Alkali resistant glass compositions

Detailed description of preferred embodiments

[0029] the description of the improvement of the disclosed glass compositions and products, they have excellent alkali resistance performance, even at high temperature, and they are made of inexpensive material. Described herein are the characteristics of the glass articles can be integrated in the composite material, which comprises an organic polymer matrix or inorganic binder matrix, or integrated into the can expect to obtain the advantages described in the other medium. The disclosed glass articles may be formed in a fiber, particulate, composite aggregate, solid or hollow micro-ball, (micro   balloons). object or any other is believed to be able to meet the structure of the special purposes. The composition disclosed herein can also be used as filling material, in order to improve the ceramic matrix composites, metal matrix composites, polymer composite, or clay-based cement compound of alkali resistance of the complex. Therefore, the discussions below of the particular glass articles such as fiber or ball application, or as a glass-based composites or glass component in the alloy, is merely exemplary, and should not be interpreted as limiting. Furthermore, in the specification of the below based on inorganic substrate examples include other matrix material, such as cement binder, geopolymerisation (geopolymer), metal and clay product. The term cement suitable for all types of cement, Portland cement, including but not limited to, lime cement, aluminum cement, cement (  cement sorel) rope auspicious ear , pozzolan cement, geopolymerisation cement (geopolymeric cement), gypsum, cement (cement   pastes), dry cement mixture and other hydraulic-curable adhesive.

[0030] according to the embodiment as disclosed herein, can be made into a glass composition containing a high concentration of alkaline earth metal oxide and iron oxide, while at the same time maintaining low concentration of the alkali metal oxide. These types of compositions has been discovered that, under high heat conditions and water pH can demonstrate the unusually good performance.

[0031] it has been recognized that, silicate glass in water environment the chemical durability depends strongly on their composition. Of special interest is the role of certain oxides, such as Al₂ O₃, with negative charge forming the same the tetrahedrom [AlO₄]^- group, which is alkali metal ions of the positive charge on the balance. Therefore, in the presence of these oxides, alkaline ion can be combined in the glass will not reduce its durability. This explains in durability in production of glass B₂ O₃ and Al₂ O₃ role. Other oxides, such as ZrO₂ and TiO₂, can be a one-to-one of the glass network to replace SiO₂. However, by this mechanism, the glass component of the impact of the overall corrosion resistance depends on the content of other components. For example, in the absence of relative to B₂ O₃ and Al₂ O₃ excess of the alkaline oxide under the condition of, the two kind of oxide is shown as the steel is not or octahedral and tetrahedral coordination structure, and they also no longer play a role in the improvement of the durability.

[0032] alkali metal ion with an aluminum-silicate network dynamic balance can be by consideration of the albite crystal (NaAlSi₃ O₈) and understood. Albite is open aluminosilicate network, wherein the Si and Al is oxygen quadrivalence coordination, are connected to each other according to the three-dimensional formed on the arrangement of the cage of the tetrahedrons. In the all of the oxygen atoms in the crystal structure or Si between the cationic Al by a covalent bond to form a "bridge". With negative the [AlO₄]^- group charge compensating ions through Na+, Na⁺ ion is located at the position of the oxygen-rich. Similar characteristics can be expected in the aluminosilicate glass.

[0033] of the containing parts Al₂ O₃ and Na₂ O the glass in, Na⁺ cation can be described as filling the complete polymerization of the oxygen-rich in the network before the cavity, therefore, with the negative of the ties the jail [AlO₄]^- group. In this case, the sodium ion and between oxygen form a ionic bond, thus reducing the degree of opening of the glass network, aluminum as in the glass network.

[0034] in the other extreme case, in the binary glass, Na⁺ cationic through non-bridge bond oxygen (NBO ' s) bound to the silicate network, the network of the glass, the chemical durability is not particularly desired.

[0035] in about 12.5-14 within the range of the pH, this is a large number of hydrated cement in an aqueous medium in the desired pH range found, most of the many glass is not durable and will is dissolved. More specifically, under the high pH, silicon dioxide is converted to a silicic acid, alumina and aluminum hydroxide formed by the reaction. Therefore, alumina will not be as in neutral or weakly alkaline environment with the durability of the glass, the beneficial effects of the same.

