JPS59501824A - Alkali-resistant glass bodies and fibers - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Alkali-resistant glass bodies and fibers A group of glass bodies that have a structure that can be made into fibers. Hydrated alkali and/or alkaline earth aluminosilicates. many different types Although mineral zeolites are known and have been described in the literature, there are 11 species. Minerals, namely anaLciyn, chabazite Azitsu, Clinoptilolite, Eliona erionite, 7 ferrierite, hyuu 2ndite (htwlatutite), laumontite (laumontit) e), mordenite, rLatroli te), phillipsitg and wayrakite ( vaairakite) constitute the major group of mineral zeolites. this The chemical and physical properties of the major mineral zeolites and many of the minor minerals are The properties of mineral zeolites are described by Lefont (supervising) industry. Minerals and rocks above (Ind, wstrial Minerals and Rocks) (4th edition, 1975) pp. 1235-1274; Breck's Zeolite Molecular Sieve 5ieves) (1974), especially the Natural Zeolite series. Volume 4 (Mineralogical Society of America) Ameri, CA): November 1977). child These publications also discuss the geological existence and proposed natural mineral zeolites. or the industrial and agricultural industries in which the natural mineral zeolite is currently used commercially. The above uses are listed.

Natural mineral zeolites have been widely described in many recent papers and patents. It is important to recognize that zeolites are a completely different class of materials. be. Due to the lack of a widely accepted system for naming synthetic zeolites And some synthetic materials can occur in structure with natural mineral zeolites. Some reports in the literature and patents show X-ray diffraction patterns suggesting similarities. A variety of synthetic zeolites are described as “synthetic” variants of natural mineral zeolites. are doing. Therefore, for example, synthetic zeolites of the type consisting of ° "analcime" or "synthetic mordenite" 　)” etc.However, it is stated in the above-mentioned Bretzk document that As shown, this method is technically unreasonable and has two, otherwise obvious Clearly distinguishable classes of materials: natural mineral zeolites and synthetic zeolites This simply led to confusion between the two. Are there any structural similarities between these two groups? However, natural mineral zeolites are different from synthetic zeolites. constitute a class of substances that are very distant and distinct in structure and properties .

Glasses are glassy substances composed mostly of silica. However, the Since Lika is a highly refractory material, substantial amounts of soda ash, lime or other The fusic material is added to the silica and the glass-forming composition is heated to a reasonable temperature. It becomes possible to be melted by Small amounts of other substances, usually elemental substances or oxidations A substance is usually added to the glass melt to give the finished glass a color or chemical resistant product. Gives special qualities such as sex.

However, until now, it has been found that in glass matrices and especially glass matrices There have been no reports regarding the significant use of zeolites as major components of gas. nine The linoptilolite and glass mixture is sooc (well below the melting point of either) is fired to produce what is described as a low-porosity, closely spaced glass composition. One experiment has been reported; See page 197 of MtLmpton.

Jill, such as in Pilkington's AR glass. In some glasses by containing conia and/or titania. Provides alkali resistance. These substances increase the alkali resistance of the glass body However, these materials are made of refractory materials that increase the melting point of such glasses. be. In addition, zirconia and titania include silica, soda, calcia (Ca1c iα) and soda lime, which is a much more expensive material than the usual components of silica glass. Zirconia and titania tend to increase the cost of the glass.

Although calcia tends to lower the melting point of glass compositions, soda lime-silica Approximately 15・ξ-cent 4 depending on the weight of the glass body (15%) to glass technology for using calcium oxide in larger amounts General precautions are required.

Purpose of the invention Producing alkali-resistant glass from modified, naturally occurring zeolite materials This is the object of the present invention.

Another object of the invention is to use naturally occurring zeolite materials in readily available alkaline earths. It is modified with similar compounds.

Another object of the present invention is to obtain relatively low temperature materials from modified naturally occurring zeolites. It is to form a glass body at a certain degree.

Brief description of the drawing Figure 1 is a graph showing the weight loss of a glass body exposed to dilute caustic soda. Ru.

Figure 2 is a graph illustrating the viscosity-temperature relationship of the glass of the present invention and commercially available window glass. be.

