduce. Slave ..., the inorganic fiber with the role of W fine strength material, such as oxidized stone oxide fiber, emulsified! Lu fiber, rich andalusite (dirty te) fiber. It is particularly advantageous to use mullite fibers. MuUite is used as a reinforcing material because it has the following characteristics: The microwave absorption characteristics of ceramic pottery materials: It is especially suitable for Fushao andalusite (mullite) material. Next, the base material will be described. As the base material, a material that is permeable to microwaves and has high thermal insulation properties should be used. If the microwave is absorbed by the substrate, the energy is consumed. As a result, the energy of the sintered object is significantly increased. In addition, in order to prevent a decrease in the temperature of the core caused by light cooling, it is desirable that the base material has a high thermal insulation property. Into a cow, said Av & material should have the characteristics of exfoliation of wealth. A substrate satisfying such characteristics may be, for example, a talman fiberboard mainly composed of oxidized oxidized stone fiber. It should be possible to use the ceramic insulation board that can transmit microwaves, and at the same time have excellent thermal insulation and fire resistance, and high peel resistance. 82103 -11-200306964 [Embodiment] Although the embodiment of the present invention is described, this is only an illustration and does not limit the present invention. First, a small amount of iron oxide and mullite fiber are added to mullite cement to form a coating material. Next, this covering material was applied to a ceramic fiber board (FMX-17SR manufactured by Toshiba Monoflux Co., Ltd.) at a thickness of 2 mm at a thickness of 2 mm. After that, it was dried at 100 ° C for 3 hours and sintered at 100 ° C for 1 hour to obtain the refractory and heat-insulating material of the present invention. Furthermore, the refractory and heat-insulating material was used with the heating layer as the inner side. A closed space of 300 X 600 X 300 mm was made. Then, a coffee cup-shaped pottery clay container having an outer diameter of 85 mm, an inner diameter of 75 mm, and a height of 85 mm was prepared as a sintered object. The pottery valley was placed in In the closed space described by uranium, microwaves with a frequency of 2.45 gHz are irradiated. The temperature near the surface of the 4 'heating layer and the sintered object is substantially the same, which increases slightly with the irradiation time of the microwave, as shown in Figure 1. It shows a 4-inch temperature rise. That is, the temperature rise time to 1300 (rC is about 100 minutes, and the microwave emitted by the short-time temperature can be transmitted through the ceramic fiber board, which mainly reaches the heating layer and the sintered object. That is, the ceramic container is absorbed and generates heat. The ceramic fiberboard that touches the heating layer can reduce the heat that escapes from the heating layer by radiation cooling and heat conduction to the outside. At the same time, the iron oxide (microwave 82103) present in the heating layer -12- 200306964 Absorption is also better than mullite. ^ ^ The heat is generated by radiating cold chills and radiating the temperature drop caused by v, and the temperature on the surface of the hot layer and the object to be sintered is reduced. J ... Therefore, the temperature of the surface of the container made of clay and the heating layer is substantially: As a result, no crack caused by thermal shock is generated, and the container made of clay can be sintered. The wave energy of the refractory and heat-insulating material will decrease, and the surface temperature of the sintered object and the heating layer is the same on the same day; the sintered object can be sintered uniformly on the same day. [Schematic description] Figure 1 (a) shows Scanning electron microscope photograph of the microstructure of the heat-generating layer with sufficient heat generation. $ 田 图 1 (b) is a scanning electron microscope photograph of the micro-structure of the heat-generating layer with insufficient heat generation. Figure 2 (a) of Tanari Fig. 2 (b) is a model diagram showing the microstructure of a heat-generating layer with insufficient heat generation. Fig. 3 is a graph showing the temperature rise of an embodiment of the present invention. Representative No. DESCRIPTION inorganic bonding material 'Fuming mullite (mullite) 1 micronized 82103-13-