[0036] it is expected that many other common glass components, such as ZnO, SnO₂, PbO, P₂ O₅, GeO₂ and other known glass ingredient has similar behavior. Therefore, glass manufacturers has been that in the past, glass cement composite material requires relatively high concentration of typical difficult fusibility oxide, for example silicon dioxide, zirconium dioxide, titanium dioxide and alumina, and low concentrations of alkali metal oxide in order to improve their durability. Increased difficult fusibility oxide provides many ordinary glass component in the alkaline resistance is not, however, because high-concentration difficult fusibility oxide, most of these types of alkali resistant glass relatively expensive, and when the cost compared with fiber reinforced the obtained high tensile strength variable not so important, their application has been limited to a specific application.

[0037] it has been found that, although the anionic under the dissociation of high pH, many oxide to become more soluble, however, with the increasingly high pH, alkaline earth metal and lanthanide series metal become more soluble. In fact, testing has shown that, the value of the pH is about 11.5, 12.5, 13.5 and 14.5 time, to achieve the maximum solubility of calcium 1, 10^-2, 10^-4 and 10^-6 m.

[0038] therefore, a preferred embodiment of the invention comprises in the conventional glass making are usually not in the calcium content can be seen, in some embodiments, the content of calcium in about 1-25 wt. %, More preferably in 5-20wt. %, Even more preferably 10-15wt. %.

[0039] interestingly, the exudation in the alkaline environment (leach   testing) test shows that, by adding the fuel composition to be offset by the other material of the benefits of high calcium content. For example, testing has shown that, a high level of alkali metal, such as more than 10 wt. The % Na₂ O or K₂ O or a combination thereof, the durability of the glass composition to have a harmful effect, even in the presence of relatively high levels of calcium circumstances. Therefore, the inventor believes that, separate a high concentration of calcium will not be able to provide the desired durability glass, but there are other element, with the increase of the calcium content of the interaction, in order to provide the desired durability glass performance, in some preferred embodiments, CaO/Na₂ O is of the opinion that the molar ratio of alkali resistance is important. In some preferred embodiment, CaO/Na₂ O typically the molar ratio of greater than 1, in some embodiments, the 2, 3, 4, 5, 10, 15, 20, 25, 30 or more.

Calcium in the present invention is illustrative of the use of, bound not wishing to be bound by theory, the inventor believes that other material can replace calcium and is applied, in order to produce the desired alkali-resistant performance. In some of these other materials, including, but not limited to, MgO and ZnO.

[0041] in addition, has been unexpectedly found, exudation test shows that, in addition to the presence of Si and Al, the leaching rate stability of (leach   rate) another important factor appears to be iron oxide. Statistical analysis shows that, with the leaching rate Fe₂ O₃ in the increase of the content of, Fe₂ O₃ increasing until approximately 15 wt. %. Statistical data shows that drawing, exudation curve at approximately 0 wt. % And 1 wt. %Fe rapid decline in between, and in approximately 15 wt. After %Fe gradually becomes gentle. Therefore, do not wish to be bound by this theory, that can be up to approximately 15 wt. % Iron oxide, typically Fe₂ O₃ forms, and the description of the content of calcium and CaO/Na₂ O molar ratio together, provides improved resistance to alkaline. The preferred embodiment comprises about 1-15wt. The % Fe₂ O₃, more preferably, at about 5-12wt. %, More preferably, at about 7-10wt. %.

[0042] Figure 1A according to the present invention describes several preferred embodiment of the preferred composition range of the ternary phase diagram illustrative of, but should never be interpreted as a limitation of the scope of the present invention. Figure 1A according to the special set forth in the preferred embodiment of the present invention containing no zirconium dioxide or titanium dioxide composition three Yuan glass within the context of the Figure.

[0043] Figure 1B depicts including up to a total of 15 wt. % Of zirconium dioxide and titanium dioxide another preferred composition range of another exemplary ternary phase diagram. In this case, 85 in the Figure 1B with the display in the material of the 15 parts of zirconium dioxide or titanium dioxide are combined, in order to produce with a preferred embodiment of the present invention of the glass formulation.

Then as containing the test data of the displayed in the form of, has been unexpectedly found that, a higher concentration of iron oxide and calcium oxide combination, than separate difficult fusibility oxide can be more effectively resist serious corrosion in the alkaline water environment. For cement composite those found in the high-temperature water of alkali in the course of the reaction is more specific, in the typical curing temperature in the process is about 180 the [...] , sustained approximately 5-10 a period of time of hours.

