DE1102351B - Alkali oxide, phosphoric anhydride, lead oxide and / or barium oxide and optionally glass containing a certain proportion of alumina - Google Patents

Description

The invention relates to glasses containing alkali oxide, phosphoric anhydride, lead oxide and / or barium oxide and optionally contain a certain proportionate amount of clay.

The invention also includes novel uses for such glasses.

The glasses according to the invention have the following composition:

Weight percent

Phosphoric anhydride (P ₂ O ₅ )
and alumina (Al ₂ O _s ) with one
Alumina content from 0 to

16% 50 to 66

Lead Oxide (PbO) and Barium Oxide (BaO). ' 9 to 13

Sodium Oxide (Na ₂ O) with a
Ratio of Sodium Oxide
to the total amount of lead oxide and barium oxide of
2 to 3.5 24 to 35

In order to influence the surface tension of the product, its meltability, its sensitivity and / or tendency to devitrify, the sodium oxide can also be partially or completely replaced by corresponding amounts of other alkali oxides, such as potassium oxide (K ₂ O) or lithium oxide (Li ₂ O ), taking into account the molecular proportions of the components.

It is also possible, in particular with the aim of improving the resistance of the glass to chemical and atmospheric influences, to replace a small part of the alkali, for example 5%, by the same proportionate amount of zinc oxide. With the same aim, a part of the phosphoric anhydride (P ₂ O ₅ ) of z. B. 5% can be replaced by an equal amount of boric anhydride (B ₂ O ₃ ). Finally, depending on the requirements placed on the product, a small percentage of lead oxide or barium oxide can be replaced by other alkaline earth oxides, such as lime or magnesia.

A content of clay gives the glasses according to the invention a low hygroscopicity, which is around becomes smaller as the proportion of alumina increases. The alumina acts to increase the sintering temperature and improving chemical and atmospheric resistance Agents.

The presence of lead oxide and barium oxide improves the meltability of the glasses. Out of consideration However, it is appropriate to comply with the commercial police regulations that exist in certain countries.

Alkali oxide, phosphoric anhydride,

Lead oxide and / or barium oxide

and possibly a certain amount

proportional amount of clay

containing glass

Applicant:

Compagnie de Saint-Gobain,
Neuilly-sur-Seine, Seine (France)

Representative: Dipl.-Ing. R. H. Bahr

and Dipl.-Phys. E. Betzier, patent attorneys,

Herne, Freiligrathstr. 19th

Claimed priority:
France of June 11, 1954 and May 11, 1955

Yves Georges Godron, Paris,
has been named as the inventor

moderate to keep the lead oxide content below 5%.

The presence of alkali oxide acts to lower the sintering temperature, but has been found that a content of alkali oxide which is above the limits given according to the invention, Products that devitrify on cooling, or even result in mixtures that are very difficult to vitrify can.

In general, it should be noted that the alkali phosphor glasses according to the invention are already comparatively low temperature of below 450 ° C, certain of them, the alumina content of which is very low is, possibly zero, sinter at a temperature below 300 ° C.

These properties of the alkali phosphor glasses according to the invention make them particularly useful for a number of industrial uses, some of which are particularly important listed below and should be explained:

1. Because of their certain water solubility, they are Glasses suitable as binders for the agglomeration of substances, especially those that are exclusively must be treated with a mineral product that is free of silica, like the one at certain catalysts in the gas-generating industry are the case, so that the use of silicate

109 530/243

3 4

Binding agents, such as water glass, is excluded. The use of a glass of the invention

Furthermore, these glasses are less acidic than phosphorus ßen composition, which has a favorable viscosity

acid or boric acid and less basic than Bi- in the temperature range between 300 and

ammonium phosphate and much less water - 550 ° C, in the same way as a lubricant more soluble than these substances. 5 when extruding metals or alloys

2. Another possibility of using the low melting point glasses, in particular of aluminum-new glasses, is as fillers or carriers for minium and aluminum alloys, which also results in trace elements that act as fertilizers. Within decent advantages, because the temperature to which that of the composition range of the glasses according to the lubricant is heated during the drawing process, of the invention can for such purposes, in particular io, be within this range. The sintering temperature in which the proportional ratio of P ₂ O ₅ : Al ₂ O _{3 of} the glasses according to the invention is set accordingly, depending on their composition, those glasses with a special composition between about 280 and 440 ° C. are selected which are due to the natural agents.

be attacked in a certain way. While the most significant of these benefits, so far still

the 15 commonly used in agriculture could never be achieved are the following:

Fertilizer when it first rains very suddenly the in a) It becomes possible to use at great speed

release and press the active ingredients contained in them. In the case of light metal alloys

decompose the glasses according to the invention can only z. B. the pressing speed 15 to

Slowly and slowly give the Phos 50 m / min.

phosphoric acid itself as well as the trace elements that 20 b) There are no large scars in the circumferential

were added, such as manganese, iron, zinc, copper areas of the product at later heat

ferrous and molybdenum oxides as well as boric acid. treatments on.

