LU84193A1 - HARD, WATER-RESISTANT, PHOSPHATE-CONTAINING CERAMIC MATERIALS AND METHOD FOR THE PRODUCTION THEREOF - Google Patents

Description

BL-329 3 / EM / BM

'* J_ Priority claim of 2 patent applications H filed in the U.S.A.

- on June 16, 1981 under No. 274.156 - on March 2, 1982 under No. 351.753

1 HARD. WATER RESISTANT. CERAMIC MATERIALS CONTAINING PHOSPHATE AND METHOD FOR THE PRODUCTION THEREOF

5

The present invention relates to hard, water-resistant, phosphate-containing ceramic materials and, in particular, to hard, water-resistant, phosphate-containing materials

Ceramic materials that do not require subsequent heat curing.

Refractory metal phosphates have long been considered: 15 suitable building and insulating materials. Compositions containing phosphoric acid, a metal oxide and metal silicates are known, but it is extremely difficult to prepare compositions comprising these components and having the required strength. Mixtures of aluminum oxide and 85% phosphoric acid, for example, are tough and difficult to handle. The handling of these mixtures can be considerably improved by diluting them with water. However, if silicate, e.g.

25 calcium silicate, added and the phosphate obtained. is cured with heat to distill off the excess water s ^ - 2 - 1, the refractory material thus obtained has a relatively low tensile strength. On the other hand, if all the components are mixed together 5 and without the addition of water, the reaction proceeds so quickly that it cannot be carried out under normal production conditions.

*

Various phosphate compositions and processes for their preparation are known. For example, U.S. Patent 2,992,930 to William Wheeler et al describes compositions of powdered zirconium or aluminum oxide, calcium silicate as a foam stabilizer, phosphoric acid, silica sol as a binder, 15 and a blowing agent, which are prepared by mixing the dry constituents which silica sol adds, the mixture is stirred with phosphoric acid and the resulting foam solidifies. In US Pat. No. 3,148,996 by Mark Vukasovich et al 20, compositions are described which solidify into hard masses without heat treatment and which are made porous by incorporating gas bubbles. These compositions contain water, an acidic phosphate consisting of ephosphorus pentoxide, calcium, aluminum-25 minium or zirconium oxide, and finely divided calcium silicates, and are obtained by preparing a viscous solution of water, phosphorus pentoxide and a suitable metal oxide, this mixture Calcium silicate is added and it is then partially hardened. Foam development is then brought about by adding an internal foaming agent or by mechanically introducing gas bubbles. U.S. Patent 3,300,675 to Jules Magder describes compositions of acidic aluminum phosphate, magnesium or zirconium-35 nium carbonate, oxide, hydroxide or silicate, and J organic or inorganic gas-generating material.

Il described to everyone. In other patents, similar phosphate foams are also described, a metal in powder form being introduced into the acid mixture, so that the formation of foam is induced by the release of hydrogen-5 gas.

Although it is clear from these references that considerable efforts have been made to develop suitable phosphate foams, there are still many problems. Most of these known foams have poor bond strength, which precludes their use as a building material. Some are sensitive to moisture, many require heat curing to improve bond strength, and most of them contain other additives to achieve the required hardness. In addition, most commercially produced foams contain blowing agents, which make the product more expensive and are sometimes responsible for the lack of binding strength.

Accordingly, it is an object of the present invention to provide solid, moisture-resistant, phosphate-containing ceramic materials which can be produced without the application of external heat.

Another object of the invention is

To provide processes for the production of hard phosphate foams without the addition of blowing agents.

30th

Another object of the invention is to provide processes for the convenient and continuous production of phosphate | to create foam, preventing the .Foam from collapsing.

'2Z · <- A - 1 These and other advantages of the invention are explained in more detail in the description below.

The invention relates to hard, water-resistant, phos-5 phosphate-containing ceramic materials which are produced from metal oxide, calcium silicate and phosphoric acid *. * can. By pre-reacting a part of the metal oxide with the phosphoric acid and / or by adjusting the temperature of the acid solution when mixing it with the other components, the property of the product to be obtained can be influenced in such a way that either foamed or non-foamed ceramic materials containing phosphate are obtained.

According to one embodiment, the process comprises the following process steps: (1) Selection of at least one metal oxide from the group containing Al ^ O ^, MgO, CaO or ZnO or their hydrates, the amount of metal oxide being about 11 to about 20 parts by weight , calculated on an anhydrous I basis, is; I (2) Preparing a reaction solution from a part of said metal oxide and about 80 to about 190 parts by weight of a phosphoric acid, corresponding to the 25 equivalent of about 55 to about 75% by weight of phosphorus pentoxide, based on the weight of the acid solution! i wherein the water of hydration of the metal oxide mentioned is included in the calculation of the phosphorus pentoxide content; and 30 (3) making a mixture of the rest: metal oxide and about 100 parts by weight of calcium i silicate. The temperature of the reaction solution is set to a desired value, and the G ·. mix i is mixed proportionally with said reaction solution l 35. The mixture obtained is brought into an I, desired shape and its components are brought together! the act. The amount of reagent f 1 i; * - 5 - ί _ 1 tion solution used metal oxide and the temperature of the reaction solution are chosen so that the time "at which the mixed mass hardens, can be approximately predetermined in relation to the 5 time at which water evaporation occurs.

According to a second embodiment, the method comprises the following process steps: (1) Preparation of a mixture containing approximately 11 to approximately 65% by weight, calculated on anhydrous

Base, at least one metal oxide selected from the group containing Al ^ O ^, MgO, CaO, ZnO or their hydrates, and about 100 wt .-% calcium silicate; and (2) preparing a reaction solution 15 from about 80 to about 190 parts by weight of a phosphoric acid solution corresponding to the equivalent of about 35 to about 75 parts by weight of phosphorus pentoxide based on the weight of the acid solution, the water of hydration of said metal oxide being included in the calculation 20 of the phosphorus pentoxide content is included. The temperature of the reaction solution is adjusted to a desired value and the mixture is partially mixed with the solution. The mixture obtained is brought into a desired shape and its components are allowed to act on one another. The temperature of the reaction solution is chosen such that the point in time at which the mixed mass hardens can be approximately predetermined in relation to the point in time at which water evaporation occurs.

