HEAT RESISTANT INORGANIC FIBER

Abstract: A high-temperature-resistant inorganic fiber comprising 4 mol% or more of at least one member selected from the group consisting of oxides of V, Fe, Co, Ni, Cr, Mn and Zr; 70 to 90 mol% of silica, which may further includes CaO, MgO, TiO₂, Aℓ₂O₃ P₂O₅.

Description: Heat-resistant inorganic fiber The present invention relates to a high-temperature resistant inorganic fiber. Most typical heat-resistant inorganic fiber is so-called ceramic fiber consisting of alumina and silica and having an average diameter of about 3 pm. In order to save oil, energy conservation measures have been taken in various types of industrial furnaces. With this trend, ceramic fiber has been recently adopted in furnace walls with considerably satisfactory results. However, furnace walls made of ceramic fiber are also subject to drawbacks such as layer separation, joint separation, cracking, and partial or overall destruction of furnace walls or ceilings. In an attempt to search for causes of these drawbacks, it has neen found that the heat resistance of the ceramic fiber used does not meet the working level or in other words the working conci tio are too severe for the ceramic fiber. Since the ceramic fiber is a glassy material, it is transfortd into a stable crystalline structure upon being heated. With this transformation, the fiber snzinks and degrades in mechanical strength, resulting in shrinkage and degradation in resiliency of a ceramic fiber product which is a collective body of the fiber. Various articles and literatures have been published on this subject. Just to show an example, such a phenomenon is shown in Leonard E. Olds, William C. Miller, John M. Pallo, "High Temperature Alumina-Silicate Fibers Stabilized with Cr2O3", Ceramic Bulletin, 59, 7, pp. 739 to 741, 1980. In this publication, Olds et al made a comparison between a conventional alumina-silicate ceramic fiber and a ceramic fiber (chromia-stabilized ceramic fiber) containing 3 to 4% of chromia. They made an analysis of the change in quality of the ceramic fibers, the stabilizing function of chromia, and the effects obtained from addition of chromia (prevention of sintering). Although the chromia-stabilized alumina-silicate ceramic fiber which Olds et al used as the subject of an experiment is superior in its heat resistance to the conventional ceramic fiber, it still does not meet the working conditions at the industrial site. In order to provide a solution to this problem, the present inventors have made extensive studies. The present inventors first realized that quartz glass does not suffer much viscosity degradation at high temperatures and is more stable against heat than other heatresistant glasses. In view of this, the present inventors searched for a suitable additive to take the 21 ace of alumina. As a result of these studies, it has been found that a heat-resistant fiber which is ¯su-va-ent cr superior in its heat resistance to the conventional ceramic fiber may be prepared from a raw material composition consisting of quartz glass with an oxide of zirconium or a metal belonging to the group V to VIII of the fourth period of the periodic table. vurthermore, this heat-resistant fiber can be prepared In similar steps and by similar apparatuses as are adopted in the manufacture -of conventional ceramic fibers. The present invention has thus been established. U.S.P. Serial No. 2,873,197 discloses easy manufacture of fiber by the spinning method by addition of zirconia (ZrO2). This method uses a raw material composition consisting of 40 to 60%by weight of silica, 20 to 45% by weight of alumina, and 3.5 to 20% by weight of zirconia. However, this composition is based on AQ203-Sio2 and is essentially different from the composition of the present invention which is based on quartz glass with ZrO2 