# Patent

## Title
Refractory product having high zirconia content

## Abstract

The present invention relates to a molten, fluid refractory product comprising, in weight percentages on the basis of the oxides and for a total of 100% of the oxides:

    
    
        ZrO2+Hf2O: remainder to 100%
        4.5%<SiO2<6.0%
        Al2O3<0.80%
        0.3%<B2O3<1.0%
        Ta2O5+Nb2O5<0.15%
        Na2O+K2O<0.1%
        K2O<0.04%
        CaO+SrO+MgO+ZnO+BaO<0.4%
        P2O6<0.05%
        Fe2O3+TiO2<0.55%
        other oxide species, optionally including Y2O3: <1.5%, where Y2O3<0.3%,

the “A/B” ratio of Al2O3/B2O3 content by weight being 0.5 to 2.0. The invention can be used in glass melting furnaces.

## Background
FIELD OF TECHNOLOGY
The invention relates to a new fused cast refractory product having a high zirconia content.
PRIOR ART
Among refractory products, a distinction is made between fused cast products, well known for the construction of glass melting furnaces, and sintered products.
In contrast to sintered products, the fused cast products most often comprise an intergranular vitreous phase binding crystalline grains. The problems posed by sintered products and by fused cast products, and the technical solutions adopted for solving them, are therefore generally different. A composition developed for making a sintered product is therefore not usable as such a priori for making a fused cast product, and vice versa.
The fused cast products, often called electrocast products, are obtained by melting a mixture of suitable raw materials in an electric arc furnace or by any other technique that is suitable for these products. The molten material is then cast in a mold, and the product obtained undergoes a controlled cooling cycle so that it reaches room temperature without cracking. This operation is called “annealing” by a person skilled in the art.
Among the fused cast products, the electrocast products with high zirconia content, i.e. having more than 85 wt. % of zirconia (ZrO2), have a reputation for their quality of very high corrosion resistance without coloration of the glass produced and without generating defects.
Conventionally, the fused cast products with high zirconia content also comprise sodium oxide (Na2O) to prevent the formation of zircon from the zirconia and silica present in the product. The formation of zircon is in fact harmful since it is accompanied by a decrease in volume of the order of 20%, thus creating mechanical stresses that cause cracking.
The product ER-1195 produced and marketed by Saint-Gobain SEFPRO and covered by patent EP-B-403 387 is now widely used in glass melting furnaces. Its chemical composition comprises about 94% zirconia, 4 to 5% silica, about 1% alumina, 0.3% sodium oxide and less than 0.05 wt. % P2O5. It is typical of products with high zirconia content used for glass furnaces.
FR 2 701 022 describes fused cast products with high zirconia content that contain 0.05 to 1.0 wt. % of P2O5 and 0.05 to 1.0 wt. % of boron oxide B2O3. These products have a high electrical resistivity. Advantageously, this makes it possible to stabilize the electric power consumption during electric melting of glass and in particular avoid any problem of short circuiting in the refractory products leading to their rapid degradation. In fact, during electric melting of glass, some of the electric current passes through the refractory products. The increase in the resistivity of these refractory products therefore makes it possible to reduce the amount of electric current able to pass through them.
WO 2009 027610 describes fused cast products with high zirconia content having a high electrical resistivity in the presence of at least one oxide selected from Nb2O5 and Ta2O5 for silica contents between 6 and 12%.
WO 2007 099253 describes fused cast products with high zirconia content having a high electrical resistivity in the presence of at least one oxide selected from CrO3, Nb2O5, MoO3, Ta2O5 and WO3. These products contain less than 1.5 wt. % of B2O3 for alumina contents between 0.1 and 2.4%.
WO 2005 068393 describes fused cast products with high zirconia content having a high electrical resistivity while minimizing the contents of BaO, SrO, MgO, CaO, P2O5, Na2O and K2O. These products contain 0.1 wt. % to 1.2 wt. % of B2O3 and between 0.8% and 2.5% of alumina, but no attention is drawn to the Al2O3/B2O3 ratio. Further, none of the examples in this document includes an alumina content of less than 0.85%; an alumina content of greater than 0.9% is preferred.
JP 63 285173 describes fused cast products with high zirconia content having a good electrical resistivity and resistance to cracking for silica contents less than 6.5%.
The current development of glasses of very high quality, in particular glasses for flat screens of the LCD type, increases the requirements for the refractory products of glass melting furnaces. In particular, there is a need for refractory products with improved electrical resistivity, without having to use dopants, while having resistance to corrosion by glass.
The present invention aims to satisfy this need.
SUMMARY OF THE INVENTION
More particularly, the invention relates to a fused cast refractory product comprising, in percentages by weight based on the oxides and for a total of 100% of the oxides:

    ZrO2+Hf2O: complement to 100%
    4.5%<SiO2<6.0%
    Al2O3<0.80%
    0.3%<B2O3<1.0%
    Ta2O5+Nb2O5<0.15%
    Na2O+K2O<0.1%
    K2O<0.04%
    CaO+SrO+MgO+ZnO+BaO<0.4%
    P2O5<0.05%
    Fe2O3+TiO2<0.55%
    other oxide species, including optionally Y2O3 (when Y2O3 is present, it is counted among said “other oxide species”): <1.5%, with Y2O3<0.3%,

the ratio “A/B” of the contents by weight Al2O3/B2O3 being between 0.5 and 2.0.



As will be seen later, surprisingly, the inventors discovered that this composition allows the refractory product according to the invention to have a good electrical resistivity and a good corrosion resistance, even though the content of dopant Ta2O5 and/or Nb2O5 is less than 0.15%.
A refractory product according to the invention can further comprise one or more of the following optional characteristics:

    
    
        The ratio A/B of the contents by weight Al2O3/B2O3 is less than or equal to 1.75, preferably less than or equal to 1.6, preferably less than 1.5, preferably less than 1.2, less than 1.1, or even less than 1.0.
        The ratio A/B of the contents by weight Al2O3/B2O3 is greater than 0.55, or even greater than 0.60.
        The content by weight of ZrO2+HfO2 is less than 95.5%, or even less than 95.0%, or even less than 94.0% and/or greater than 90.0%, or greater than 91.0%, or even greater than 92.0%.
        The content by weight of silica SiO2 is greater than 4.6%, greater than 4.8%, greater than 4.9%, and/or less than 5.5%.
        The content by weight of Al2O3 is greater than 0.2%, or even greater than 0.3%, or even greater than 0.35%.
        The content by weight of alumina Al2O3 is less than 0.75%, less than 0.70%, less than 0.60%, less than 0.55%, or even less than 0.50%.
        Alumina Al2O3 is only present as impurities.
        The content by weight of B2O3 is greater than 0.35%, or even greater than 0.40%, or even greater than 0.45%.
        The content by weight of B2O3 is less than 0.90%, or even less than 0.80%, or even less than 0.70%, or less than 0.60%, or less than 0.55%.
        The content by weight of (Ta2O5+Nb2O5) is less than 0.10%, less than 0.05%, or is even virtually zero.
        The content by weight of (Na2O+K2O) is less than 0.04.
        The oxides of iron and/or of titanium and/or of calcium and/or of strontium and/or of barium and/or of magnesium and/or of zinc and/or of phosphorus are only present as impurities.
        The content by weight of oxides of iron and/or of titanium, Fe2O3+TiO2, is less than 0.4%, preferably less than 0.3%, preferably less than 0.2%.
        The content by weight of oxide of calcium and/or of strontium and/or barium and/or of magnesium and/or of zinc is less than 0.2%, preferably less than 0.1%.
        The total content by weight of oxides of calcium and/or of strontium and/or barium and/or of magnesium and/or of zinc, CaO+SrO+BaO+MgO+ZnO, is less than 0.3%, preferably less than 0.2%, less than 0.1%, less than 0.05%.
        The total content by weight of the “other oxide species” is less than 1.0%, less than 0.6%, less than 0.5%, or even less than 0.3%.
        The “other oxide species” only consist of impurities and the total content by weight of the “other oxide species” is less than 0.6%, less than 0.5%, or even less than 0.3%.
        The content by weight of yttrium oxide Y2O3, which forms part of the “other oxide species” is less than 0.25%.
        The content by weight of SnO2+CuO is less than 0.05%.
    
    


According to a particular embodiment, the invention proposes a fused cast refractory product comprising, in percentages by weight based on the oxides:

    92.0%<ZrO2+Hf2O<95.0%
    4.5%<SiO2<6.0%
    Al2O3<0.55%
    0.35%<B2O3<0.55%
    Ta2O5+Nb2O5<0.05%
    Na2O+K2O<0.04%
    CaO+SrO+MgO+ZnO+BaO<0.2%
    other oxide species (other than ZrO2, Hf2O, SiO2, Al2O3, B2O3, Ta2O5, Nb2O5, Na2O, K2O, CaO, SrO, MgO, ZnO, and BaO): complement to 100%,

the ratio “A/B” of the contents by weight Al2O3/B2O3 being between 0.6 and 1.2.



