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The invention relates to a glass composition having a high zirconium oxide content, and to uses thereof.
Glasses having a high zirconium oxide content have mainly been described in connection with alkali-resistant glass fibers for concrete reinforcement. Compared with E-glass, a substantially alkali-free aluminoborosilicate glass, fibers made from known Zr02 containing glasses do have higher alkali resistance, but, in particular, their resistance in cement over a long period is inadequate. The alkali resistance of concrete-reinforcing fibers is of importance and is therefore usually to the fore during glass development, since the cement sets under highly alkaline conditions (pH values up to about 12.5). Besides the alkali resistance, however, the other chemical resistance, in particular the hydrolytic resistance, is clearly also of importance for long-term use as a reinforcing agent in concrete since it improves the long-term resistance.
Glasses which exhibit high resistance both to water, acids and caustic lyes are interesting for a wide variety of applications, for example for pharmaceutical packaging or for inspection windows in process tanks, in particular if they additionally have high heat resistance.
A feature for high heat resistance is a high glass transition temperature Tg. In glasses having a high Tg, experience has shown that the so-called compaction (shrinkage) is low. This is shrinkage of glass parts during temperature treatment below the Tg, a property which can only be determined with sufficient accuracy with great experimental complexity and is of importance, for example, for applications in which very
strict standards are set for the shape fidelity of the glass parts, for example for applications in display technology.
For optical applications, glasses having high negative anomalous partial dispersion in the blue spectral region (A Pg,F) are extremely interesting for correction of image aberrations. A disadvantage of the glasses in this series that have been disclosed hitherto is that they either have large amounts of PbO, which is undesired from environmental points of view, and have poor chemical resistance or that large amounts of the very expensive raw materials Nb20s and in particular Ta205 have to be used for lead-free substitution products, which makes economical manufacture much more difficult. Lead-free glasses of this type are disclosed in DE-A 27 29 706.
A wide variety of specifications in the patent literature which describe alkali-resistant glasses having high ZrC>2 contents are also already known, but these still have disadvantages.
British Patent Specification GB 1,290,528 describes glass compositions for the production of glass fibers which comprise from 13 to 23 mol% of R20 (0 - 2% of Li20, remainder Na20) . Glasses having such a high alkali metal content, as also occur in European Patent Specification EP 0 446 064 Bl, which describes glass fiber materials for components of exhaust systems for internal-combustion engines (13 - 18% by weight of Na20 + K20>, exhibit poor hydrolytic resistance.
The same applies to the glass fibers in accordance with DE 17 96 339 C3 based on a glass comprising 11% by weight of Na20 and 1% by weight of Li20 and to the glasses converted into fibers in DE 40 32 460 Al,
comprising 10 - 15% by weight of Na20 and 0.1 - 2% by weight of K20.
The glass compositions from German Laid-open Specifica¬tion DE-A 2 406 888, which likewise have a high alkali metal content {10 - 25% by weight of R20)\ comprise up to 2 0% by weight of oxides of the rare earth metals, for example cerium oxide or also naturally occurring mixtures of these oxides.
Rare-earth metal oxides, to be precise together with T1O2 in an amount of 0.5 - 16% by weight, where the TiC>2 content is at most 10% by weight of the glass, are also present in the glasses from German Laid-open Specification DE 31 07 600 Al. They furthermore comprise 0.1 - 1% by weight of Cr203. An essential aspect here is that the chromium is substantially in the trivalent state.
German Laid-Open Specification DE-A 26 14 395 describes ^Oj-free glasses, which have to comprise 0.5 - 10% by weight of Cr203 + Sn02 for their alkali resistance, components which have the following disadvantages: Cr203 Dnly dissolves in the glass flux with difficulty, and problems can also occur on use of chromium salts due to "chromium knots". Sn02 is a good nucleating agent and ;herefore promotes crystallization. The glasses iurthermore require 0.05 - 1% by weight of SO3 as melt assistant, which can result in interfering foam and slow-hole formation.