Outline of the invention The present invention constructs a glass composition that has remarkable alkali resistance in an alkaline environment. to be accomplished. Such glass compositions contain relatively high alkaline earth metal oxides, especially It is characterized by a calcia content and a low silica content. In particular, these The glass composition contains alkaline earth compounds, especially calcium compounds or calcium Substances containing and magfusium compounds are added to produce low silica, high alkali Earth oxides, especially calcia, °naturally occurring zeolas that produce glass compositions guided by the site. In addition, a glass body formed from the above glass composition, especially a fiber fibers are included within the scope of the present invention.

Detailed description and preferred embodiments The present invention contains relatively high amounts of one or more alkaline earth metal oxides. silica, alumina, calcia and calcia. The present invention relates to a glass containing a combination of shea and magnesia. reacted in advance Particularly useful alkali-resistant glasses containing naturally occurring zeolites include: Composition within the range of about 30% by weight Niji Liquor to about 60% by weight alumina From about 20% to about 20% by weight, Calcia - from about 20% to about 60% by weight Kurashiki Magnesia About 0% to about 30% by weight (calcia plus magnesia content is about 30% by weight) % to about 60% by weight).

Preferred compositions contain at least 27% by weight of calcia and at least 13% by weight. Contains alumina. having calcia present at about 27% to about 35% by weight Glass bodies such as fibers are particularly useful.

Such glasses, together with naturally occurring zeolites, can be used, for example, in the form of limestone. or calcium compounds such as those found in dolomite. It is easily and inexpensively formed by melting a magnesium compound and a magnesium compound. Being able to do this is important, as will be explained later. Such glass , in many cases calcium is present on a weight basis in approximately the same amount as silica. Therefore, it is described as low to medium alumina, calcium silicate glass. be able to.

The alkali-resistant glass composition is composed of naturally occurring zeolite substances and calcium carbonate. can be easily formed by mixing. Date: March 22, 1982 No. 360,516 to Clough et al. As has been shown, many naturally occurring zeolite materials can form glass under suitable conditions. can be formed. Zeolites have many uses as glass forming materials. It has points. Naturally occurring zeolites have already undergone a reaction51 and The various elements contained therein are intimately mixed and react with each other. . Also, zeolite materials are particularly useful since they have very low sulfur content. Useful. In particular, varying amounts of alkaline earth metal substances, especially calcium compounds or or a combination of calcium and magnesium within the following composition range, i.e. weight percent. The percentages expressed in cents are about 60% to about 78% silica and about 6% alumina. from about 30% to about 30%, about 1 to about 3% Fe2O3, about 0.01 to about 15% calcia %, magnesia about 0% to about 5%, botasea about 1% to about 2%, soda about 1% % to about 2% of zeolite to form a very useful glass body. can be formed.

Many other compounds, although in very small quantities, are present in zeolites, as found in most minerals. Can exist in light. Other compounds are present in amounts less than 1% by weight and usually Present in an amount less than 0.1% by weight. Such substances include vanadium, titanium Compounds such as aluminum, copper, zinc, tungsten, zirconia, etc.

Naturally occurring zeolites have various ratios of components within the above composition range. Approximately 1 :2.0 ratio is observed in analcyme, laumontite, phillipsite, etc. Many naturally occurring zeolites have a ratio of about 1=5 alumina to silica. has a ratio. These high alumina zeolas in raw glass forming batches The use of alumina materials, if desired, may include materials having an alumina content of greater than about 20%. Manufacturing of laths is permitted.

In particular, from 40% to about 70% by weight mixed with zeolite, and especially about The addition of calcium carbonate, from 40% to about 60% by weight, After melting the material, a glass is produced which has excellent resistance to alkaline environments. Sara These glasses are advantageously melted at temperatures from about 1250c to about 1500tZ'. do. In addition, zeolite can be mixed with dolomite (dolomite) with a similar weight percentage. ), i.e. about 40% to 70% by weight of dolomite. The resulting glass has properties comparable to those formed by the addition of calcium carbonate. This results in a glass having a Although carbonates are the preferred reactants, alkaline earths Other salts or compounds of similar metals, especially calcium and magnesium, may be utilized. It would also be possible.