added thereto. It is an object of the present invention to provide an inorganic fiber which is excellent in heat resistance and which undergoes only small changes (or shrinkage) in fiber length at high temperatures. In order to achieve the above object of the present invention, there is provided a heat-resistant inorganic fiber which consists of not less than 4 moi% of at least one member selected from the group consisting of oxides of vanadium (V), iron (Fe), cobalt (Co), nickel (Ni), chrome (Cr), manganese (Mn), and zirconia (Zr); 70 to 90 mol% of silica; and if desired the third component consisting of an inorganic material which does not affect the heat-resistivity of the fiber and does promote the stability of the vitrification of the fiber. The basic composition of the inorganic fiber of the present invention includes silica as the first component; at least one oxide of a metal such as V, Cr, ,^4n, Fe, Co, Ni, and Zr as the second component; and if desired the third component consisting of an inorganic material which does not interrere with vitrification such as at least one metal oxide sected from calc- (CaC), magnesia (NgO), titania (TiG2), alumina (At203) and phosphorus pentoxide (P2O5). The metal oxide as the second component must be ccntained in the amount of not less than 4 mol% and preferably 5 mol%. The addition of the second component significantly improves heat resistance of the fiber and renders the molten silica electrically conductive. Molten silica exhibits a large electrical resistance. However, addition of a metal oxide as the second component as described above renders the mixture electrically conductive and facilitates melting in an electric furnace. Silica is contained in the amount of 70 to 90 mol% and preferably 75 to 85 mol%. If the amount of silica is less than 70 mol%, it will be deviated from the basic glass phase of quartz glass. The resultant increase of the third component inevitably gives glass of poor heat-resistivity and degraded stability. Then, the metal oxide tends to crystallize, resulting in formation of a large amount of shots (or unfiberized granule) and degradation in the manufacturing yield of the fiber. On the other hand, if the amount of silica exceeds 90 mol%, the viscosity of the molten silica increases to prevent the molten silica from flowing out of the electric furnace. In contrast to this, in the fiber of the present invention, most of the metal oxide is part of the glass at ambient temperature and prior to heating, or is aissolved in the liquid phase in the quartz glass. Only a small amount of metal oxide remains in the solid phase. For this reason, the third component which does not significantly degrade the heat resistance of the glass may be added to the raw material composition for stabilizing the glass consisting of silica and the metal oxide. Examples of particularly preferable compositions according to the present invention may include Si02-Cr O -Ak203 and SiO2 -ZrO2-Al2O3-FeO. The raw material mixture of the mixing ratio as aescribed above is prepared into a fiber according to the method for manufacturing a conventional ceramic fixer. More specifically, the raw materials are melted in an electric furnace of a structure as disclosed in U.S.p. Serial No. 2,686,821, and the molten mixture rowing out of a gate is blown by air or vapor using a nozzle disclosed in U.S.P. Serial No. 3,476,324 to prepare the fiber. The composition of the fiber according to the present invention as described above has superior heat resistance to that of the conventional ceramic fiber or the alumina-silicate ceramic fiber containing chromia which is disclosed in U.S.P. Serial No. 3,449,137. This invention can be more fully understood from the following detailed description when taken in conjunction with the accompanying drawings, in which: Figs. 1A to 