Disclosed herein the many embodiments, whether to fiber, in the form of ball or other inclusions, the composition of the have such, it contains relatively low alkali metal oxide, less than about 10%, but rich in iron and calcium oxide, Fe₂ O₃ +CaO in about 2-40wt. The range of %. Optionally, ZrO₂ and TiO₂ in may be added to the glass composition, in order to further improve in the strongly alkaline environment of the alkaline resistance. Furthermore, other oxides, such as P₂ O₅ and ZnO, can also contribute to further improve the glass article in the high pH environment alkaline resistance.

[0046] has been unexpectedly found that, on the exposed glass of the crystalline layer ("passivation layer") can be through the glass in the strong alkaline solution through water heat-condition processing in the present invention certain inherent in the composite cladding formed on glass composition. In saturated calcium hydroxide in the alkaline solution, in about 12-14 pH value of, approximately 180 the [...] , to carry on heat treatment of water glass article, the outer surface of the glass article forming a passivation layer. Figure 2B display the passivation layer. In several preferred embodiments, wherein the glass article is a hollow ball, the thickness of the passivation layer is preferably less than the thickness of the furnace. In some embodiments, the thickness of the passivation layer of the ball wall thickness of less than about 10%, even more preferably, the thickness of the passivation layer of the ball wall thickness of less than about 5%, in some embodiments, hollow ball wall thickness of less than about 2%.

[0047] it is extremely important that the passivation layer is produced, because it shows that, disclosed herein are the preferred alkali-resistant glass formulation for the cement compound or inorganic polymeric compound is particularly advantageous. Because cement compound or inorganic polymeric compound generally require curing, such as hydration or high pressure autoclave of the steps in the process of manufacturing, the passivation layer will be the glass component in the composite on the surface of and integrally formed at the same time. Glass compositions containing passivation layer, for example, reinforcing fibers or micro-ball, will lead to the ratio of the alkali resistance of the other traditional may have the better the durability of the composite. Therefore, this invention is a particularly preferred embodiment is cement, ceramic or inorganic polymeric compound material, which contains a alkaline-resistant as disclosed herein is made of the contents of the glass formulation, wherein the contained object is provided with a passivation layer, the passivation layer is in the composite materials formed in-situ in the process of manufacturing.

[0048] it has been found that the, includes a relatively high concentration of the oxide iron and calcium , in water to form the passivation layer in the heat treatment process. To rich in iron and calcium oxide in the glass composition by adding a small percentage of zirconium dioxide, the formation of the passivation layer to further promote and improve the impermeability of the passivation layer. Subsequently the energy disperse X-ray (EDX) analysis of the inspection that the passivation layer, iron and calcium oxide is enriched, alkali metal oxide is the consumption is reduced.

[0049] through experiment and testing, the inventor has already know, ZAR glass exposed on the market for cement environment, and to the increase of the content of calcium and zirconium of silicon dioxide and the reduction of the alkali metal content, but will not lead to the compositions of the present invention is similar to the formation of the passivation layer.

[0050] in the present invention the round glass composition of the glass bead is formed on the passivation layer of the checks indicate EDX, without the added zirconium is formed on the passivation layer of the glass article rich in iron and calcium oxide and containing low content of alkali metal oxide. Added to the parent glass 1-6 wt. % Passivating layer formed by zirconium rich in iron and calcium oxide, but this is not the case for the zirconium dioxide. The passivation layer from contain saturated solution of calcium hydroxide in the cement around the absorption of calcium. Zirconium dioxide in the formation of the passivation layer not play a major role, it is only the inherent solubility of silicon dioxide is reduced.

[0051] based on extensive corrosion test, the inventor found that, according to embodiments of the present invention glass with the best commercial glass of good and sometimes better corrosion resistance, the commercial glass contains very high zirconium dioxide content, or even contain up to 15 wt. More zirconium dioxide and %. Commercialization of zirconium dioxide glass electronic photomicrograph shows that, when passing the same water is not formed when the heat condition of the glass of the present invention is similar to the passivation layer.

[0052] in the passivation layer of the service life of the cement products, the provision of the protective function of preventing the alkali corrosion. Through the first will contain a different number of iron and calcium oxide two kinds of glass through the same heat treatment of water to form a passivation layer, the discovery confirmed. Two sample, glass and glass A B, is comparing the alkali-resistant. Glass A is based on preparation of the composition of the present invention, glass B bead is obtained by the coal ash (cenosphere), its regular is used as the cement system durability of the glass. There are two times of the glass containing A B and iron oxide of the glass to glass B nine times of calcium oxide. However, the glass-containing glass B A almost 1.5 times that of the alumina.