Glass-forming compositions are made by combining finely ground limestone with finely ground limestone, such as the composition shown above. It can be easily formed by mixing with a zeolite material. Zeo Light substances are crystalline substances that have been pre-reacted, mostly alkyl silicate. Minium calcium, so it can be easily and effectively mixed with limestone calcium carbonate. Reacts to form a glass composition with high calcia loading . Approximately 10,000% by weight equal to the total weight of zeolite and calcium carbonate Calcia content of 40% to 50% calcium carbonate is 60% to 70% by weight It tends to give a slightly lower melting point than amounts containing % calcium carbonate.

Upon cooling, the glass material has a strength substantially equal to that of typical soda-lime silicate glass. degree and other qualities and about 10 times that of typical soda lime silicate window glass. It exhibits good physical properties with a to 20 times better alkaline solution resistance. Also, The lucia content increases from about 40% to about 50% by weight of calcium carbonate in the mixture. Resistance to alkaline corrosion tends to increase as the size increases and further 7 Glasses with 40% amount tend to decrease slightly with 0% amount of calcium carbonate contributes to less tolerance to dilute caustic soda.

In addition to increasing the durability of the glass in alkaline environments, the high calcia content Glasses also have other advantages. Calcia addition reduces fluctuations in the zeolite composition. It tends to stabilize.

Zeolites are naturally occurring substances and are homogeneous or uniform in their composition. Not one. Zeolites also contain iron, which tends to give the glass a brown color. Ru. On the other hand, calcia is a brighter material that is preferable to brown-tinted glass for many purposes. It tends to give a bright green color.

Zeolites contain relatively substantial amounts of water, or hydrated substances. water Hydrated crystalline materials have a general tendency to melt at lower temperatures than non-hydrated materials. However, Therefore, rather than starting the glass-forming operation with silica, it is possible to There are further advantages to starting with reacted zeolites.

The melting range of the calcia-modified aluminum silicate glass of the present invention is range that allows the drawing of glass fibers through a mold, i.e. approximately 12507? do not have It falls within the range of about 1.5000. Glass fibers can also be produced by spinning or other techniques. can be formed. However, the formation of continuous strands is difficult with platinum or white metal. This is best accomplished by drawing molten glass through an opening in a gold-rhodium body. It will be done.

Fibers as continuous strands or mats of the glass composition of the invention but substances that are highly alkaline in nature, such as cement and plaster. It is particularly useful because it can be used to strengthen Such fibers are also available in various types. It can be used to strengthen the organic matrix of plastics. However, that Reinforcement of cement with fibers such as asbestos has until now been used for that purpose. This provides a particularly advantageous application as it has often been used in various health and or) The use of asbestos is being discontinued due to environmental concerns.

Example I Naturally occurring zeolite is finely ground and mixed with granulated limestone or dolomite. It was then melted to form a glass body and fibers. Zeolite composition and added Temperatures of about 1250C to about 1500C depending on the amount of limestone or tomite The melting was carried out batchwise in small crucibles at 30°C. (some typical limestone and Dolomite-modified zeolite glass compositions are shown in Table I. Naturally occurring zeolites contain up to about 20 percent volatile matter by weight, e.g. For example, they contain calcium or magnesium compounds, although they contain water. easily into a homogeneous mass in the presence of 12 13 Singular 1159-501824 (5) Table ■ glass composition 5in261.48 72.0 61.0A120310.20 1.3 1. 5Fe2033.00 - - CaO16,658,23,O Nα20 2.14 14.3 16.5Zr O221,0 Table ■ glass properties Zeolite glass window glass commercially available Properties (no calcia added) AR glass density d, (,!i’/cc) 2.57 2.50 2.74 Thermal properties (Tension coefficient/?T) 70X10-790 cutting 0-780×10-7 quenching Tg (01014 poise 592 530 692 strain T, (010・722　536　755 Littleton softening TS (smell 107.6 poise 934 712 - T(C) 103 poise 130 0 1200 1500 Chemical durability (weight loss) 5%N (ZOH9CC, 72R between 5,1 41.9 5.4H200,93, 00B 5chi HC15, 83, 93, 1 mechanical nature Glass Knoop hardness (kg Ann”) 471 575 - Fiber (20 microns) Tensile strength p, 9z) 145 mowing 0150 mowing 03175×103 Young modular <psi) 5. lX10 7.5X106 7.7X106 Calcia and (or) magnesia-modified naturally occurring zeolite glasses, especially Compounded chemical resistant AR-glass, two factors better than window glass It shows good alkali resistance with a factor of 20 (see Table ■). These modified enzymes Moisture resistance of olite glass is equal to AR-glass and much more than window glass. it was good.