)E-A 30 09 953 describes glass fibers which, besides ;r02, must contain Th02. This component is necessary in order to achieve alkali resistance. Owing to its radio¬activity, however, it is desirable to be able to omit this component.
EP 0 500 325 Al discloses glass fibers containing 5 -18 mol% of Ti02. Their resultant chemical resistance is achieved at the expense of very high susceptibility to crystallization, which is particularly disadvantageous with respect to the spinnability of the glass melt to give fibers.
The Patent Specification DD 293 105 A5 describes a process for the production of highly alkali-resistant glass fibers and products produced therefrom, in which the glass melt to be spun, besides Si02, R2O3, Zr02» RO and R2O (K20, Na20 and/or Li20), also contains fluoride. This fluxing agent can only be omitted if Li20 is present.
JP 62/13293 B2 describes glass compositions containing at least 5% by weight of B2C>3 for the core glass and cladding of glass fibers. Zr02 is merely an optional component. Although these glasses have high water resistance, this cannot, however, be guaranteed over the entire composition range owing to the high B2O3 contents at the same time as relatively high alkali metal contents, since water-soluble alkali metal borate phases can easily form.
DE-A 2 323 932 describes glass fibers which contain both P2O5 and also B203 in addition to very high contents of Zr02 (8 - 16 mol%). The alkali metal content can vary within a broad range (1.5 - 25 mol%). Although such a high Zr02 content greatly increases the alkali resistance, P20s reduces it again however. In addition, the hydrolytic resistance cannot be adequate over the entire composition range.
GB 2 232 988 A describes Zr02-containing glass fibers which are coated with a thermoplastic resin in order to improve their alkali resistance. Owing to this additional process step, fibers of this type can only
be produced expensively and in a complex manner. Fiber materials which can be used are glass fibers from the Si02 -Zr02 -R20 system with a fairly large variation latitude of the components and with further merely optional components, since, owing to the coating, the corresponding properties of the glass lose importance.
DE-A 29 27 445 describes glass compositions having high Zr02 contents, namely 18 -24% by weight. Although the glasses consequently have high alkali resistance, a high content has, however, an adverse effect on the processing properties and devitrification stability.
By contrast, CZ 236 744 describes glass fibers made from mineral raw materials for cement reinforcement which contain only from 5 to 10% by weight of Z1O2, a content with which high alkali resistance can only be achieved with difficulty.
It is an object of the invention to provide a glass which has not only high caustic lye resistance, but also high hydrolytic resistance and good acid resistance and which has high heat resistance and good processing properties. This object is achieved by the glass having a high zirconium oxide content.
The glass according to the invention comprises from 54 to 72% by weight of Si02. At higher contents, the meltability would be impaired, while at lower contents, glass formation would be more difficult. At least 55% by weight are particularly preferred.
A1203, present in amounts of from 0.5 to 7% by weight, particularly preferably up to
6% by weight, likewise serves to improve glass formation and makes a
significant contribution toward improving the chemical resistance. However, excessively high contents would, in particular in the case of Zr02-rich and low-R20 compositions, result in an increased tendency toward crystallization. With increasing content of AI2O3, the Zr02 solubility drops indirectly; however, this can be countered within the given limits by the presence of the alkali metal oxides. It is therefore preferred for the Al203/Na20 weight ratio to be
An essential aspect for the high alkali resistance is the Zr02 content of the glass. It is therefore at least > 10% by weight. The maximum content is restricted to
The alkali metal oxide(s) (2 -
Of the alkaline earth metal oxides, which are present in the glass to the extent of greater than 5% by weight and at most 24% by weight, CaO is present in an amount of 3 - 11% by weight, preferably 3 - 10% by weight, while MgO is present in an amount of 0 - 10% by weight, SrO in an amount of 0 - 8% by weight and BaO in an
amount of 0 - 12% by weight, preferably 0 - 10% by weight, are optional components.