According to a third embodiment, the process according to the invention comprises the following process steps: (1) selection of at least one metal oxide from the group containing Al ^ O ^, MgO, CaO or ZnO or their Hy-35 drate, the total proportion of the metal oxide being approximately * Is 11 to about 65 parts by weight, calculated on a water-> free basis; - 6 - "~ 1 (2) preparing a reaction solution from a part of the metal oxide and about 80 to about 190 parts by weight of a phosphoric acid solution, corresponding to the equivalent of about 35 to about 75% by weight of 5 phosphorus pentoxide, based on the weight of the acid solution, the hydrated water of said metal oxide being included in the calculation of the phosphorus pentoxide content; and, ’(3) preparing a mixture of the remaining 10 metal oxide and approximately 100 parts by weight of calcium silicate. The mixture is mixed proportionally with the reaction solution, the material mixture obtained is brought into a desired shape and the components are allowed to act on one another. The amount of metal oxide used to prepare the reaction solution is chosen so that the point in time at which the material mixture hardens can be predetermined approximately with respect to the point in time at which water evaporation occurs.

20th

According to a fourth embodiment of the present invention, there is provided a suitable composition which enables the production of a hard, water-resistant, phosphate-containing ceramic material, which composition (1) selects from about 11 to about 65 parts by weight, calculated on an anhydrous basis, of at least one metal oxide from the group containing A120 ^, MgO, CaO, ZnO or their hydrates; (2) about 80 to about 190 parts by weight of a phosphoric acid solution, equivalent to about 35 to about 75 percent by weight phosphorus pentoxide, based on the weight of the acid solution, the hydrate water of said metal oxide being included in the calculation of the phosphorus pentoxide content 35 becomes; and (3) contains about 100 parts by weight of calcium silicate-1 kat.

j * v.

'i- _ i - 7 -' - 1 According to a fifth embodiment of the invention, a hard, water-resistant, phosphate-containing ceramic material is obtained, obtained by the reaction of (.1) about 11 to about 65 parts by weight, 5 calculated on an anhydrous basis, at least a metal oxide selected from the group containing A ^ O ^ »MgO, CaO, ZnO or their hydrates; (2) from about 80 to about 190 parts by weight of a phosphoric acid solution containing the equivalent of about 35 to about 75 percent by weight phosphorus pentoxide based on the weight of the acid solution, taking the water of hydration of the metal oxide into account the phosphorus pentoxide content is included; and (3) about 100 parts by weight of calcium silicate.

15

The components used to practice the invention are all commercially available. Calcium silicate (100 parts by weight) is preferred in the invention, although satisfactory results can also be obtained with other silicates. Calcium silicate occurs naturally and is known as wollastonite. When using this material in powder form, as described below, suitable foamed or non-foamed products can be obtained. For foam generation, the particle size is preferably kept so small that the majority of the silicates pass through a 0.074 mm sieve.

In order to obtain a satisfactory ceramic material containing phosphate, a whole range of metal materials can be used! oxides such as Aluminum oxide, magnesium oxide, calcium oxide and zinc oxide can be used. These oxides are used in powder form, with smaller particle size (0.043 nm sieve or less) 35 generally giving better results. Hydrated forms of the oxides can also be used; / I * - 8 - ~ ~ 1 they are preferred in many cases. When using a hydrate, the water of hydration must be taken into account so that there is no excess water for the reaction. This can be accomplished by 5 the water of hydration when calculating the phosphorus | Including pentoxide content in the phosphoric acid solution; "· Pulls.

! About 5 11 to about .65 parts by weight of metal oxide, calculated on an anhydrous basis and based on 100 parts by weight of calcium silicate, can be used to practice the present invention; however, about 13 to 26 parts by weight of metal oxide is preferred, and the most preferred level is about 15 to 20 parts by weight. The amount of oxide to be used depends on whether it is in hydrated form and / or it depends on its reactivity.

20 Anhydrous magnesium oxide reacts with phosphoric acid much faster than anhydrous aluminum oxide. For example, the former reacts within minutes, while the latter can take hours depending on the temperature of the acid solution. However, using 25 hydrated forms dramatically reduces the difference in response time. Hydrati- | Magnesium oxide reacts faster than anhydrous magnesium oxide, and it also reacts much faster than hydrated aluminum oxide. Nevertheless, I 30 hydrated aluminum oxide is essentially more reactive than water-free aluminum oxide, because it reacts with the phosphoric acid solution after only a few minutes and not after hours. On | the influence of the reaction times will be discussed in more detail in the following 35.

| . In order to obtain suitable products, all of the oxides mentioned can be used alone or in combination, but water-free (calcined) magnesium oxide and hydrated aluminum oxide are particularly preferred for carrying out the invention. Magnesium oxide increases the strength and resistance to moisture of the end product, while aluminum oxide improves the hardening properties.

: 'Phosphoric acid is available in various concentrations 10, with 85% being the most common concentration of orthophosphoric acid. Other connections, e.g. Polyphosphoric acid, which after dilution with water give phosphoric acid, are also suitable for carrying out the invention, provided that the total water content of the reaction system is not too high. Excess water must be avoided, because otherwise the products obtained, although they are water-resistant, have only a low strength. On the other hand, too little water is also disadvantageous, not only because the materials are then difficult to mix, but also because only high-density foams are obtained in the production of foamed products.

I - 125 In general, phosphoric acid is suitable if it corresponds to the equivalent of about 35 to about 75% by weight phosphorus pentoxide, based on the weight of the acid solution. Preferably the phosphorus phosphorus equivalent is about 40-70%, and more preferably the equivalent of about 45-65% is more preferred.

The remaining portion of the acid solution is formed by water, including water of hydration of the metal oxide for reasons of calculation. From about 80 to about 190 parts by weight of i; 35 acid solution, preferably 90 to about 150 parts by weight of acid solution, may be used, but most preferred are about 100 to about 130 GeF V; major parts of acid.

Although the components used to implement the invention have been known for a long time, the advantages achieved by combining these components according to the invention were never recognized. It has been found that a product can be obtained which is water-resistant and does not require heat curing if the way in which the components are combined is appropriately controlled and excess water is avoided. Although Applicant 10 is not bound by any theory regarding the nature of the reactions taking place in accordance with the invention, there are obviously two independent but related phenomena, namely water evaporation and the binding of the materials. The heat generated by the reaction participants evaporates the water, whereby the water vapor can act as a foaming agent. The bonding (hardening) takes place within approximately the same period of time, as a result of which a solid, ceramic-like material is obtained. These two processes 20 are referred to here as “evaporation” or as “evaporation stage” or as “hardening” or as “hardening stage”.

