Compositions: ceramic – Ceramic compositions – Glass compositions – compositions containing glass other than...
Reexamination Certificate
2000-03-23
2001-11-06
Group, Karl (Department: 1755)
Compositions: ceramic
Ceramic compositions
Glass compositions, compositions containing glass other than...
C065S455000
Reexamination Certificate
active
06313050
ABSTRACT:
The present invention relates to the field of artificial mineral wool. It is aimed more particularly at mineral wool intended for manufacturing thermal and/or acoustic insulation materials or soilless-culture substrates.
It concerns more particularly mineral wool of the glass wool type.
This type of mineral wool is usually fiberized by so-called “internal” centrifuging processes, i.e. those using centrifugers rotating at high speed and filled with holes. They are in fact well suited to fiberizing mineral wool of the glass wool type, broadly having a composition relatively rich in alkaline metal oxides and having a lower liquidus temperature and a higher viscosity at the fiberizing temperature than rock wool or basalt wool. This type of process is described in particular in Patents EP-0 189 354 or EP-0 519 797.
To the known criteria of industrial and economic feasibility and of quality level have in recent years been added that of biodegradability of mineral wool, namely its ability to be rapidly dissolved in a physiological medium, so as to prevent any potential pathogenic risk associated with the possible accumulation of the finest fibres in the body by inhalation.
The object of the invention is therefore to improve the chemical composition of mineral wool, especially of the glass wool type, the improvement being aimed especially at increasing its biodegradability and/or at reconciling biodegradability with ability to be fiberized by internal centrifuging (without, however, excluding other fiberizing methods).
The subject of the invention is a mineral wool capable of being dissolved in a physiological medium, which comprises the constituents below in the following percentages by weight:
SiO
2
38-52%, preferably at least 40%,
especially 41-48% or 45-50%
Al
2
O
3
16-23%, preferably 17-21% or 17-20%
RO (CaO and/or MgO)
4-15%, preferably 5-12% or 5-11%
R
2
O (Na
2
O and/or K
2
O)
16-25%, preferably 17-22% or 1720%
B
2
O
3
0-10%, especially at least 1%, preferably 3-
9% or 4-10%
P
2
O
5
0-3%, preferably 0-1.5%, especially 0 or
greater than 0 and at most 0.5%
Fe
2
O
3
(total iron)
0-3%, preferably 0-1.5%, especially
about 0.01 to 1%
TiO
2
0-2%
(Throughout the rest of the text, any percentage of a constituent of the composition should be understood to mean a percentage by weight).
The selection of such a composition has allowed a whole graph of advantages to be built up, especially by varying the many complex roles that a number of its specific constituents play.
Thus, what is involved is a mineral wool composition of the glass-wool type, in which its content of alkali metal oxides (R
2
O) essentially in the form of Na
2
O and/or K
2
O is greater than its content of alkaline-earth metal oxides (RO), which is essentially in the form of CaO and/or MgO. The content of iron oxide (measured in the form of Fe
2
O
3
, but corresponding, by convention, to the total iron content) is very moderate or even zero; on the other hand, the boron oxide content is significant.
The viscosity at fiberizing of such a composition is suitable for internal centrifuging.
As regards biodegradability, it was already known that certain compounds such as P
2
O
5
, could considerably improve this in mineral compositions especially of the glass-wool type, while other oxides, such as alumina, seemed, on the contrary, to have a tendency to reduce it, at the very least in neutral pH. Reference may be made, for example, to Patent EP-412 878. However, a massive addition of P
2
O
5
(or, for example, the omission of alumina) has not proved in the context of the invention to be the most judicious approach. This is because other considerations may arise, for example economic ones (P
2
O
5
coming from expensive raw materials) and also technical ones—the changes in the proportions of P
2
O
5
, and especially of alumina, in the composition may cause other of its properties to vary in an undesirable or unknown manner. Thus, P
2
O
5
is not without influence on the viscosity of the composition, just like alumina. However, most particularly in the case of compositions of the glass-wool type to be fiberized by internal centrifuging, to which the invention applies most advantageously, the viscosimetric behaviour of the composition is an important criterion to be suitably controlled.
The invention has therefore established a judicious compromise in the following manner: the composition may contain P
2
O
5
, but in a moderate amount of at most 3 or 1.5%. Thus, its beneficial effect on biodegradability is retained, without excessive addition which is expensive and tends to increase the liquidus temperature of the composition.
By suitably adjusting the contents of the other main constituents of the composition, namely RO, R
2
O, B
2
O
3
and SiO
2
, the Al
2
O
3
content has, on the other hand, been significantly increased, this being at least 16 to 17%. The alumina content may thus advantageously be at least 18%, especially at least 19 or at least 20%.
It has been found that this combination allowed the biosolubility criteria, both measured in vitro tests in neutral pH and in in vitro tests in acid pH, to be satisfactorily met. Indeed, the matter of knowing which pH is most representative of the in vivo physiological medium, especially that of pulmonary regions, has not been definitively resolved. A high alumina content seemed up to now to be favourable to rapid dissolution in acid pH, but slight/slow dissolution in neutral pH.
The invention makes it possible to obtain a high level of biosolubility, at least measured in vitro, whatever the pH, by selecting a high alumina content, but by adapting the content, especially of RO, R
2
O and B
2
O
3
, so as to maintain its beneficial effect in acid pH without being made to suffer in neutral pH.
The preferred CaO content of the composition according to the invention is advantageously chosen between 4 and 11%.
In parallel, the preferred MgO content is chosen between 0.1 and 7%, especially between 0.3 and 6.5%.
In fact, it is usual to choose a CaO content which is higher than the MgO content, for a given total content of alkaline-earth metal oxides, especially for raw material cost reasons. The MgO content may thus be chosen to be very low or even zero (for example between 0 and 1%) or to be higher, for example between 2 and 6%.
According to a first embodiment, the CaO/MgO ratio may thus be ≧1.25 especially ≧5 and even ≧10.
However, it has proved useful, in the context of the invention, to propose a second embodiment consisting in providing MgO contents comparable or even greater than CaO contents. MgO/CaO ratios may thus be greater than ≧0.8 or even greater than or equal to 1 or 1.05: this ratio which is different in the respective CaO and MgO contents, could have a favourable impact on the biodegradability of the composition.
The Na
2
O content of the composition is at least 12%, especially between 13 et 19.5%, while the preferred K
2
O content is at least 0.5%, especially between 0.5 and 8%.
As in the case of the CaO and MgO contents of alkaline-earth metal oxides, in the case of alkali metal oxides the composition usually has a markedly higher Na
2
O than K
2
O content. For a given total content of alkali metal oxides, K
2
O may thus have a very low or zero content (for example, less than 3%, especially between 0.5 and 2.5%). However, it is possible within the scope of the invention to also provide a significantly higher K
2
O content, for example about 5 to 7%, something which, for example, may represent up to more than one quarter or even of more than one third, by weight, of the total sum of the alkali metal oxides in the composition.
Advantageously, the composition contains alkaline-earth and alkali metal oxides in the following proportion: R
2
O/RO>1.8 especially between 2 and 4.
It should be noted that the sum SiO
2
+Al
2
O
3
allows the viscosimetric behaviour of the compositions to be largely controlled: it is preferred for this sum to be at least 60%, especially about 61 to 67%.
As regards the content of iron oxide (s) (total iron), this is optional, as m
Bernard Jean-Luc
De Meringo Alain
Laffon Fabrice
Group Karl
Isover Saint Gobain
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