[0053] glass sample through heat treatment of water, and then in 5 molar concentration of the solution of sodium hydroxide in the 90 under [...] standard accelerating corrosion test. Although ASTM   C   1203-91 test standard use 10% aqueous sodium hydroxide solution to test the resistance of alkaline, however, because the test glass strong durability, select a more strong alkaline solution to accelerate the test. The 20% of sodium hydroxide solution (5 molar concentration) to accelerate the corrosion test.

[0054] 8 hours after testing, the commercially available glass B, as a result of corrosion lead to material losses is almost two times. A test under the same conditions after a week, the material losses glass B A is almost three times that of the glass. These findings indicate that, two times due to the presence of iron and calcium oxide and of forming the passivation layer with high aluminum content than the microbead glass composition.

[0055] Figure 2A and 2B is superbead (cenosphere) and glass article according to the present invention the mode of execution of the hydrothermal conditions for two of the processing after scanning electron photomicrograph (SEM photomicrograph). As see, according to the present invention the generated map 2B and 2C in the glass article, indicates that form the passivation layer. Think, the formation of the passivation layer greatly improves the natural glass in the strongly alkaline environment the capacity of the lower resistant to corrosion attack.

[0056] subsequent testing and SEM and EDS analysis has shown that, when passing the same condition, the commercially available superbead and other alkali-resistant glass did not form this type of passivation layer. -do not wish to bound by theory, the inventor believes that, from the glass passivation layer is in the formulation of the material formed from, then re-deposition onto the surface. This is confirmed by the experiment from, wherein SiO₂ and Al₂ O₃ exudation of sharp decline over time, indicate that these substances in fact re-deposition onto the article surface, such as in the following table 1 is shown.

Table 1 of the invention in different from the wt in the glass composition. %

[0057] if the above table 1 is shown, although Na₂ O from exudation of 5h to 19h on the increase, SiO₂ and Al₂ O₃ sharp decline in exudation of, this shows that the two component re-deposited onto the surface of the glass article. Therefore, as desired, a passivation layer rich in Si and Al chemical formula. Furthermore, the passivation layer further comprises mg, and Fe Ca, as confirmed by the EDS analysis. Interestingly, when using this invention describes the glass composition, the addition of the zirconium dioxide and at no substantial impact on the formation of the passivation layer, but improves the quality and uniformity of the passivation layer.

The 20 wt. % Hydroxide in the 95 under [...] that accelerated corrosion tests, provided by the present invention the glass formulation prepared containing passivation layer of the ball, been proved to have stronger alkali-resistant characteristic, as shown in the embodiment of the.

[0059] in the test of the, order to measure the glass composition described herein and made of glass articles of several kinds of commercial alkaline-resistant alkaline resistance of the glass. The total proportion of the dissolved glass (fraction) within the pressurized container is the 180 in its [...] for pH containing saturated calcium hydroxide and lithium hydroxide to regulate the synthesis of assessed in solution. In this kind of environment similar to the high-pressure autoclave of hydration of the cement mixture found in the aqueous environment. However, the use of lithium hydroxide and is not an ordinary cement, sodium hydroxide or potassium hydroxide, this is to the inductively coupled plasma mass spectrometer (inductively   coupled   plasma   spectroscopy, ICP) the measured background concentration is minimized. Due to such substitution, the derived exudates sodium and potassium concentration accurately be measured.

Experimental data

Embodiment the A and B, and commercial grade hollow superbead (cenosphere) products and several kinds of commercially available compared with of microspheres, prepared according to the method described herein of the leaching rate of particles.

A embodiment

[0061] for alkaline aqueous solution is 2.343 g/l of LiOH and 0.080 g/l the Ca (OH)₂ of preparing, in about pH 13.0. Including commercial test material the temperature of the hollow microsphere can be obtained (in the 4   Comers   power   plant production, sale   Cement by Phoenix), the commercialization of natroncalk micro-ball (by Spherical   Industrial   Solutions, with tradenames SISCOR Toronto-Canada sales) and according to one embodiment of the invention synthetic production of the spherical particle, it is referred to as sample X. The alkali solution is heated to the 180 [...] , the test material in the solution for 5 hours. For all of the three kinds of material, in the 15 ml solution to the solid content of 0.25 g. The test is from 180 the sustained [...] 5 hours of the following. Table 2 summarizes these three kinds of test sample the composition of the main oxide.