To carry out the invention, the reaction solution 25 is preferably made by adding a desired amount

Metal oxide made for phosphoric acid solution. In addition, liquid additives such as surfactants can also be incorporated into the

Reaction solution are incorporated. The remaining metal oxide and the entire calcium silicate are then combined with one another and mixed with a solid additive, such as reinforcing fibers, thickeners, pigments and the like. The temperature of the reaction solution is preferably set to a desired value and the solution is mixed proportionately with the 35 remaining dry constituents. The material mixture is brought into the desired shape and £ 4 «

X

/ t - 11 - 1 allows the components of the system to interact. The products obtained do not require heat curing and can be placed in boiling water without any adverse effects. They are 5 not sensitive to heat. In practice, some products were heated to 871 ° C without any significant loss of strength.

It was found that the evaporation and hardening times related to each other determine the property of the product to be obtained. For example, if the vaporization stage is reached before the curing stage, the water vapor will cause the mixture to foam before the mass hardens. In contrast, when hardening occurs first, the material is unable to foam and the water vapor escapes through the gaps. The influence of the latter sequence of stages will be discussed in detail later, but in 20 two cases a product is obtained which does not require heat curing and is nevertheless water-resistant.

Two factors that affect the above-mentioned processes are, on the one hand, the amount of metal oxide previously reacted with the phosphoric acid and, on the other hand, the temperature of the reaction solution at the time it is mixed with the other dry constituents. If only one of these factors is controlled, a ceramic-like product can still be produced. However, both parameters are preferably controlled in order to make handling easier and to obtain a better product.

How these factors can be varied is shown in the following. In general, the extent r of the foaming occurring during the subsequent mixing and before the hardening of the material mixture becomes ».

‘T

The less metal oxide reacts with the phosphoric acid beforehand, provided the temperature of the acid solution is not too low. In contrast, if a relatively large amount of metal oxide -5 reacts with the phosphoric acid beforehand, less foaming occurs before the mass hardens. If a corresponding amount of metal oxide reacts beforehand, essentially no foaming occurs. This is evident from the fact that the previous addition of metal oxide extends the duration of the exothermic reaction or water evaporation reaction.

The temperature of the reaction solution in the subsequent mixing stage can also have a significant influence on the end product. The higher the temperature of this solution, the stronger the water vapor development and the earlier the water evaporation occurs when the reaction solution is mixed with the 20 remaining dry components. Accordingly, at higher temperatures, there is a greater likelihood of obtaining foams with voids or foams that foam quickly and then collapse. However, this effect can be somewhat weakened by adding a surfactant 25 to the reaction solution.

If the temperature is too low, the exothermic reaction can be suppressed so that no foaming takes place. In addition, too low a temperature can have an adverse effect in that the material obtained can have a relatively low bond strength. The optimum temperature of the reaction solution may vary depending on which reactants are used, but it has generally been found that satisfactory results can be achieved at a temperature range between about 1.7 ° C to about 27 ° C.

- 13 - - 1 The preferred temperature range for foam generation is around 3.4 ° C to 7.5 ° C, preferably 4.5 ° C, unless, as shown below, «a foaming agent is added.

5

In practice, besides the amount of previously reacted material and the temperature of the acid solution, there are other factors to consider, many of which depend on the type of product 10 being made. Foam formation is aimed at ensuring that the foam reaches a desired level at about the point at which curing begins. The water evaporation causing the foaming should essentially be timed so that after hardening the product has a uniform cell size with the correct size and that the final density is reached. The cell size is affected by the rate of water evaporation and the viscosity of the acid solution. The viscosity depends on the type of oxide (s) used and the temperature of the acid solution.

Solutions with different viscosities are obtained by dissolving different oxides in phosphoric acid. For example, if increasing amounts of magnesium oxide are added to a portion of a titer of an acid solution (e.g. 8590), viscosity grades are found to vary between approximately 50 cp and 1000 cp when the temperature of the acid solution is 22.5 ° C.

30 However, if comparable molar amounts of aluminum oxide are added to a second portion of the same acid solution at 22.5 C, viscosity values of approximately 50 cp to only 400 cp are found. In order to obtain better foams, the viscosity of the acid solution 35 solution when mixing with the other components preferably / not more than 400 cp. Accordingly, \ ’ß - 14 - - - 1, the viscosity of the reaction solution when using the magnesium oxide, in addition to its tendency to vigorous foaming, represents a second limitation when using this material.

5

The higher the viscosity of the reaction solution, the worse the components can be mixed and the lower the foam quality of the product obtained. For this reason, it is often appropriate to use 10 more than one oxide. Accordingly, a

Oxide used to prepare the reaction solution and another can be mixed with the calcium silicate. Optionally, the oxide can also be used as a mixture, both for forming the reaction solution and for mixing with the calcium silicate. Since there are a number of possibilities, all possible variations in the scope of application! included invention and the invention should not be limited to these two examples.

| 20 i

The density of the final product depends to a large extent on the amount required for the preparation of the reaction solution metal oxide used, i.e. the more metal oxide, the greater the density. As a rule, foams with a density of! about 0.64072 g / ci? up to about 0.24027 g / s? it lasts when about 0 to 0.3 part of metal oxide per part of P2O5 in the acid solution is used to prepare the reaction solution. If ί 30 more than 0.3 part of metal oxide is used, however, an unfoamed ceramic product is to be expected. However, the upper limit of the amount of previously reacted material is limited by practical considerations such as Viscosity, conditional, which is why usually no more than 35 509a of the metal oxide can be suitably prereacted.

r4 k / * - 15 -. _ 1 Further considerations such as particle size, surface properties and reinforcing materials also determine the foams. Because of the tendency of such materials to promote the formation of a fine cell structure, a small and uniform particle size is most preferred in the present invention. As mentioned earlier, metal oxides that pass through a 0.043 mm sieve and calcium silicate *. which passes through a 0.074 mm sieve is preferred.

10th

Cell size also depends on the surface properties of the material, and the use of one or more surfactants to promote cell stability is often appropriate. Any surfactant that is not attacked by the phosphoric acid can be practically used. A particularly suitable surfactant is dimethylcocamine, which Armak sells under the name Aramox DMC. However, this material must be handled with care as it is irritating to the skin and eyes.

20th

Since foams have porous properties, they “usually have a lower tensile strength than non-foamed materials. It is therefore often advisable to add reinforcing fibers to the strength of the foam.

25 Polyester, glass, polypropylene and nylon have been used with success, among others, although the conditions under which the end product is to be used can affect the choice of fiber. For example, glass fibers are much more stable than organic fibers when used at high temperatures. As a rule, fiber lengths are from 0.375 cm to; 2.54 cm is suitable, with fibers of approximately 1.27 cm in length being particularly preferred.