The alkaline earth metal oxides reduce the melt viscosity, suppress crystallization and also contribute toward an improvement in the alkali resistance. BaO in particular reduces the tendency toward crystallization. If the alkaline earth metal oxide content were too low, the meltability and processing properties in the glasses would be impaired excessively, and they could no longer be converted into fibers, and the Zr02 solubility would also be too low. At a content greater than the maximum content mentioned, the glasses would devitrify, and crystallization would likewise occur. A total content of alkaline earth metal oxides of at most 23% by weight is preferred.
B203 is an optional component and improves the meltability by reducing the viscosity. However, its content should remain restricted to less than 5% by weight, since B203 impairs the alkali metal resistance and in particular the acid resistance. It is preferred to restrict the maximum B2O3 content to 4% by weight.
The glass may furthermore comprise 0 - 4% by weight of Ti02 and 0 - 6% by weight, preferably 0 - 5% by weight, of La203. Addition of La203 improves the meltability of the glass, broadens the glass formation range and increases the refractive index. La203 and Ti02 prin¬cipally contribute toward an improvement in the hydrolytic and caustic lye resistance, with La203 being more effective than Ti02. Excessive contents of La203 and Ti02 reduce the acid resistance and result in crystallization.
A particularly preferred group of glasses according to the invention is the B203-free glasses of the following composition range (in % by weight, based on oxide):
Si02 58 - 71; Al203 0.5 - 10 - 5 -24, La203 0-1.
Besides the very high caustic lye and hydrolytic resistance inherent in all the glasses according to the invention, these glasses also have very high acid resistance. They belong not only to caustic lye class 1 and hydrolytic class 1, but also to acid class 1.
The glass may furthermore comprise up to 2% by weight, preferably up to 1% by weight, of each of Fe203, Mn02 and Ce02, where the sum of these three components should also not exceed 2% by weight, preferably should not exceed 1% by weight. These compounds are the usual impurities in naturally occurring raw materials of the glass constituents. In particular on use of the glasses according to the invention for the production of fibers for concrete reinforcement, inexpensive raw materials are of importance. On use of the glasses for optical purposes, the requirements of the purity of the glasses and thus of the purity of the raw materials are generally significantly greater. Here, the said sum and in particular the Fe203 content are preferably below 0.005% by weight.
For fining, the glasses may comprise conventional fining agents in conventional amounts, thus, for example, arsenic oxide, antimony oxide, chlorides, for example as CaCl2 or BaCl2, or, as preferred, Sn02. Fluoride is preferably omitted in all these glasses, but in particular in those having high Zr02 contents (> 12% by weight) . At the high melt temperatures of Zr02-rich glasses, the effort in avoiding environ¬mentally harmful emissions would be very high.
Examples:
Twenty examples of glasses according to the invention were melted from conventional raw materials in Pt/Rh crucibles and cast to give blocks. In addition, fibers were drawn by the re-drawing method.
Table 1 shows the composition (in % by weight, based on oxide) of the glasses and their main properties. These are the coefficient of thermal expansion 020/300 [10~S/K] , the glass transition temperature Tg [°C], the working point VA [°C], the density p [g/cm3] , the modulus of elasticity E [GPa], the temperature at which the glass has an electrical volume resistivity of 108 Q cm, TK100 [°C], and the hydrolytic resistance H in accordance with DIN/ISO 719 [ug of Na20/g] , the acid resistance S in accordance with DIN 12116 [mg/dm2] and the lye resistance L in accordance with ISO 675 (= DIN 52322) [mg/dm3] . Also shown are the optical data, the refractive index nd, the Abbe number v^ and the anomalous partial dispersion in the blue region of the spectrum A P9,F- Table 1 does not show the fining agents, whose contents correspond to the respective remainder to 100%.
The glasses according to the invention have high chemical resistances:
On determination of the hydrolytic resistance H in accordance with DIN/1 SO 719, in which the base equivalent of the acid consumption is given as ^9 of Na20/g of glaas grit, a value of 31 means that a glass belongs to hydrolytic class 1 ("highly chemically resistant glass"}. This is satisfied for the glasses according to the invention.