Preferably, the other oxide species represent less than 2.5%, less than 2.0%, less than 1.5%, less than 1.0%, less than 0.5%, or even less than 0.3%.
The invention also relates to a method for manufacturing a refractory product according to the invention, comprising the following successive steps:

    
    
        a) mixing raw materials so as to form an initial charge,
        b) melting said initial charge until a molten material is obtained,
        c) casting and solidification of said molten material, by cooling, so as to obtain a refractory product,

said method being characterized in that said raw materials are selected so that said refractory product is according to the invention.

    
    


Preferably, oxides for which a minimum content is required, notably ZrO2, SiO2, B2O3 or precursors of these oxides, are added systematically and methodically. Preferably, the contents of these oxides in the sources of the other oxides, where they are conventionally regarded as impurities, are taken into account.
Preferably, cooling is controlled, preferably so as to be carried out at a rate of less than 20° C. per hour, preferably at a rate of about 10° C. per hour.
The invention also relates to a glass melting furnace comprising a refractory product according to the invention, or a refractory product manufactured or that can be manufactured by a method according to the invention, in particular in a region intended to be in contact with molten glass. In a furnace according to the invention, the refractory product can advantageously form part of a tank for making glass by melting, notably by electric melting, where it may come in contact with molten glass at a temperature greater than 1200° C.
DEFINITIONS
The contents of oxides by weight refer to the total contents for each of the corresponding chemical elements, expressed in the form of the most stable oxide, according to the convention that is usual in the industry; therefore this includes the suboxides and optionally nitrides, oxynitrides, carbides, oxycarbides, carbonitrides, or even the metallic species of the aforementioned elements.
A “molten material” is a liquid mass which, to conserve its shape, must be contained in a container. It can contain some solid particles, but of an insufficient amount to be able to structure said mass.
“Impurities” means the inevitable constituents, introduced unintentionally and necessarily with the raw materials or resulting from reactions with these constituents. The impurities are not necessary constituents, but are merely tolerated. For example, the compounds included in the group of the oxides, nitrides, oxynitrides, carbides, oxycarbides, carbonitrides and metallic species of iron, titanium, vanadium and chromium are impurities.
“Dopant” here means the constituents Ta2O5 and/or Nb2O5.
Unless stated otherwise, all the contents of oxides in the products described and claimed are percentages by weight based on the oxides.


DETAILED DESCRIPTION OF THE INVENTION
In a fused cast product according to the invention, high content of zirconia ZrO2 makes it possible to meet the requirements of high corrosion resistance without coloration of the glass produced and without producing defects that impair the quality of said glass.
In a product obtained by melting, HfO2 cannot be dissociated chemically from ZrO2. In the chemical composition of such a product, ZrO2+HfO2 therefore denotes the total content of these two oxides. However, according to the present invention, HfO2 is not added deliberately in the initial charge. HfO2 therefore only denotes traces of hafnium oxide, this oxide always being naturally present in sources of zirconia at contents generally less than 2%. For clarity, the content of zirconia and traces of hafnium oxide can therefore be denoted either by ZrO2+HfO2 or by ZrO2, or by “zirconia content”.
The content of hafnium oxide HfO2 in a product according to the invention is less than 5%, generally less than 2%.
The presence of silica SiO2 notably permits the formation of an intergranular vitreous phase that can effectively accommodate the changes in volume of the zirconia during its reversible allotropic transformation, i.e. during transition from the monoclinic phase to the tetragonal phase.
However, addition of silica must be limited in order to obtain high corrosion resistance. Moreover, too high a content of silica might cause defects in the glass through detachment of stones (pieces of refractory product resulting from loss in cohesion of the product), which is regarded as poor behavior in application.
The presence of alumina promotes the formation of a stable vitreous phase and improves the castability of the products in the mold. An excessive content leads to instability of the vitreous phase (formation of crystals), which has an adverse effect on feasibility, in particular in the presence of boron oxide. The content by weight of alumina must therefore remain limited.
The presence of a content by weight of B2O3 in a proportion such that the ratio A/B of the contents by weight Al2O3/B2O3 is less than or equal to 2.0 makes it possible to increase the electrical resistivity.
The oxides Na2O and K2O have an adverse influence on electrical resistivity. The content by weight of Na2O+K2O must therefore be less than 0.1%. In particular, the content of K2O must be less than 0.04%.
According to the invention, the content by weight of Fe2O3+TiO2 is less than 0.55% and that of P2O5 is less than 0.05%. In fact, these oxides are known to be harmful and their content must preferably be limited to traces introduced as impurities with the raw materials.
Unless stated otherwise, the “other oxide species” are the species that are not listed above, namely species other than ZrO2, Hf2O, SiO2, Al2O3, B2O3, Ta2O5, Nb2O5, Na2O, K2O, CaO, SrO, MgO, ZnO, BaO, P2O5, Fe2O3 and TiO2. In one embodiment, the “other oxide species” are limited to species whose presence is not particularly desired and which are generally present as impurities in the raw materials.
Conventionally, in a fused cast product, the oxides represent more than 98.5%, more than 99%, or even roughly 100% of the mass of the product. It is the same in a product according to the invention.
A product according to the invention can be manufactured conventionally according to steps a) to c) described less than:

    
    
        a) mixing raw materials so as to form an initial charge,
        b) melting said initial charge until a molten material is obtained,
        c) solidification of said molten material, by cooling, so as to obtain a refractory product according to the invention.
    
    


In step a), the raw materials are selected so as to guarantee the contents of oxides in the finished product.
In step b), melting is preferably effected through the combined action of a fairly long electric arc, not causing reduction, and mixing which promotes reoxidation of the products.
To minimize the formation of nodules of a metallic appearance and prevent the formation of cracks or crazing in the final product, it is preferable to perform melting in oxidizing conditions.
The long-arc melting process described in French patent No. 1 208 577 and its additions No. 75893 and 82310 is preferably used.
This process consists of using an arc furnace whose arc is struck between the charge and at least one electrode some distance from said charge and adjusting the length of the arc so that its reducing action is minimized, while maintaining an oxidizing atmosphere above the molten bath and mixing said bath, either by the action of the arc itself, or by bubbling an oxidizing gas (air or oxygen, for example) in the bath or by adding substances that release oxygen, such as peroxides or nitrates, to the bath.
Melting can in particular take place at a temperature greater than 2300° C., preferably between 2400° C. and 2500° C.
In step c), cooling is preferably carried out at a rate of less than 20° C. per hour, preferably at a rate of about 10° C. per hour.
A product of the invention manufactured in this way consists of grains of zirconia surrounded by a vitreous phase. The zirconia can be monoclinic to more than 80%, more than 90%, more than 99% or roughly 100%, as percentage by weight. The vitreous phase can comprise more than 50%, or even more than 70%, of silica, between 5% and 20% of B2O3 and between 1% and 20% of alumina, in percentages by weight based on the vitreous phase. The silica, B2O3 and alumina can represent more than 95%, more than 97%, or even roughly 100% of the weight of the vitreous phase.
Any conventional method of manufacturing fused products based on zirconia intended for applications in glass melting furnaces can be employed, provided that the composition of the initial charge allows products to be obtained having a composition according to that of a product according to the invention.
EXAMPLES
The following non-limiting examples are given for the purpose of illustrating the invention.
In these examples, the following raw materials were used:

    
    
        zirconia containing mainly, on average by weight, 98.5% ZrO2+HfO2, 0.2% SiO2 and 0.02% Na2O,
        zircon sand at 33% silica,
        boron oxide of purity greater than 99%.
    
    


The raw materials were melted by the conventional process of arc furnace melting and then the molten material was cast to obtain blocks with the dimensions 220 mm×450 mm×150 mm.
Example 1 corresponds to the product ER1195, marketed by Saint-Gobain SEFPRO, and constitutes the reference.
For all the products obtained, crystallographic analysis reveals crystals of monoclinic zirconia surrounded by a vitreous phase typically having more than 70% of silica. All of the silica as well as the other oxide species with the exception of zirconia are in the vitreous phase.
The chemical analysis of the products obtained is given in Table 1; this is an average overall chemical analysis, given in percentages by weight.
In the following Table 1, * indicates that the example is outside of the invention, and an empty cell corresponds to a content less than or equal to 0.05 wt. %.
Cylindrical bars of product 30 mm in diameter and 30 mm high were extracted from the various examples of blocks produced. These bars were submitted to a potential difference of 1 volt at a frequency of 100 hertz at 1500° C. or 1600° C. respectively for measuring the electrical resistivity, “R1500” and “R1600” respectively.