Table 2

[0062] according to table 2 (upper surface), all three of the specific surface area of the sample is relatively close. Sample X is the present invention in a preferred embodiment. As seen, is different, wherein the sample X containing the highest content of calcium oxide and iron oxide. Furthermore, sample X contains much lower than other sample of the silica content. Though the sample X containing than hollow microsphere samples with high alkali content of, but lower than SISCOR sample.

[0063] table 3 illustrates (in the table below), the ICP determination of exudation of the main oxide related percentage and exposed surface area and time of the leaching rate of associated normalized.

Table 3

[0064] according to the above table 3, it is clear that, the smallest sample X presenting an exudation amount of, the hollow beads and then sequentially SISCOR. Leaching rate and composition directly related to performance of the alkali-resistant. Because low exudation, prepared according to the composition of the sample X should be provided the particles than the other two commercial available alkali-resistant glass of any kind of cement hydration of resistance is found in the capacity of the alkaline environment.

B embodiment

[0065] in the following embodiment, the commercialization of testing the product, including 3M-S32: SCOTCHLITE, Minnesota by 3M   Corp. Manufacturing; PORAVER, of Toronto, Canada   Industrial the manufacturing   Solution Spherical; SPHERIGLASS, the PQ   Corp by the United States. Manufacturing; and SIL-CELL ,   Corp the Silbrico by the United States. Manufacturing. Table 4 lists the B in the embodiment containing product of the main oxide.

Table 4

[0066] in the following table 5 are shown in the table 4 sample listed in under the conditions described in front of 5h from the exudation data obtained:

Table 5

[0067] from the above table 5 can be seen, separate high silicon dioxide content of the material (SIL-CELL) and the material of high-silica and calcium oxide (3M-S32) strongly hydrated cement such as the high pressure autoclave of the environment experienced by the impact of the aqueous alkaline solution, thus further support the conclusions: separate CaO can not provide acceptable alkali-resistant. Similarly, SPHERIGLASS PORAVER and, although they have a medium amount of CaO, are easy to both the alkaline aqueous solution in the high temperature environment is subjected to etching, this also enhances the view of the inventors, i.e., CaO to meet the need of other ingredients in order to provide the desired alkali-resistant.

C embodiment

[0068] test C for example, to quantify to the invention in the mode of execution of the impact of a small amount of zirconium dioxide, in order to confirm the improved alkali-resistant. In the following embodiment, sample 1A, 1B, and 1C 1D according to the present invention is the implementation of the preparation. Of these alkali resistant glass using the sample is by the fly ash, sodium hydroxide, zirconium silicate and sugar of the formulation consisting of. Sample is through according to table 6 in the display of mixed formulation of these ingredients.

Table 6. The formulation of sample

[0069] sample 2A containing nominal content is 0% zirconium dioxide commercially available alkali resistant glass sample. Sample 2B containing nominal content is 15% zirconium dioxide commercially available alkali resistant glass sample. Sample 2C containing nominal content is 16% zirconium dioxide commercially available alkali resistant glass sample. Sample 2D containing nominal content is 17% zirconium dioxide commercially available alkali resistant glass sample. These compositions are listed in the following table 6 in.

[0070] the sample 1A, 1B, and 1C 1D each slurry into homogeneous, in into a flat disc, the cured at room temperature for about 5 minutes. The obtained product in about 50 degree c further drying about 20 hours, then it is grinding and screening in order to get the size in a range of 106 the to   m 180 the powder   m. In a next step, powder in 0.14g/min feed rate of the feed to about 1200-1400 the vertical heating tube type furnace [...]. The obtained particle is collected on the funnel shaped collecting device, the device is covered with a thin wire mesh screen at the bottom of the of the furnace. Application of mild at the tail end of the funnel in order to help collect particles of the air pump. Check using the microscope, observation of the shapes and forms of the product, in order to ensure that is completely melted, then, each sample is exposed to through the improved laurance solution (  Lawrence   Solution Modified), in the 180 and the [...] 135 under the pressure of   psi 5 hours, to evaluation of alkali resistance.

[0071] the composition of each sample, and bleed data are listed in the following table 7.