3. A particularly essential and new industrial c) Likewise, the emergence of a mean Field of application that opens up possibilities for the new cavity in the end region of the compact Glasses according to the invention are avoided as lubricants 25.

in the extrusion of non-ferrous metals or d) The glass composition according to the invention, metal alloys. Known to arise in the can ^of the surface of the rods or the extrusion molding of such metals or metal alloys without the use of the same Pießprofile vergroße difficulties essentially due to the dilute hydrofluoric acid, for example. B. already by great friction between the pressed block and 30 diluted nitric acid, and in the case of the tools of the press. Even through glasses with a low alumina content

The effect of this large friction local temperature i ^"one will be removed water.
Raises of the block which lead to the formation of cracks Below will give rise to some examples of glass in the pressed profile. Furthermore, given compositions according to the invention, the central part of the billet is deformed faster than the 35, ^{but without this being limited to} the specified subsidence in contact with the tools of the press.
Parts. This results in local, increased example 1
Tensions and a heterogeneous structure of the er- ", -, ^ 111
Testimony by the appearance of large glass without alumina
Scars on the circumference of the drawn products at 40. The vitrifiable mixture has the following heat treatments. Further settlement:

forms at the end of the drawn body to a hydrated trisodium length, which is up to 20% of the total length of the produced phosphate 109 50 parts
nisses can reach a middle cavity. Monoammonium phosphate ". '.'. '. 64 parts

In order to reduce the occurrence of such surface cracks, 45 red lead 5 15 parts

avoid, one has so far been forced to use the feed barium carbonate ............. 10/70 parts

speeds significantly reduce and on

The mixture is melted at 900 ° C. in the quartz crucible to distribute the frictional heat in the tools and allow the melt to be placed on a table. Apart from the fact that such a 50 cast. The glass obtained is slightly opalescent, the mode of operation reduces the performance of the press, but shows no tendency towards devitrification. Its neither prevents the later occurrence of large composition is in weight percent as follows: scars in the circumferential areas nor the formation ρ q. 57 ° / o
a central cavity in the product. p ^ q ⁵ 4 45 o / _o

It is already a process for extrusion 55 BaO 7 * 45%>

or -drawing of difficult to press metals in the jq- _a q 3110%

Heat known, at which between the ²

pressing block and the tools of the press, ins- The glass is pulverized or on the appropriate

in particular the drawing nozzle, the container and the drawing grain size (from 0.15 to 0.30 mm). One

needle, one under the action of the heat of the 60 disk of 145 X 3 mm in size passes through

Blocks wholly or partially melting, but viscous sintering at a temperature of 285 ° C in

permanent substance, e.g. B. make a glass, a salt or a 25 minutes.

Slag that meets these conditions. . , _o

is brought. Example 2

However, none of these previously proposed 6 ₅ The vitrifiable mixture has the following relationships

Lubricant allows, in completely satisfied- setting:

way to overcome the difficulties of hydrated trisodium

which is 81.3 parts when extruding non-ferrous phosphate

metals or metal alloys of the above-mentioned diammonium phosphate 61.7 parts

Kind of surrender. 70 red lead 4.6 parts

Claims (1)

5 6 barium carbonate 6.9 parts contain a certain proportional amount of alumina - anhydrous alumina 9.9 parts of the glass, characterized by a content of boric acid f '^ parts 50 to 66 percent by weight phosphoric acid an- zinc oxide 4 reile hydride (P2 O5) and alumina (Al2 O3) ". ,,.,. ,,. "ΟΛ10 r, ^. , with an alumina content of The mixture is melted at 92Cr C in the yuarzt crucible q bjg ^ 0 / and the melt is poured out. Up to 13 percent by weight of lead oxide (PbO) results in a very clear, non-opalescent glass and barium oxide (BaO) / percent by weight of the following composition: 35 percent by weight sodium oxide: io (Na2O) with a ratio of ^ 2 O5 48.8% sodium oxide to the total amount of lead oxide and barium oxide between 2 and 3.5. PbO 4.5% Ba O 5.4% * 5 2nd glass according to claim 1, characterized in that the sodium oxide, taking into account NaO O 25.8% of the molecular proportions of the constituents, is replaced by other alkali oxides How potassium oxide The glass is pulverized or replaced by the desired (K2O) and lithium oxide (Li2O). Grain size (from 0.15 to 0.30 mm) crushed. A 20 3rd glass according to claim 1 and 2, characterized by a disc of 145 χ 3 mm in size can be characterized by the fact that the alkali oxide is potassium oxide (K2O) sintering at a temperature of 450 ° C within or a mixture of sodium oxide (Na2O) of 25 minutes. and potassium oxide (K2O) or a mixture of “. 1 <j sodium oxide (Na2O) and lithium oxide (Li2O) eisPie 25 or a mixture of potassium oxide (K2O) and a lubricant when extruding aluminum lithium oxide (Li2O) or a mixture of minium alloys with a content of: Sodium oxide (Na2O) , Potassium oxide (K2O) and C11 j go / o lithium oxide (Li2O) are used. "'02% ^" glass according to one or more of the requirements of' 25Vo 3 ° Proverbs 1 to 3, characterized in that a 03% small proportion of the alkali oxide in the 2n 56% order of magnitude of, for example 5%, based on Na2O Zinc oxide has been replaced by the same proportionate amount of particularly suitable glass in percent by weight. the following composition: 35 5. Glass according to one or more of the PQ ep go / ,, Proverbs 1 to 4, characterized in that a ^ y Q "X0If) small proportion of the phosphoric acid 23 4 5% anhydride in the The sintering temperature of this glass is in Proverbs 1 to 5, characterized in that it is close to 370 ° C. The possible pressing speed low percentage of lead oxide or lead is 18 m / min. The product has no central cavity in its barium oxide due to at least one other oxide rearward area 7. Glass according to one or more of claims 1 to 6, characterized in that the patent claims: glass contains at least one trace element such as manganese, iron, copper and molybdenum oxides elder 1. Alkali oxide, phosphoric anhydride, lead 8. Application of the glass composition according to oxide and / or barium oxide and optionally one of claims 1 to 7 for enamelling purposes. © 109 530/243 3.61