35 When manufacturing non-foamed * phosphate-containing ceramic materials, such factors as particle size, viscosity, temperature and surface egg *? _ I%! - 16 - - - 1 less important because the cell structure is irrelevant. Consequently, the use of materials with larger particle sizes and of reaction solutions with higher viscosity is also possible, provided that the handling of the reactants is guaranteed. The temperature of the reaction solution can also be higher since the non-foamed materials do not collapse. In addition, no surfactant is required because problem 10 of the cell structure does not arise.

Aside from these considerations, the goal of producing a non-foamed ceramic is comparable to that of producing a foamed material, with the difference that in the case of non-foamed materials, it is necessary to postpone the evaporation stage until the mass has hardened in order to expand the phosphate-containing material prevent. The best way to do this is to prereact a larger amount of metal oxide. However, it should be noted that the water can escape from the unfoamed material. If the internal pressure of the structure becomes too high due to the water pressure, the hard ceramic material can shatter. For this reason, it is often advisable to incorporate porous fillers for the production of non-foamed phosphate-containing ceramic materials

In the creation of passages through which the water vapor can escape. Such fillers 30 are, for example, vermiculite and pearlite.

I Surprisingly, the applicant has also | found that by the combination of the invention; method using the known foaming agents 35 satisfactory foamed products can be obtained. In the prior art, the use of materials that produce carbon dioxide or carbon dioxide! - 17 - 1 alien, on hydrogen or hydrogen-producing '' * materials, as well as on other organic or inorganic gas-generating materials in the production of phosphate-containing products. Such 5 agents are also advantageous in the production of the hard, water-resistant, phosphate-containing ceramic materials according to the invention.

Although practically all known foaming agents can be used, only the results obtained using various carbonates are supported by examples. Carbonates such as MgCO ^, CaCO ^, ZnCO ^, U ^ CO-j and the like, or mixtures thereof, which form relatively insoluble phosphates are preferred. However, MgCO ^ 15 is particularly preferred because, for example, it produces foams with fairly uniform cell size and with generally suitable density. Other carbonates such as ^ £ 00 ^ and I ^ CCX ^, which form relatively soluble phosphate salts, 20 can also be used, in those cases where the leakage of the phosphate from the resulting phosphate-containing ceramic material has no adverse effect.

-

When using dry foaming agents, it is usually advisable to combine them with the other I. * Mix dry components containing the calcium silicate and part of the metal oxide; however, they can also be added separately. Since the foam formation obtained with these agents does not go through! 30 water evaporation is induced, it is not desirable to let the exothermic reaction take place before hardening. Therefore, it is usually necessary to lend a larger amount of the metal oxide with the; React phosphoric acid beforehand. However, this often leads to an undesirable increase in the viscosity of the acid solution. Consequently, if an added foam former is used, the necessity | , dig result in a slight dilution of the acid solution in order to be able to regulate the viscosity. It should be noted, however, that there is no excess of water, since 5 the use of additional water, combined with the previous reaction of a larger amount of metal oxide, * leads to the temperature of the exothermic

Response decreases, which increases the likelihood of obtaining phosphate-containing ceramic materials with unsatisfactory performance data.

It should also be borne in mind that the temperature of the reaction solution at the time of mixing with the dry components can often be higher if the foaming is achieved using dry foaming agents than if it is caused by water evaporation, since the hardening before the Onset of the exothermic reaction must take place. Therefore, when using dry foaming agents, it is often desirable that the temperature of the reaction solution be in a preferred range of about 10 ° C to 15.5 ° C, rather than in the range previously mentioned in connection with water evaporation-induced foaming from about 25 3.4 ° C to 7.5 ° C.

Of course, a liquid foaming agent, such as fluorinated hydrocarbon with a boiling point! point lower than the temperature at which foam hardening occurs. Examples of such hydrocarbons are the Freon-11 or Freon 113- sold by DuPont

Hydrocarbons can be added to and mixed with the acid solution, or they can be separated; 35 be added when mixing with the solid components. Non-fluorinated hydrocarbons with an appropriate boiling point of -4¾ can also be used. • —ir '· * f Jl; * · - 19 -. 1 det, but they are due to the with their

Use associated fire hazard much less suitable.

5 The manner in which these foaming agents are added, whether liquid or dry, is left to the person skilled in the art or can depend on a number of factors, such as the type of product desired and / or the type of device used. Under certain circumstances, the property of the foaming agent can dictate the way in which it is used. For example, carbonates enter into a chemical reaction with the acid solution, which is why they must not be added to the acid solution too early in the course of the reaction. In contrast, fluorinated hydrocarbons cause foaming by changing from the liquid to the gaseous state, which is why they can be kept in contact with the acid solution, provided that the temperature of the mixture remains low enough. However, it must be admitted that in the latter case the fluorinated hydrocarbons form a two-phase system with the acid solution. Care should therefore be taken to ensure that the two-phase system 25 is mixed uniformly before being mixed with the solid components.

Since, according to the prior art, there is a whole range of materials which can be used in a wide variety of ways to produce the ceramic materials according to the invention containing phosphate-j, the term "foaming agent" used in the present application is intended to encompass all of these materials, provided that , Phosphate-containing products with 35 the properties mentioned above are obtained.

Vorteile t The advantages of the present invention are based on the

: V

The following examples, in which all constituents are expressed in parts by weight, are shown.

EXAMPLES

5

example 1

A phosphate-containing foam was produced from the following components:

Parts per io component weight in g 100 parts CaSiO? Α1203 · 3Η20 14.42 36.04 85% H3P04 41.58 104.0 (61.6% P205) 15 CaSi03 40.0 100

Surfactant 0.04 0.1

When these ratios are calculated on the basis of the metal oxide in anhydrous form and with the involvement of the hydrate water as part of the acid solution, the following ratios are obtained:

Component parts per 100 parts CaSi03 25 A1203 23.56 75.9% H3P04 116.5 (55% P205)

CaSi03 100

Surfactant 0.1 30

The reaction solution was prepared by adding 1.04 parts of A1203.3H20 to 104 parts of phosphoric acid and stirring the mixture with moderate stirring for about 15 minutes until a clear solution was obtained. The surfactant (0.1 part) was added to the 35 reaction solution, which was then cooled to 4.5 ° C. The other dry components (100 parts calcium silicate and 35 / V

21-2 parts of aluminum oxide trihydrate) were mixed and fed to a continuously operating Readco device. The reaction solution was also introduced into the Readco-5 mixer, but through a different feed opening. The ingredients were mixed proportionally, loaded onto a conveyor belt covered with a thin cushioned canvas and leveled. Foaming started after about 1.5 minutes and the mass became hard within 2 minutes. This gave a 2.54 cm thick and 12.70 cm wide continuous block of foamed material. The foamed material had a fine cell structure and a density of 0.28852 g / cm ^. The compressive strength of the material was 0.29580 kg / cm2 according to ASTM D1621, 15 and the modulus of rupture according to ASTM C209 was 0.34510 kg / cm '. No signs of cracks were observed after placing 20 g of the material in boiling water for 1/2 hour and allowing it to dry, nor after moistening it with 50 g of water at room temperature and allowing it to dry.