Table 7

[0072] as can be seen, according to the invention is sample 1A, 1B, and 1C 1D have very considerable leaching rate, the addition of a small amount of zirconium dioxide only slightly improved their alkaline resistance. Furthermore, though the sample 2B, 2C and 2D leaching rate of showing a more low, but they contain very high amount of zirconium dioxide, and therefore the material cost and the required molten energy, many expensive production cost. Sample 2A, a non-ZR commercial available alkali-resistant glass, and the prepared according to the present invention compared with the sample of the, display on the alkaline resistance.

Is although the embodiment of the inventive concept herein is the definition of restrictive, they do pointed out that a number of interesting trends. On the basis of a hundred test and the test result of the widespread use of statistical analysis, it has been found that the, there is a class of non-zirconium dioxide glass, they provide exceptional alkali-resistant characteristics, can be made of cheap material. Think, these non-zirconium dioxide glass demonstrate their alkali resistance characteristic, this is because the increasing amount of CaO and the interaction between the Fe, and contains relatively low R₂ O (wherein R₂ O is composed of basically K₂ O, Na₂ O and Li₂ O composition). In particular, the inventor considers that, as the increased CaO/R₂ O molar ratio, Fe concentration and in some embodiments Zr and/or Ti is added to the glass composition, under the environment of high pH alkaline resistance can be improved. In some embodiments, CaO/R₂ O molar ratio of greater than 1. In other preferred embodiments, the molar ratio can be greater than 2 or 3, or higher. For example, testing and analysis has been determined, the desired alkali-resistant glass can be economically manufactured according to the following composition:

> 35% SiO₂

1-25% CaO

1-15% Fe₂ O₃

1-10% R₂ O, and

A certain number of Al₂ O₃, the SiO₂: Al₂ O₃> 1.

[0074] alternatively, can be added can be as high as approximately 10 wt. %, Or even up to about 15 wt. The % ZrO₂ +TiO₂ described in order to further improve the alkali resistance of the glass. Figure 1A and 1B provides a display of the exemplary composition range of a ternary phase diagram, its respectively comprises 0 wt. % And 15 wt. The % ZrO₂ +TiO₂. Prepared by the description of the composition of the cement is particularly suitable to be applied to the glass article, wherein the cement products in the high-temperature water to heat conditions (for example, 100 the above [...]) curing, such as experienced in an autoclave. As discussed above, with the described by forming the composition of the glass and of the glass article in accordance with the described processing, the glass can be forming a passivation layer on an outer surface of the article, thus further increasing their alkaline resistance.

[0075] although the preceding description and according to embodiments of the present invention limits the production of the sample containing ZrO₂ and TiO₂, but believes that medium number of these ingredients, for example, can be up to approximately 15 wt. The combination of %, will be able to further increase the alkali resistance of the sample, and, therefore, some embodiments of the invention include can be up to approximately 15 wt. %, More preferably can be up to approximately 10 wt. The % ZrO₂, TiO₂ or their combination.

[0076] although the inventor has already identify high-temperature heat treatment of water result in unique described in this invention is forming a passivation layer on the glass article, however the inventor further believes that in the low-temperature water of the passivation layer can also be formed under thermal conditions. The passivation layer is considered to be from the glass substrate by the components of the re-deposition is formed, high-temperature water in the lower heat condition is accelerated. However, if given sufficient time, the low temperature (for example, less than approximately 100 the [...]) of the alkaline solution is that it is also able to produce similar results. In particular, in the 35 [...] and 95 the temperature of [...] , in using 2.343 g/l of LiOH and 0.080 g/l the Ca (OH)₂ made of is about pH 13.0 alkaline aqueous solution in the test had been carried out. Inventor has already found that, even in the 35 [...] , passivation layer begins to form, and if given sufficient time, substantially continuous passivation layer that will be formed, and the surface of the coated glass article. In fact, test display, if in about 95 the time adequate [...] , the continuous passivation layer is formed on the surface of the glass article.

[0077] in addition, inventors believe that, the passivating layer can be formed through other methods, for example by glass material from priority from the surfaces of the articles (preferential   leaching). As an alternative, metal hydroxide or dissolved inorganic compounds such as nitrate, chloride, sulfate, silicate, borate, phosphate and the like, and the glass ingredient can also be the reaction of forming a passivation layer on the glass surface.

[0078] therefore, the general method can be formed by passivation layer ooze out and re-deposition, through the glass material from the, on a priority basis, from the surface of articles, or through contact solution soluble substances in the chemical reaction of the glass.