Modified zeolite glasses are more resistant to acidic environments than window glass or AR glass. Inexpensive, easily melted and formed glasses with low resistance There are many alkaline environments that cannot be tolerated. For example, cement and plaster It is not possible to be reinforced using cheap fiberglass materials and on the other hand Zirco Glasses such as near-containing AR-glass cannot be used in such inexpensive objects. Too expensive.

Glass composition of calcia or calcia magnesia modified naturally occurring zeolites The relationships between objects are illustrated in FIG. by alkaline medium, i.e. 5% NaOH solution. The susceptibility to corrosion is determined by adding about 40% to 60% by weight calcium carbonate to the glass batch. As the weight loss of glass with calcia content determined by the addition of Si expressed.

Figure 2 is a graph showing the relationship between the viscosity of calcia-modified zeolite compared to window glass. For example: Calcia modified zeolite has a steep curve, which is It exhibits a higher temperature performance range that is better than window glass even if the melting temperature is similar. temperature unit is the degree of Celsius.

Example■ Is the glass fiber a molten glass formed from calsilyl carbonate or modified naturally occurring zeolite? It passes through the platinum bushing at a temperature of about 1300C (bu, shing). and was continuously stretched.

The continuous fibers had properties comparable to fibers of similar composition described in Example 2.

Glass sets containing such large amounts of calcia or calcia and magnesia such that the composition is fiber-forming and has a tensile strength comparable to commercially available window glass. It is significant to have good mechanical properties. These modified zeolite glasses The species is relatively low in iron content and has a non-offensive bright green color.

Remarkable resistance to alkaline environments makes these especially in fiber or flake form glass to concrete, plaster and other inorganic matrices of alkaline nature makes it an excellent reinforcing material for Reinforcing materials in cement and concrete bodies Asbestos was the standard spreading agent due to the possible presence of health hazards. The foregoing is significant in that it is considered undesirable.

The glasses of the invention have excellent resistance to moisture deterioration and does not deteriorate or deteriorate in quality during storage.

The low sulfate content of naturally occurring zeolites is an ingredient in glass-forming processes. Temperatures are important for their use as temperatures.

Sulfates produce sulfur dioxide and other undesirable sulfur compounds during the glass melt state. It has a tendency to deteriorate. Environmental concerns include sulfates, sulfites and other sulfur compounds This restricts the use of any raw material in the glass manufacturing process.

Although the present invention was described as having a large amount of calcia, instead of calcia It has been observed that at least a small amount of substitution of other alkaline earth metal oxides Should be. For example, magnesium compounds, especially magnesium carbonate, are In batch production for bath melting into potash glass, Can be substituted in place of um. Similarly, barium, strontium and and beryllium compounds, and many of these It is a naturally occurring substance found in the same geographic region as light.

Oxides of alkaline earth metal elements include elements having a valence of 3 or more, such as silicon, Boron and phosphorus (these include their oxides, i.e. silica, boron oxide and phosphorus) A term applied to various oxides that can form three-dimensional network structures. It is not considered a glass forming agent. The divalent alkaline earth metal element is alkali gold It is more tightly bound in glass than other elements.

The sources of alkaline earth metals for forming oxides in the glasses of the present invention are: As stated: Alkaline earth metal compound source Calcium carbonate lime ash Magnesium carbonate 80 mites Magnesium silicate serpentine Strontium carbonate Strontianite calcium carbonate and magnesium carbonate Sources of barium, strontium, or It's more plentiful and cheaper. Also, beryllium oxide combined within the glass body Although objects are not harmful, metals are considered to be poisonous.

The zeolite-derived glasses of the present invention have not only outstanding alkali resistance but also good processability and It is worth noting that it has excellent strength and strength. These glasses can be of any shape, e.g. containers , in the form of sheets, fibers etc. and especially for any application where transparency or colorlessness is not required. can be used for. Glasses are organic or inorganic matrices, especially Flakes, foams (microspheres), fibers, etc. to reinforce cement, silastar, etc. It can be used as

Although zeolites can be present in varying amounts in glass-forming batches, zeolites are generally Wright provides an important portion of glass-forming materials such as silica and alumina . Preferably, the major amount of glass forming agent present is provided by the zeolitic material. Yes.