Example 2 25 A phosphate-containing foam was made from the same components used in Example 1. The reaction solution was obtained by adding 1.04 parts of A ^ O ^. ^ E ^ O 104 parts of a phosphoric acid I and stirring the mixture with moderate stirring for 15 minutes 30 ° until a clear solution was obtained. Then the surfactant was added to the reaction solution (0.1 part) too. The remaining dry constituents (100 parts of calcium silicate and 35 parts of aluminum oxide trihydrate) were mixed and fed to a continuously 35 ″ Readco device. The reaction solution, which was at room temperature, was also placed in the Readco mixer, but through a different feed opening. The components were mixed • proportionally therein, loaded onto a conveyor belt covered with a thin 5-pad canvas and leveled. Foaming began after about 42 seconds and the mass hardened within about 50 seconds. One got egg in this way. NEN 2.54 cm thick and 12.70 cm wide, 10 go through the block of foamed material. The foamed

Material had a rough, uneven cell structure and a density of 0.2723 g / cnr5. The compressive strength of the material according to ASTM D1621 of the material was 0.24650 kg / cm ^ and the modulus of rupture according to ASTM C209 p 15 was also 0.24650 kg / cm. No signs of cracks were observed after placing 20 g of the material in boiling water for 1/2 hour and allowing it to dry, nor after moistening and drying with 50 g of water at room temperature.

Example 3

A phosphate-containing foam was made from the following components:

Component Weight in g parts per 100 parts CaSiO, -5 Α1205 · 5Η20 11.44 30.1 30 MgO (calcined) 3.0 7.9 80% H3P04 43.56 114.63 (58.0% P205)

CaSiO ^ 38 100

Surfactant 0.3 0.79 35 polyester fibers 0.2 0.53 with a length of 1.27 cm 'Ti When calculating these ratios on the basis of

X

- 23 - * t 1 of the metal oxide in anhydrous form and taking into account the water of hydration as part of the acid solution, the following conditions occur: 5

Component parts per 100 parts CaSiO ·? A1203 19.7

MgO (calcined) 7.9 10 73.3% H3P04 125.03 (53.2% Pz05)

CaSi03 100

Surfactant 0.79

Polyester fibers 0.53 15 with a length of 1.27 cm

The reaction solution was prepared by adding 1.15 parts of AlgOj ^ HgO 114.63 parts of a phosphoric acid and stirring the mixture with moderate stirring for about 15 minutes until a clear solution was obtained. The surfactant (0.79 parts) was added to the reaction solution, which had previously cooled to 4.5 ° C. The remaining dry ingredients (100 parts calcium silicate, 28.95 parts aluminum oxide trihydrate, 7.9 parts 25 magnesium oxide and 0.53 parts polyester fibers) were mixed and fed to a continuously operating Readco device. The reaction solution was also dropped into the

Readco mixer introduced. The components were mixed proportionally in a mixer, loaded onto a conveyor belt covered with a thin cushioned canvas and leveled. Foaming started after about 57 seconds and the mass hardened within 1 min. 51 seconds. In this way a 2.54 cm was obtained; 35 thick and 12.70 cm wide, continuous block of foamed material, which had a fine cell structure, and a density of 0.3043 g / cm ^. The material had a compressive strength according to ASTM D1621; ’.1 ___ - 24 - 1 0.4930 kg / cm ^ and a modulus of rupture according to ASTM C209 of 2 0.3944 kg / cm. No signs of cracks were observed after 20 g of the resulting material had been placed in boiling water and allowed to dry for 1/2 hour, nor after having been moistened with 50 g of water at room temperature and allowed to dry.

Example 4 10

A phosphate-containing foam was made from the following components:

Component weight in g parts per 100 "r. Parts CaSiO ^, 15 -3 Α12 ° 3 · 3Η2 ° 16.0 40.0 85% H3P04 40.0 100.0 (61.6% P205)

CaSiO ^ 40.0 100.0 2o surfactant 0.04 0.1

When these ratios are calculated on the basis of the metal oxide in anhydrous form and including the water of hydration as part of the acid solution, the following ratios result:

Component parts per 100 parts CaSiO ^ A1203 26.15 30 74.7% H3P04 113.85 (54.1% P205)

CaSiO, 100 5

Surfactant 0.1 35 The reaction solution was prepared by adding 5 parts A1203. ^ H20 100 parts phosphoric acid and the mixture with moderate stirring for about 15 minutes - 25 -. _ 1 stirred until a clear solution was obtained. The

Reaction solution, which at this time was 4.5 ° C

cooled, the surfactant (0.1 part) was added * * The remaining dry constituents (100 parts calcium- »5 silicate and 35 parts aluminum oxide trihydrate) were mixed together and fed to a continuously operating Readco device. The reaction solution was also introduced into the Readco mixer, but through a different feed opening. The 10 constituents were mixed proportionally in the mixer, loaded onto a in a conveyor belt covered with a thin cushioned canvas and leveled. Foaming began after about 1 minute and 45 seconds and the mass hardened within about 2 minutes and 5 seconds 15. In this way, a 2.54 cm thick and 12.70 cm wide, continuous block of foamed material with a fine cell structure and a density of 0.46452 g / cm ^ was obtained. The material had a compressive strength of 0.59160 kg / cm | 20 in accordance with ASTM D1621 and a breaking modulus of 0.59160 kg / cm2 | according to ASTM C209. No signs of cracking were observed after placing 20 g of the material in boiling water for 1/2 hour and allowing it to dry, nor after moistening it with 50 water at room temperature and allowing it to dry.

Example 5 30 An unfoamed phosphate-containing ceramic material was produced from the following components;

Component weight in g parts per 100 parts CaSiO- ^ —— -3 A ^ O ^. -jI ^ O 18.4 40.89 I 35 8550 H3P04 39.6 88.0 (61.650 P205)

CaSiO-j 45.0 100 - 26 - \,.