[0079] although the inventors it has been found that, through the glass passivation layer can be the binding articles formed in situ by cement composite, however, unexpectedly found that, by using appropriate passivating layer can be in the solution treatment in the outside of a cement composite. Therefore, preparation of the glass articles can be after processing to form the passivation layer. In a preferred embodiment, the glass article through water heat treatment conditions to carry out the after-treatment, such as, for example, containing alkaline solution in the pressurized container the 100 [...] and 400 the between [...] for a predetermined period of time. Contains a predetermined number of Ca (OH)₂ alkaline solution can be removed and recycled, for the processing of a new a batch of glass articles, and the glass article itself can utilize the washing, drying and packaging of powder of the traditional technology to washing, drying and packaging.

[0080] the inventor also has been determined, the passivation layer can also be lower than the 100 [...] formed in the temperature of the glass article, this saves on the need of a pressurized container in the process. Forming a glass article, a passivation layer can then be coupled to the needs of the other application in durability. Optionally, coating or other type of surface layer can be increased in order to improve the compatibility of the glass and the material matrix.

[0081] therefore, described herein can be according to the composition of the glass article and method for manufacturing, followed by processing to form a passivation layer, is then integrated into the same in a desired application.

[0082] through the described production method and composition of the glass articles can be taken in the form of many shapes. Although fiber and ball already in front of the main to be used as described in the examples, other shapes are possible, and is considered within the scope of the disclosure. Other shapes can include, but are not limited to, object.; solid or hollow ball; fabric ; and continuous, the short, braided or blown fiber. Glass articles can also be a foamed glass.

[0083] is of special note, the disclosed unique glass formulation of the value of another to produce the structure of the glass sheet (glass   flake). As used herein, unless otherwise specified, a sheet having a width and a substantially uniform thickness of material, wherein the width is substantially greater than the thickness. In many embodiments, the sheet with an irregular shape in a top view.

[0084] sheet can be formed, for example, by forming a thin sheet glass (glass fleet), this piece is then divided into smaller particles. Forming a glass sheet by a method of reverse rotation of the drum is to convey the molten glass substrate. In a preferred embodiment, this has produced glass sheet and the roller spacing corresponding to the final cross-sectional dimension of the sheet, the roller spacing in some cases can be in about 1-3 the level of   m.

[0085] another accepted method is to pass the proper size of molten glass mould is squeezed. Through any one of these methods, the thickness of the glass or pitch of the roller depends on the geometric size of the mould. According to these methods of production of the glass sheet, the thickness of the flake can be an almost unlimited in order to adapt to changes to the final use of the flake. However, most of the use of the flake typically need to be less than about 1000 the thickness of   m. Therefore, has less than about 1000 the thickness of the flake is   m of production, in other embodiments, can produce thickness of less than about 500 the  m, the 250  m, the 100  m, the 50  m, the 20  m, the 10  m, the 5  m, the 2   m and 1 the sheet   m.

Production of the glass flake a method is the other of the molten glass can be sprayed into the air. For example, the molten glass can be through the spraying nozzle of suitable shape, this makes the shape of the spray form an appropriate glass, then the glass is quenching or in other mode is cooling, in order to meet desired shape.

[0087] according to any suitable method for producing the glass sheet can be further through to record any crushed the size of the processing, the techniques such as ball milling, or other is designed to the glass is reduced to the size of the smaller the appropriate process. In one particular embodiment, the production of some slice width 10 the the   m the 10,000  m, in a thickness of about an 1   m to the 10  m.

[0088] production of the glass flake according to another method, the ball is produced, as described elsewhere herein, ball is crushed or in other way in order to form the hemispherical sheet is broken, for example, in Figure 2C those displayed. Of course, semi-spherical sheet will naturally, in one or more directions is bent on; nevertheless, the size of the sheet can form the desired, so that the sheet exhibits a desired function or aesthetics. A flake imitates evenly from Zhang, for example, a glass production of those sheet-method, the width of the flake is the ball diameter is reduced to a relatively small size. As the sheet width of the ball diameter ratio of zero, close to the plane of the sheet.

[0089] in a preferred embodiment, a diameter of approximately 30 the to   m 1000 the ball is broken between   m, formed in approximately the width of the 5   m to 200 the flake size   m. The thickness of the sheet depends on the wall thickness of the ball, in many embodiments, the resulting can be the thickness of the flake is about 0.5 the   m to about 10 the order of magnitude of   m.