On determination of the caustic lye resistance in accordance with ISO 695 (= DIN 52322), a weight loss of up to 75 mg/dm2 means that the glass belongs to lye class 1 ("weakly lye-soluble"), which is satisfied for the glasses according to the invention.
On determination of the acid resistance S in accordance with DIN 12116, a weight loss of up to 0.7 mg/dm2 means that the glass belongs to acid class 1 ("acid resistant"), from more than 0.7 to 1.5 mg/dm2 means that the glass belongs to acid class 2 ("weakly acid-soluble" ) and from > 1.5 to 15 mg/dm2 means that the glass belongs to acid class 3 ("moderately acid-soluble"). The glasses according to the invention belong to acid class 3 or better.
The glasses which belong to acid class 1 (see by way of example glasses A6, All, A12, A15, A16 and A20) are thus so-called 1-1-1 glasses, i.e. they belong to class 1 in each of the three aspects of chemical resistance.
The glasses are very highly suitable as container glass, especially for chemically aggressive substances, in particular liquids.
The glasses according to the invention have high transition temperatures Tg of at least 640°C. They are
thus suitable for uses in which highly thermally resis¬tant glasses are required, for example also as compo¬nents of parts in exhaust systems with catalytic converters which are subjected to high temperatures. Owing to their low compaction, which is associated with a high transition temperature, the glasses are also highly suitable for use as substrate glasses in display technology.
The glasses according to the invention have coefficients of thermal expansion a2o/3oo of from 4.1 x 10"6/K to 8.0 x 1CT6/K and are thus fusible to tungsten and molybdenum and are highly suitable as fusing glass for these metals.
The glasses can be chemically tempered by ion exchange, as a result of which they are also highly suitable for applications in which increased shatter resistance is important, for example as substrates for EDP storage , media.
The glasses according to the invention can readily be converted into glass fibers. Owing to the good chemical resistance of the glasses, which results in increased r long-term durability, these glass fibers are extremely suitable for the reinforcement of concrete parts. Both use as short fibers and as continuous fibers (produc¬tion of concrete/glass fiber composites) is possible.
The glasses have good processing properties. For example, they can be converted into blocks, sheets, rods, tubes and fibers and can also be employed in these forms, depending on the application.
The optical data of the glasses, namely a refractive index n
region A Pg/F of up to -0.0130 also make them interesting for optical applications, for example for glasses for the correction of chromatic aberrations.
J It is surprising that, besides the good properties described with respect to thermal, mechanical and chemical parameters, the glasses also have very inter¬esting optical properties, in particular a negative
anomalous partial dispersion in the blue spectral > region (A Pg,F) ■ It has hitherto only been known here
that this property is caused in combination with
relatively low Abbe numbers (glasses of the flint type
vd
a high Abbe number (crown type vd > about 55), this
property can also be caused by the alkaline earth metal
oxides MgO - BaO and rare-earth elements La203, Gd203,
Yb203, LU2O3, etc., often in combination with the glass
former B203.
For the first time, glasses having a negative A Pg,F with low to moderate Abbe numbers which have relatively low concentrations of alkaline earth metal oxides, B203 and, if desired, La203 as rare-earth metal oxide and are free from the expensive components Nb205 and Ta20s are now available here.
We claim:
1. Glass having a high zirconium oxide content characterized by a
2. The glass as claimed in claim lwherein it comprises a composition (in % by weight, based on oxide) of
4. The glass as claimed in any one of the preceding claims having a hydrolytic resistance H in hydrolytic class 1, an acid resistance S in acid class 3 or better, a caustic lye resistance L in lye class 1, a glass transition temperature Tg of at least 640°C and a coefficient of thermal expansion a2o/3oo °f fr°m 4.1 x 10"6 to 8.0 x 10"6/K, a refractive index nd of from 1.53 to 1.63, an Abbe number-Dd of from 47 to 66 and a negative anomalous partial dispersion in the blue spectral region A Pg,F of up to -0.0130.
5. Glass fiber consisting of a glass as claimed in any one of the preceding
claims.
6. Glass having high zirconium oxide content, substantially as herein
described and exemplified.
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