Other glass forming agents, fluxes and typical additives to glass forming compositions include: , which may be included in the batch, although it may somewhat affect the properties of the resulting glass. You can also let For example, an additional 7 liters, such as soda or bottasia, in the batch. Tuxus may tend to lower the melting temperature of the bath, but it also affects the alkali resistance of the glass produced. It may decrease somewhat. The presence of very small amounts of other substances affects the properties of the resulting glass. It will generally not change quality significantly.

Of course, batch formulations with optimal amounts of silica, alumina and alkaline earth metal compounds can be used. It is within the scope of this invention to mix zeolites from various sources to obtain be.

OIQ 20 30 40 50 60 70 → xCaω3<v-’gy,> C'aCO3ozuit: 4=-r, urrr,, kaIll, etc [-5 excellent Friend σqi1

Claims (1)

[Claims] 1 Naturally occurring alkaline mixed with a significant amount of alkaline earth metal-containing substances Contains moisture-reacted zeolite, high alkali resistance when formed into a glass body A glass-forming composition comprising: 2. the zeolite is present as from about 40% to about 70% by weight; Claims wherein the alkaline earth metal-containing material is present from about 60% to about 30% by weight The glass-forming composition of Box 1. 3. The method according to claim 1, wherein the alkaline earth metal-containing substance contains calcium carbonate. Glass forming composition. 4. The alkaline earth metal-containing substance contains a substantial amount of at least one magnesium 2. The glass-forming composition according to claim 1, comprising a rubber compound. 5. The method according to claim 3, wherein the calcium carbonate-containing material is provided as dolomite. Glass forming composition. 6. At least a portion of the calcium carbonate contains magnesium, barium, and strontide. The gas of claim 3 can be replaced by a compound of um or beryllium. A composition for forming lath. 7. A sufficient amount of alkaline earth metal compound at a temperature of about 1250C to about 1400C A glass body is created by melting naturally occurring pre-reacted zeolites in the presence of A method of forming an alkali-resistant glass body comprising forming. 8. The weight of the obtained glass body is about 20, calculated as alkaline earth metal oxide. % to about 60% by weight of alkaline earth metal oxides. pre-reacted zeolite and at least one added alkaline earth Glass containing similar metal components and having high alkali resistance when formed into a glass body Forming composition. 9. Claim 8, wherein the added alkaline earth metal component is a calcium component. Composition of. 10. The obtained glass body contains about 30% to about 60% by weight of silica and about 9. The composition of claim 8 containing from 2% to about 20% alumina by weight. 11. The obtained glass body contains about 30% to about 60% by weight of silica and about 10. The composition of claim 9 containing about 20% alumina by weight. 12. The amount of calcia plus magnesia is about 30% to about 60% by weight. Under these conditions, the glass body thus obtained has a content of about 20% by weight (and about 60% by weight). Claim 1 containing lucia and about 0% to about 30% by weight magnesia. Composition of 0. 13 The amount of calcia plus magnesia is about 30% by weight to about 60% by weight wherein the glass composition contains about 20% to about 60% by weight of calcia. and the set of claim 11 containing from about O to about 30 by weight magnesia. A product. 14. The glass composition contains about 27% to about 60% by weight of calcia. The composition of claim 8. 15. The glass composition comprises about 30% to about 60% by weight silica and about 13% by weight silica. Contains 1 to about 20% by weight of alumina2. The composition of claim 14. 16. The glass composition contains about 27% to about 35% by weight of calcia. The composition of claim 15. 17. The glass composition contains about 40% to about 60% of the zeolite and from about 60% to about 30% by weight calculated as potassium earth metal oxide; 9. The composition of claim 8 containing an added alkaline earth metal component. 18. The set of claim 9, wherein said calcium component consists essentially of calcium carbonate. A product. 19. The added alkaline earth metal component is a calcium component and a magnesium component. 9. The composition of claim 8, comprising a mixture with minutes. 20. The composition according to claim 8, wherein the alkaline earth metal component is dolomite.