[0090] in the relevant manufacturing described in the literature several kinds of methods for sheet glass, any of them is suitable for producing all of the unique material as described herein. However, embodiments disclosed herein relate to the unique glass formula is generated which has until now it was able to achieve the very desirable characteristic of the unique sheet.

[0091] in addition to the outside to change shape, and through the described herein a method for the production of glass can also be with other mineral, clay, polymer, ceramic, metal or glass combine and form the composite material or glass alloy.

[0092] in one embodiment, alkali-resistant glass formulation can be made into fiber form. In some preferred embodiments, alkali-resistant glass fibers are in the form of a continuous strip. In other embodiment, alkali-resistant glass fibers are in the form of chopped fibers. Glass fibers can be prepared by the rotary process, wherein the glass formulation is molten, fall into the "rotator", with numerous holes of the peripheral wall, the role of the glass by the centrifugal force through these holes to form a fiber. In some preferred embodiments, can also be to the preferred alkali-resistant glass formulation by adding additive in the softening temperature of the glass in order to reduce and/or melt temperature, so this makes it more easy to form with a specific shape or form of the glass particles or article.

[0093] in one embodiment, the formulation described can be of the alkaline resistance of the glass article described in the Patent application in the method of preparation by one kind of:25 February 2004 submitted by the applicant, the title of invention is "METHODS   AND FORMULATIONS   PRODUCTS   PRODUCING   DENSITY   LOW   FOR" the, series of number 10/787, 894 common in the United States Patent application, all the same in that introduced as a reference. Furthermore, other methods and articles can also be used and production, for example in the Patent application and described those disclosed in: the applicant filed 25 August 2003, title of invention is "Synthetic   Microspheres   Same   Methods   Making   and   of" the, series of number 10/648, 184 common in the United States Patent application, all the same in that introduced as a reference. According to the invention discloses several preferred embodiments, the use of unique glass formulation production microsphere. The disclosed preferred embodiment preferably uses far more than heated dropper (  drop   tube heated) speed of the capacity of the production method for the production of the ball. For example, heated dropper per hour can be applied to the order of magnitude of about one gram of the production speed of the ball. Different, many of the disclosed herein the ball embodiment of the methods of implementation and the combustion in the furnace is greater than approximately 1.000 grams per hour speed of production, this far exceeds the capacity of drop tube furnace. In fact, the inventor described herein can make use of the new glass formulation to greater than about 0.5 (tonnes/H)   MT/hr speed production of alkali resistance of the ball. In other preferred embodiment, speed of production is that 1MT/hr, 2 MT/hr, 3MT/hr or more.

[0094] in addition, the disclosed glass can be used to form a having a multi-phase aggregate of synthesis, for example, in glass structure has a combination of an amorphous phase and crystal phase. Because the raw material of not completely melt or crystallization in the cooling process, the phases can exist in the glass. Degree of crystallinity can be through the roasting conditions or cooling conditions to control. Moreover, other phase, such as gas, may be present in the glass material is formed. The result is than totally homogeneous glass article with low density aggregate of synthesis. In a preferred embodiment, the synthetic aggregates of controlling roasting condition is to produce, for example, and the baking temperature of the residence time in the furnace, in order to produce the right the glass material containing crystal phase material and/or bubbles aggregate of synthesis part of the glass, thus creating a heterogeneous material. Of course, the described non-homogeneous glass can be used for forming the sheet, fiber, ball or any other desired configuration.

[0095] in some preferred embodiments, according to the content disclosed in the above preparation of the glass particles, aggregate, sheet or fiber is used for increasing the mechanical performance of the composite material. In a preferred embodiment, fiber, flake, aggregate forms of alkali resistant glass is used to improve compound cement product or the tensile strength of the polymer product. In another preferred embodiment, the expanded, foaming or hollow alkali-resistant glass particles can be used for making the cement compound and polymeric compound having a low density. In other preferred embodiment, alkali-resistant glass particles can also have other beneficial effects, such as reducing humidity change (moisture movement), heat change (  movement thermal), improve the tivs, reduce cost or improve the processing performance, denaturation or for instance class controllability.

The despite using the description of some embodiments, given in order to clarify these embodiments are alternative embodiments of this invention, and should not be construed as limiting the scope of the invention. For example, although it was already disclosed in the cement composite glass formula uses a unique, but the polymer, metal and to be able to benefit from the characteristics of the glass described herein is utilized in the other material on the basis of the unique articles made of glass formula, is within the scope of the present invention.