1D are graphs showing the rate of change (%) in the fiber length as a function of changes in temperature according to an example of the ceramic fiber according to the present invention; Figs. 2A and 2C are graphs showing the rate of change (%) in the fiber length as a function of changes in temperature according to another example of the present invention; Figs. 3A to 3E are graphs showing the rate of change (%) in the fiber length as a function of changes in temperature of the ceramic fiber according to further examples of the present invention (excluding Fig. 3C); and Figs. 4A and 4B are graphs showing the rate of change (8) in the fiber length as a function of changes in temperature of the ceramic fiber according to a still further example of the present invention. The present invention will now be described by way of its examples. The tests conducted to confirm the effects of the present invention were the simple heat resistance test using a gas cigarette lighter, measurement of the rate of change in the fiber length, and the thermal linear shrinkage test of a blanket. In the simple heat resistance test using a gas cigarette lighter, a heat-resistant fiber is brought into direct contact with the flame of the cigarette lighter. All of the conventional alumina-silicate ceramic fibers shrink from the fiber ends and disappear from the sight. Therefore, the quality of the fibers according to the present invention and the prior art may be readily determined. According to the measurement of the rate of change in the fiber length, one fiber is heated at gradually increasing temperatures and expansion and shrinkage of the fiber are measured. In this case, a platinum wire is used as a support wire for suspending the fiber. A fiber with shots attached to its distal end is selected so as to suspend the fiber substantially vertically. The shots serve as a weight. If the fiber selected does not have such shots, fine powder of ceramic fiber is suspended in a colloidal silica solution, and one drop of the resultant coating cement is attached to the distal end of the fiber and is dried. In the thermal linear shrinkage test of a blanket, part of the fiber sample is stirred with water to remove most of the shots and is used to prepare blankets according to the conventional method. Then the thermal linear shrinkage is measured. Examples will now be described. Example 1 (Chromia is used as the metal oxide) Used as raw materials were Australian Fremantle siliceous sand as a silica source, "Aecrox-R" (trade mark) manufactured by Pfizer-Quigley Inc. as chromia, "A-21" (trade mark) manufactured by SUMITOMO CHEMICAL CO., TD. as 21um na, and other industrially available chemicals. The raw materials as described above were melted in an electric furnace having a gate of 25 mm width. The electric furnace was inclined to gradually flow the resultant molten material which was blown with com cesse air rrcm a nozzle disclosed in U.S.P. Serial No. 3,426,324. The compressed air had a pressure of 730 kg/cm2, and was fed at a rate of 10 m3/min. The prepared fiber was collected in a fiber collection chamber defined by metal nets. The amount of fiber shots was relatively small. The results of X-ray diffractiometry confirmed no presence of crystalline structure. Dart of the fiber was brought into contact with the flame of a cigarette lighter. If no shrinkage was observed with the naked eye, the fiber was determined to be "excellent" (this also applies to the subsequent examples). If shrinkage was observed but was significantly smaller than that obtainable with the conventional ceramic fiber, the fiber was determined to be "good" (this also applies to the subsequent examples). Measurements were also made of the softening point, the blanket shrinkage and so on. The measurements of the rate of change in the fiber length are