1 When calculating these ratios on the basis of the metal oxide in anhydrous form and under. Including the hydrate water as part of the acid * solution results in the following relationships: »5

Component parts per 100 parts CaSiO, I - - A1203 26.73 73.2.% H3P04 102.16 10 (53.1 # P205)

CaSiO ^ 100

The reaction solution was prepared by adding 9.78 parts of A ^ O ^. ^^ O 88 parts of phosphoric acid 15 and stirring the mixture with moderate stirring for about 15 minutes until a clear solution was obtained. The remaining dry constituents (100 parts of calcium silicate and 31.1 parts of aluminum oxide trihydrate) were mixed together and one worked continuously 20 tendency Readco device supplied. The reaction solution was also fed to the Readco mixer at room temperature, but through a different opening.

The components were mixed proportionally in the mixer, loaded onto a conveyor belt covered with a thin cushioning canvas and leveled. No foaming occurred and the mixture hardened to a solid mass in 2 minutes and 10 seconds. The hard, ceramic-like material had a density of 0.96108 g / cm 4.

30th

Example 6 | A phosphate-containing ceramic material was made from- | / the components manufactured: P *! 35 "| I ** »H · -------- - 27 -« 1 component weight in g parts per 100

Parts CaSiO, A1203.3H20 17.44 38.76 72% H3P04 40.56 90.13 5 (52.18% P205)

CaSi03 45 100

Vermiculite 4 8.89 (0.096108 g / cm5) 10 When calculating these ratios based on; Laying the metal oxide in anhydrous form and including the water of hydration as part of the acid solution results in the following ratios: 15 component parts per 100

Share CaSi03 A1203 25.34 63% H3P04 103.55 (45.4% P205) 20 CaSi03 100

Vermiculite 8.89

The reaction solution was prepared by adding 7.65 parts of A1203.3H20 to 90.13 parts of phosphoric acid 25 and stirring the mixture with moderate stirring for about 15 minutes until a clear solution was obtained. The remaining dry constituents (100 parts of calcium silicate, 31.11 parts of aluminum oxide trihydrate and 8.89 parts of vermiculite) were mixed together and fed to a 30 continuously operating Readco device.

The reaction solution was also fed to the Readco mixer at room temperature (22.5 ° C.), Qedcch through another opening. The ingredients were mixed proportionally in the mixer, loaded onto a conveyor belt covered with a thin 35 'upholstery canvas, and Sv leveled. No foaming occurred. and the Λ - 28 - - - 1 mixture hardened to a solid mass within 2 minutes and 30 seconds. The hard, ceramic-like material had a density of 0.94506 g / cm ^.

«* 5 Example 7

This example shows the use of a known dry foaming agent in the process according to the invention for the production of a phosphate-containing ceramic material. A phosphate-containing foam was produced from the following components:

Parts per

Component Weight in g 100 parts CaSiO- ^ 15 A1203.3H20 8.97 17.94 68% H3P04 56.03 112.06 (49.3% P205)

CaSi03 50.00 100.0

MgC03 2.0 4.0 2o MgO (calcined) 7.0 14.0

Talc filler 10.0 20.0

When calculating these ratios on the basis of the metal oxide in anhydrous form and under. 25 Including the hydrate water as part of the acid solution, the following proportions result:>

Component parts per 100 parts CaSiO ^ 30 A1203 11.72 64.4% H3P04 118.27 (46.7% P205)

CaSi03 100.0

MgC03 4.0 S5 MgO (calcined) 14.0

Talc filler £ 20.0 "Ά I · '......

- 29 - «! "1 The reaction solution was prepared at room temperature by adding 17.94 parts of Al ^ O ^. ^^ O while stirring 112.06 parts of phosphoric acid solution. The receive. The clear solution was cooled to 12.6 ° C. The remaining 5 dry components (100 parts calcium silicate, 4.0 parts magnesium carbonate, 14 parts magnesium oxide and 20 parts filler) were mixed together and fed to a continuously operating Readco device. The reaction solution with a> 10 temperature of 12.6 ° C was also in the Readco

Mixer introduced, ôeàoch through another feed opening. The components were mixed proportionally in the mixer and loaded onto a conveyor belt covered with a thin cushioned canvas. Due to the 15 acid present in the mixture, foaming occurred when the material was removed from the mixer. The foaming material was leveled and hardened within approximately 1 minute and 30 seconds.

An exothermic reaction induced by vapor evolution 20 occurred 30 seconds later. The hard, foamed material had a fine cell structure and a density of 0.19221 g / cm. The compressive strength according to ASTM D1621 of this material was 0.44370 kg / cm ^, and the breaking modulus according to ASTM C209 p 25 was 0.19720 kg / cm. This material floated in the water, which means that the water could not easily penetrate the foam material.

Example 8 30

This example illustrates the use of a known liquid foaming agent in the manufacture of the phosphate-containing ceramic material according to the invention. A phosphate-containing counterpart was placed; 35 consisted of the following components: * f - Γ - 30 - ». 1 component weight in g parts per 100

Parts CaSiO- * A1203.3H20 9.0 18.0 80.2% H ^ P04 53.0 106.0 5 (58.2% P205)

CaSiO ^ 50.0 100.0

Freon-11 4.0 8.0

MgO (calcined) 5.0 10.0

Talc filler 10.0 20.0 10

When calculating these ratios on the basis of the metal oxide in anhydrous form and taking into account the hydrate water as part of the acid solution, the following quantitative ratios result:

Component parts per 100 parts CaSiO ^ A1203 11.8 2o 75.8% H3P04 112.2 (55% P205)

CaSiO ^ 100.0

Freon-11 8.0

MgO (calcined) 10.0. 25 talc filler 20.0

The reaction solution was prepared at room temperature by mixing 10 parts of A ^ O ^. ^^ O with 106 parts of phosphoric acid with stirring, whereupon the reaction solution was cooled to 12.6 ° C. The remaining dry ingredients (100 parts calcium silicate, 8 parts alumina trihydrate, 10 parts magnesium oxide and 20 parts filler) were mixed together and fed to a continuously operating Readco-35 device. There the ingredients were mixed proportionally and the Freon-11 by a

A

separate row mixer added to ensure good dispersion. The mixed material verb - 31 - 1 left the mixer and within 3 minutes the foam started to appear. After 4 minutes, hardening occurred and after 4 1/2 minutes the exothermic reaction occurred. The coarse-line foam obtained had a density of 0.3043 g / cm ^.

The invention is not only intended to be limited to the examples and descriptions above, but also encompasses all of the 10 l variation options set out in the claims.

t I

fr / / 4.