TABLE 1









Compositions by weight




(as percentage based on oxides)
















ZrO2
SiO2
B2O3
Al2O3
Na2O
A/
R1500
R1600



(%)
(%)
(%)
(%)
(%)
B
(Ω · cm)
(Ω · cm)



















1*
Com-
4.0

1.20
0.3

70



2*
plement
4.5
0.40
0.80

2.0
110
80


3*
to
4.1
0.40
0.61

1.5
107
81


4 
100%
5.0
0.52
0.50

1.0
142
123


5 

5.1
0.52
0.40

0.8
160
132









The results show that the products of the invention tested have remarkable electrical resistivity despite the absence of dopant (Ta2O5+Nb2O5). In particular, all the inventive examples exhibit performances very largely superior to those of the product ER1195 (example 1).
Comparison of examples 2* and 3* shows that a decrease in the NB ratio of between 2.0 and 1.5 has no positive effect if the silica content is less than or equal to 4.5%.
Comparison of examples 3* and 4 shows, conversely, that a decrease in the A/B ratio of between 1.5 and 1.0 accompanied by an increase in the silica content of between 4.1% and 5.0% has a very positive effect.
Example 3* also shows that excessively low silica contents limit performances.
Comparison of examples 4 and 5 shows the positive effect of the decrease in the A/B ratio to between 1.0 and 0.8.
Finally, measurements showed that the resistance to corrosion by molten glass of the products of the invention is equivalent to that of the reference example 1*.
Of course, the present invention is not limited to the embodiments in the examples, which are given for purposes of illustration.

## Claims

1. A fused cast refractory product comprising, in percentages by weight based on the oxides and for a total of 100% of the oxides:
ZrO2+Hf2O: complement to 100%
4.5%<SiO2<6.0%
Al2O3<0.80%
0.3%<B2O3<1.0%
Ta2O5+Nb2O5<0.15%
Na2O+K2O<0.1%
K2O<0.04%
CaO+SrO+MgO+ZnO+BaO<0.4%
P2O5<0.05%
Fe2O3+TiO2<0.55%
other oxide species, optionally including Y2O3: <1.5%, with Y2O3<0.3% the ratio “A/B” of the contents by weight Al2O3/B2O3 being between 0.5 and 2.0.

2. The product as claimed in claim 1, wherein the ratio A/B is less than 1.5.

3. The product as claimed in claim 1, wherein Nb2O5+Ta2O5<0.10%.

4. The product as claimed in claim 3, wherein Nb2O5+Ta2O5<0.05%.

5. The product as claimed in claim 1, wherein the content by weight of silica SiO2 is greater than 4.8%.

6. The product as claimed in claim 1, wherein the content by weight of B2O3 is less than 0.80%.

7. The product as claimed in claim 6, wherein the content by weight of B2O3 is less than 0.55%.

8. The product as claimed in claim 1, wherein the content by weight of Al2O3 is less than 0.70%.

9. The product as claimed in claim 8, wherein the content by weight of Al2O3 is less than 0.55%.

10. The product as claimed in claim 1, wherein the content by weight of Y2O3 is less than 0.25%.

11. The product as claimed in claim 1, wherein the content by weight of Na2O+K2O is less than 0.04%, the content by weight of oxides of iron and/or of titanium, Fe2O3+TiO2, is less than 0.4%, the content by weight of P2O5 is less than 0.05%, the total content by weight of oxides of calcium and/or of strontium and/or of barium and/or of magnesium and/or of zinc, CaO+SrO+BaO+MgO+ZnO, is less than 0.3%, and the total content by weight of “other oxide species” is less than 0.6%.

12. The product as claimed in claim 1, comprising, in percentages by weight based on the oxides:
92.0%<ZrO2+Hf2O<95.0%
4.5%<SiO2<6.0%
Al2O3<0.55%
0.35%<B2O3<0.55%
Ta2O5+Nb2O5<0.05%
Na2O+K2O<0.04%
CaO+SrO+MgO+ZnO+BaO<0.2%
oxide species other than ZrO2, Hf2O, SiO2, Al2O3, B2O3, Ta2O5, Nb2O5, Na2O,
K2O, CaO, SrO, MgO, ZnO, and BaO: complement to 100%,

the ratio “A/B” of the contents by weight Al2O3/B2O3 being between 0.6 and 1.2.

13. The product as claimed in claim 1, wherein the content by weight of Al2O3 is less than 0.50%.

14. The product as claimed in claim 1, wherein the ratio A/B is less than 1.1.

15. A glass melting furnace comprising a product as claimed in claim 1 in a region intended to be in contact with molten glass.