shown in Figs. 1A to 1D. Table 1 EMI8.1 Test <SEP> Cr2O3 <SEP> SiO2 <SEP> Al2O3 <SEP> TiO2 <SEP> MgO <SEP> RO <SEP> * <SEP> Gas <SEP> Cigarette <SEP> Softening <SEP> Blanket <tb> No. <SEP> Lighter <SEP> Test <SEP> Point <SEP> Shrinkage <SEP> ** <tb> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> ( C) <SEP> (%) <tb> a <SEP> 5.0 <SEP> 75.0 <SEP> 20.0 <SEP> 20.0 <SEP> Excellent <SEP> 1,440 <SEP> or <SEP> 4.3 <tb> higher <tb> b <SEP> 8.75 <SEP> 82.5 <SEP> 8.75 <SEP> 8.75 <SEP> Excellent <SEP> 1,440 <SEP> or <SEP> 2.5 <tb> higher <tb> c <SEP> 12.0 <SEP> 85.0 <SEP> 3.0 <SEP> 3.0 <SEP> Excellent <SEP> 1,440 <SEP> or <SEP> 1.4 <tb> higher <tb> d <SEP> 15.0 <SEP> 80.0 <SEP> 5.0 <SEP> 5.0 <SEP> Excellent <SEP> 1,440 <SEP> or <SEP> 2.1 <tb> higher <tb> e <SEP> 10.0 <SEP> 88.0 <SEP> 2.0 <SEP> 2.0 <SEP> Excellent <SEP> 1,440 <SEP> or <SEP> 1.6 <tb> higher <tb> f <SEP> 12.5 <SEP> 85.5 <SEP> 2.0 <SEP> 2.0 <SEP> Excellent <SEP> 1,440 <SEP> or <SEP> 1.7 <tb> higher <tb> g <SEP> 10.0 <SEP> 87.5 <SEP> 2.5 <SEP> 2.5 <SEP> Excellent <SEP> 1,440 <SEP> or <SEP> 1.4 <tb> higher <tb> h <SEP> 12.5 <SEP> 75.0 <SEP> 12.5 <SEP> 12.5 <SEP> Excellent <SEP> 1,440 <SEP> or <SEP> 2.3 <tb> higher <tb> i <SEP> 15.0 <SEP> 80.0 <SEP> 5.0 <SEP> 5.0 <SEP> Excellent <SEP> 1,440 <SEP> or <SEP> 1.9 <tb> higher <tb> j <SEP> 9.0 <SEP> 87.5 <SEP> 3.5 <SEP> 3.5 <SEP> Excellent <SEP> 1,440 <SEP> or <SEP> 2.3 <tb> higher <tb> k <SEP> 12.5 <SEP> 82.5 <SEP> 5.0 <SEP> 5.0 <SEP> Excellent <SEP> 1,440 <SEP> or <SEP> 1.8 <tb> higher <tb> * RO = Al2O3 + TiO2 + MgO ** 1,400 C for 24 Hours Example 2 (The metal oxide is chromia and iron oxide) Indian chrome ore was used as a metal oxide. The chemical analysis of this ore provided the results shown in Table 2 below: Table 2 (% in weight) EMI9.1 <tb> Cr2O3 <SEP> FeO <SEP> SiO2 <SEP> Al2O3 <SEP> MgO <tb> 58.3 <SEP> 16.4 <SEP> 4.0 <SEP> 12.3 <SEP> 11.2 <tb> The procedures of Example 1 were followed, except for the additional above analysis, to prepare the fiber. The resultant fiber was subjected to the same tests as in Example 1. The obtained results are shown in Table 3 below: Table 3 EMI10.1 Test <SEP> Cr2O3 <SEP> FeO <SEP> MeO <SEP> * <SEP> SiO2 <SEP> Al2O3 <SEP> MgO <SEP> RO <SEP> ** <SEP> Gas <SEP> Cigarette <SEP> Softening <SEP> Blanket <tb> No. <SEP> Lighter <SEP> Test <SEP> Point <SEP> Shrinkage <SEP> *** <tb> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> ( C) <SEP> (%) <tb> l <SEP> 7.16 <SEP> 4.27 <SEP> 11.43 <SEP> 81.1 <SEP> 2.25 <SEP> 5.20 <SEP> 7.45 <SEP> Godd <SEP> 1,230 <SEP> 4.0 <tb> m <SEP> 7.74 <SEP> 4.61 <SEP> 12.35 <SEP> 79.6 <SEP> 2.44 <SEP> 5.61 <SEP> 8.05 <SEP> Godd <SEP> 1,380 <SEP> 3.8 <tb> n <SEP> 6.33 <SEP> 3.77 <SEP> 10.10 <SEP> 83.3 <SEP> 1.99 <SEP> 4.59 <SEP> 6.58 <SEP> Godd <SEP> 1,350 <SEP> 4.2 <tb> o <SEP> 4.97 <SEP> 2.96 <SEP> 7.93 <SEP> 86.9 <SEP> 1.56 <SEP> 3.60 <SEP> 5.16 <SEP> Excellent <SEP> 1,440 <SEP> or <SEP> 3.3 <tb> higher <tb> p <SEP> 8.96 <SEP> 1.91 <SEP> 10.87 <SEP> 85.9 <SEP> 0.99 <SEP> 2.28 <SEP> 3.27 <SEP> Excellent <SEP> 1,440 <SEP> or <SEP> 2.0 <tb> higher <tb> q <SEP> 10.1 <SEP> 2.22 <SEP> 12.32 <SEP> 83.8 <SEP> 1.77 <SEP> 2.71 <SEP> 3.88 <SEP> Excellent <SEP> 1,440 <SEP> or <SEP> 1.8 <tb> higher <tb> r <SEP> 8.34 <SEP> 3.10 <SEP> 11.44 <SEP> 83.2 <SEP> 1.63 <SEP> 3.77 <SEP> 5.40 <SEP> Excellent <SEP> 1,440 <SEP> or <SEP> 2.3 <tb> higher <tb> s <SEP> 7.32 <SEP> 3.58 <SEP> 6.68 <SEP> 82.8 <SEP> 1.89 <SEP> 4.36 <SEP> 6.25 <SEP> Excellent <SEP> 1,440 <SEP> or <SEP> 3.3 <tb> higher <tb> * MeO = Cr2O3 + FeO ** RO = Al2O3 + Mgo *** Same as in Table 1 The measurements of the rate of change in the fiber length are shown in Figs. 2A to 2C. Example 3 (Other metal oxides) The procedures of Example 1 were followed except that cobalt oxide, vanadium pentoxide, nickel oxide, and iron oxide were used as the metal oxides. The resultant fibers were