Claims (52)

1. A process for producing a hard, water-resistant, phosphate-containing ceramic material, since - 5 characterized in that it comprises the following process steps: Providing a metal oxide, namely about 11 to about 65 parts by weight, calculated on an anhydrous basis, at least one metal oxide -10 selects from the group A ^ O- ^, MgO, CaO, ZnO or their hydrates, preparing a reaction solution from a part of the said metal oxide and approximately 80 to approximately 190 parts by weight of a phosphoric acid solution, corresponding to the equivalent of approximately 35 to 75% by weight of phosphorus pentoxide, based on the weight of the acid solution, the water of hydration of the metal oxide mentioned being included in the calculation of the phosphorus pentoxide content, 20 Prepare a mixture of the remaining metal oxide and about 100 parts by weight of calcium silicate, adjust the temperature of the reaction solution mentioned to a desired value, proportionally mix the said mixture with '25 of the reaction solution, and provide the material mixture obtained in one! - Desired form, in which the components are then allowed to act on one another, the amount of metal oxide used to prepare the reaction solution; 30 and the temperature of the reaction solution so chosen that the time of hardening of this mixed material with respect to the time of arrival; \ tend water evaporation can be roughly predetermined \. ? 35 2. The method of claim 1, characterized in that about 13 to about 1 part 26 parts of metal oxide, about 100 parts of calcium silicate and about 90 to about 150 parts of a phosphoric acid solution, corresponding to the equivalent of about 40 to about 70% phosphorus pentoxide, can be used. 3. The method according to claim 1, characterized in that about 15 to about 22 parts of metal oxide, about 100 parts of calcium, 'io ciumsilikat and about 100 to about 130 parts of a phosphoric acid solution, according to the equivalent; from about 45 to about '65% phosphorus pentoxide. 15 4) Method according to one of claims 1, 2 or 3, characterized in that the temperature of the reaction solution is approximately in the range of 1.7 to 27 ° C. 20 5) Method according to one of claims 1, 2 or 3, characterized in that the temperature of the reaction solution is approximately in the range between 3.4 and 7.5 ° C. 25 6) Method according to one of claims 1, 2 or 3, characterized in that j the temperature of the reaction solution is approximately 4.5 ° C. I 30 7) Method according to one of claims 1, 2 or 3, | characterized in that the particle size of the metal oxide is not larger than 8 | 0.043 mm and the particle size of the calcium silicate | is not larger than 0.074 mm. 35 s - 8) Method according to one of claims 1, 2 or 3, Î characterized in that I "« t · j ^ said metal oxide is aluminum oxide trihydrate. I ♦ 1 9) Method according to one of claims 1, 2 or 3, characterized in that the metal oxide is magnesium oxide 4 5 10) Method according to one of claims 1, 2 or 3, characterized in that said metal oxide is a mixture of aluminum oxide trihydrate and magnesium oxide 1 ° n) Water-resistant, phosphate-containing ceramic product according to one of the methods described in claims 1, 2 or 3. 12. Ceramic products according to claim 11, characterized in that they have a foamed structure. 13. Ceramic products according to claim 11, characterized in that they have a non-foamed structure. 14. Ceramic products according to claim 13, characterized in that they contain a filler. 25th 15. The method according to any one of claims 1, 2 or 3, characterized in that »said reaction solution contains a surfactant. 30 16) Method according to one of claims 1, 2 or 3, characterized in that; said mixture contains fibrous reinforcing material I. 35 17) Method according to one of claims 1, 2 or 3, r characterized in that said material mixture contains a foaming agent. * 1 18) Method according to claim 17, characterized in that this foaming agent is a carbonate selected from the group MgCO ^, CaCO ^, ZnCO ^ or Li ^ CO ^. 5 19. The method according to claim 17, characterized in that said foaming agent is a fluorinated hydrocarbon with a boiling point which is below the temperature at which the said mixture of materials becomes hard. 20. A method for producing a hard, water-resistant, phosphate-containing ceramic material, characterized in that it comprises the following 15 process steps: producing a mixture of approximately 11 to approximately 65 parts by weight, calculated on an anhydrous basis, at least one metal oxide selected from the group Al ^ O ^, MgO, CaO, ZnO or their hydrates, and 20 about 100 parts by weight of calcium silicate, preparing a reaction solution from about 80 to about 190 parts by weight of a phosphoric acid solution, corresponding to the equivalent of about 35 to about 75% by weight of phosphorus pentoxide, based on the weight of the acid solution, the water of hydration of said metal oxide being included in the calculation of the phosphorus pentoxide content, setting the temperature of said reaction solution to a desired value, 30 Proportional mixing of the mixture mentioned with the reaction solution, and provision of the material mixture obtained in a desired form in which the constituents are allowed to act on one another, the temperature of the reaction solution being chosen so that the time at which the material mixture hardens can be roughly predetermined with regard to the point in time of the water evaporation that occurs. 21. The method of claim 20, characterized - 5 indicates that about 13 "to about 26 parts of metal oxide, about 100 parts of calcium silicate and about 90 to about 150 parts of a phosphoric acid solution, corresponding to the equivalent of about 40 to about 70% phosphorus pentoxide , 10 are used. / 22. The method of claim 20, characterized in that about 15 to about 22 parts of metal oxide, about 100 parts of calcium 15 silicate and about 100 to about 130 parts of a phosphoric acid solution, corresponding to the equivalent of about 45 to about 65% phosphorus pentoxide, are used . 20 23) Method according to one of claims 20, 21 or 22, characterized in that the temperature of the reaction solution is approximately in the range of 1.7 to 27.0 ° C. 25 24) Method according to one of claims 20, 21 or 22, characterized in that - the temperature of the reaction solution is approximately in the range from 3.4 to 7.5 ° C. 30 25) Method according to one of claims 20, 21 or 22, characterized in that the temperature of the reaction solution is approximately 4.5 ° C. 1 35 26) Method according to one of claims 20, 21 or 22, characterized in that i! 1 J the particle size of the metal oxide is not larger than r- <1 0.043 mm and the particle size of the calcium silicate is not larger than 0.074 mm. 27. The method according to any one of claims 20, 21 or v 5 22, characterized in that the metal oxide is aluminum oxide trihydrate. 28. The method according to any one of claims 20, 21 or 22, characterized in that 10 is the metal oxide magnesium oxide. 29. The method according to any one of claims 20, 21 or 22, characterized in that hei said metal oxide is a mixture of aluminum oxide trihydrate and magnesium oxide. ; 30) Water-resistant, phosphate-containing ceramic product according to the method described in claims 20, 21 or 22. 31. Ceramic products according to claim 30, characterized in that they have a foamed structure. 25th 32. Ceramic products according to claim 30, characterized in that they have an unfoamed structure. 