subjected to the same test as in Examples 1 and 2 and the obtained results are shown in Table 4 below. Referring to Table 4, x and y are Comparative Examples wherein the amount of silica is outside the range defined according to the present invention. The rate of change in the fiber length of each fiber is shown in Figs. 3A to 3E. Table 4 EMI12.1 Test <SEP> SiO2 <SEP> CoO <SEP> V2O5 <SEP> NiO <SEP> FeO <SEP> MgO <SEP> CaO <SEP> MnO2 <SEP> Gas <SEP> Cigarette <SEP> Softening <tb> No. <SEP> Lighter <SEP> Test <SEP> Point <tb> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> ( C) <tb> t <SEP> 74.6 <SEP> 25.4 <SEP> Good <SEP> 1.260 <tb> u <SEP> 82.4 <SEP> 17.4 <SEP> Good <SEP> 1,390 <tb> v <SEP> 70.0 <SEP> 30.0 <SEP> Good <SEP> 1.200 <tb> w <SEP> 89.2 <SEP> 10.8 <SEP> Excellent <SEP> 1,440 <tb> x <SEP> 65.3 <SEP> 34.7 <SEP> Poor <SEP> 1,050 <tb> y <SEP> 68.9 <SEP> 31.1 <SEP> Poor <SEP> 1,140 <tb> z <SEP> 74.5 <SEP> 25.5 <SEP> Good <SEP> 1,240 <tb> &alpha; <SEP> 76.7 <SEP> 15.0 <SEP> 8.3 <SEP> Good <SEP> 1,380 <tb> ss <SEP> 81.4 <SEP> 12.0 <SEP> 6.6 <SEP> Good <SEP> 1,350 <tb> &gamma; <SEP> 72.1 <SEP> 18.0 <SEP> 9.9 <SEP> Good <SEP> 1,350 <tb> # <SEP> 75.8 <SEP> 11.9 <SEP> 12.3 <SEP> Good <SEP> 1,370 <tb> # <SEP> 72.1 <SEP> 13.0 <SEP> 14.9 <SEP> Good <SEP> 1,340 <tb> Example 4 The raw materials of the composition as shown in Table 5 below were used and the same procedures as in Example 1 were followed to prepare a fiber. The resultant fiber was subjected to the same tests as in Example 1. The obtained results are shown in Table 5 below. In bl (Comparative Example), since the amount of silica was less than 70 mol%, the simple cigarette lighter test provided unsatisfactory results. The rate of change in fiber length of each fiber (al, bl and cl) is shown in Figs. 4A and 4B. Table 5 EMI14.1 Test <SEP> ZrO2 <SEP> FeO <SEP> SiO2 <SEP> P2O5 <SEP> Al2O3 <SEP> CaO <SEP> Cr2O3 <SEP> Gas <SEP> Cigarette <SEP> Softening <SEP> Blanket <tb> No. <SEP> Lighter <SEP> Test <SEP> Point <SEP> Shrinkage <SEP> * <tb> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> (mol%) <SEP> ( C) <SEP> (%) <tb> al <SEP> 21.9 <SEP> 4.2 <SEP> 70.3 <SEP> - <SEP> 3.6 <SEP> - <SEP> - <SEP> Good <SEP> 1,300 <SEP> 3.0 <tb> bl <SEP> 22.7 <SEP> 4.2 <SEP> 65.2 <SEP> - <SEP> 5.6 <SEP> 2.3 <SEP> - <SEP> Poor <SEP> 1,100 <SEP> 4.8 <tb> cl <SEP> 9.7 <SEP> 5.4 <SEP> 79.1 <SEP> - <SEP> 5.8 <SEP> - <SEP> - <SEP> Good <SEP> 1,280 <SEP> or <SEP> 2.5 <tb> higher <tb> dl <SEP> 4.1 <SEP> 5.0 <SEP> 81.2 <SEP> - <SEP> - <SEP> 2.0 <SEP> 4.5 <SEP> Good <SEP> 1,300 <SEP> 2.5 <tb> el <SEP> 11.4 <SEP> - <SEP> 79.2 <SEP> - <SEP> 4.2 <SEP> - <SEP> 3.2 <SEP> Good <SEP> 1,300 <SEP> 2.3 <tb> fl <SEP> 17.7 <SEP> - <SEP> 74.1 <SEP> 5.2 <SEP> - <SEP> 3.0 <SEP> - <SEP> Good <SEP> 1,250 <SEP> 2.7 <tb> * Same as in Table 1

Claims: Claims: 1. A high-temperature-resistant inorganic fiber consisting essentially of not less than 4 mol% of at least one member selected from the group consisting of oxides of vanadium (V), iron (Fe), cobalt (Co), nickel (Ni), chrome (Cr), manganese (Mn) and zirconium (Zr); and 70 to 90 mol% of silica. 2. A high-temperature-resistant inorganic fiber according to claim 1, further comprises an inorganic material which does not interfere with vitrification. 3. A high-temperature-resistant inorganic fiber according to claim 2, wherein the inorganic material is at least one member selected from the group consisting of calcia (CaO), magnesia (MgO), titania (TiO2), alumina (At203), and phosphorus pentoxide (P2O5). 4. A high-temperature-resistant inorganic fiber according to claim 1, wherein the silica is included in the range of 75 to 85 mol%.

Inventors: ARAI, KENJI, ENDO, SHIGEO, HIRATA, KIMIO, ITO, AKIRA, MISU, YASUO
Applicants: TOSHIBA MONOFRAX COMPANY LTD.
Application year: 1982
Main classification: C03C13
IPC codes: C23C30, C03C13