30 33) Ceramic products according to claim 32, characterized in that they have a filling! Contain fabric. 34. The method according to any one of claims 20, 21 or! 35 "22, characterized in [that said reactive solution contains a surfactant. I / μ ** -— 1 35) Method according to one of claims 20, 21 or 22, characterized in that said mixture contains a fibrous reinforcing material . 5 v 36. The method according to any one of claims 20, 21 or 22, characterized in. * that the material mixture contains a foaming agent. 10 37) Method according to claim 36, characterized in that the foaming agent mentioned is a carbonate from the group MgCO ^, CaCO ^, ZnCO * or Li-CO-. is. 323 15 38) Method according to claim 36, characterized in that said foaming agent is a fluorinated hydrocarbon with a boiling point which is below the temperature at which said material mixture hardens. 20th 39. Process for producing a hard, water-resistant, phosphate-containing ceramic material, characterized in that it comprises the following process steps: 25 Providing a metal oxide, namely about 11 to about 65 parts by weight, calculated on an anhydrous basis, at least one metal oxide selected from the group Al ^ O ^, MgO, CaO, ZnO or their hydrates, preparing a reaction solution from a part of the 30 metal oxide mentioned and about 80 to about 190 parts by weight of a phosphoric acid solution, correspondingly! the equivalent of about 35 to about 75% by weight of phosphorus pentoxide, based on the weight of the acid solution, the water of hydration of said metal oxide 35 being included in the calculation of the phosphorus pentoxide content, * producing a mixture of the remaining metal oxide and about 100 parts by weight of calcium silicate, i proportional mixing of the said mixture with i * 1 of the reactant solution, and provision of the material mixture obtained in a desired form in which the components are allowed to interact, 5 the amount of the metal oxide used to prepare the reaction solution v being so is chosen so that the point in time of hardening of this material mixture can be roughly predetermined with respect to the point in time of the evaporation of water. * 10 40. The method of claim 39, characterized in that about 13 to about 26 parts of metal oxide, about 100 parts of calcium silicate and about 90 to about 150 parts of one 15 phosphoric acid solution, equivalent to about 40 to about 70% phosphorus pentoxide, may be used. 41. The method according to claim 39, characterized in that approximately 15 to | about 22 parts of metal oxide, about 200 parts of calcium silicate, and about 100 to about 130 parts of a phosphoric acid solution, equivalent to about 45 to about 65% phosphorus pentoxide, 25 can be used. 42. The method according to any one of claims 39, 40 or 41, characterized in that the particle size of said metal oxide is not 30 greater than 0.043 mm and the particle size of the mentioned | calcium silicate is not greater than 0.074 mm. ; 43) Method according to one of claims 39, 40 or 41, i characterized in that! 35 the metal oxide is aluminum oxide trihydrate. j r i 44) Method according to one of claims 39, 40 or 41, l:, characterized in that; /. 1 said metal oxide is magnesium oxide. 45. The method according to any one of claims 39, 40 or 41, characterized in 5 that the metal oxide mentioned is a mixture of aluminum oxide trihydrate and magnesium oxide. 46. Water-resistant, phosphate-containing ceramic product * 10 according to the method described in claims 39, 40 or 41. 47. Ceramic products according to claim 46, characterized in that they have a foamed structure. 48. Ceramic products according to claim 46, characterized in that they have an unfoamed structure. 20th 49. Ceramic products according to claim 48, characterized in that they contain a filler. 25 50) Method according to one of claims 39, 40 or 41, characterized in that said reaction solution contains a surfactant. I 51) Method according to one of claims 39, 40 or 30 41, characterized in that said mixture contains a fibrous reinforcing material. i ί 52. The method according to any one of claims 39, 40 or i 35 41, characterized in that j i that the material mixture mentioned has a foaming agent ί. contains. Ί? i J! ί V * - 11 - 1 53) Method according to claim 52, characterized in that this foaming agent is a carbonate from the group MgCO ^, -CaCO ^, ZnCO ^ or Li ^ CO ^. 5 54. The method according to claim 52, characterized in that this foaming agent is a fluorinated hydrocarbon having a boiling point which is below the temperature at which 10 the material mixture mentioned hardens. 55. Composition suitable for producing a hard, water-resistant, phosphate-containing ceramic material, characterized in that this composition contains the following constituents: approximately 11 to approximately 65 parts by weight, calculated on an anhydrous basis, at least one metal oxide from the group Al ^ O ^, MgO, CaO or ZnO or their 20 hydrates, approximately 80 to approximately 190 parts by weight of a phosphoric acid solution, corresponding to the equivalent of approximately 35 to approximately 75% by weight of phosphorus pentoxide, based on the weight of the acid solution, the water of hydration of the metal oxide being used in the calculation of the Phosphorus pentoxide content, and about 100 parts by weight of calcium silicate. 30 56) Composition according to claim 55, characterized in that it contains about 13 to about 26 parts of metal oxide, about 100 parts of calcium silicate and about 90 to about 150 parts of a phosphoric acid solution, corresponding to the equivalent 35 of about 40 to about 70% phosphorus pentoxide. j 57. The composition of claim 55, characterized in that it contains approximately 15 to approximately 22 parts of metal oxide, approximately 100 parts of calcium silicate and approximately 100 to approximately 105 parts of a phosphoric acid solution equivalent 5 from about 55 to about 65% phosphorus pentoxide. t * 58) Composition according to one of Claims 55, 56 or 57, characterized in that the particle size of the metal oxide mentioned is not greater than 0.043 mm and the particle size of the calcium silicate is not greater than 0.074 mm. 59. Composition according to one of claims 55, 56 15 or 57, characterized in that the metal oxide mentioned is aluminum oxide trihydrate. 60. Composition according to one of claims 55, 56 or 57, characterized in that 20 that said metal oxide is magnesium oxide. 61. Composition according to one of claims 55, 56 or 57, characterized in that it is a mixture of aluminum oxide trihydrate and 25 contains magnesium oxide. 62. Composition according to one of claims 55, 56 or 57, characterized in that it contains a surfactant. 30th 63. Composition according to one of claims 55, 56 or 57, characterized in that it contains a fibrous reinforcing material. 35 i> 64) Composition according to one of claims 55, 56 or 57, characterized in - ^ ___ n e t that it contains a foaming agent. I f «4 1 65) Composition according to claim 64, characterized in that this foaming agent is a carbonate from the group MgCO ^, CaCO ^, ZnCO ^, or Li2C0 ^. 5 66. Composition according to claim 64, characterized in that this foam. * is a fluorinated hydrocarbon with a boiling point that is below the temperature at which * 10 the mentioned mixture of materials hardens. 67. Hard, water-resistant, phosphate-containing ceramic material which is obtained by reacting (1) about 11 to about 65 parts by weight, calculated on an anhydrous basis, at least one metal oxide selected from the group containing Al ^ O ^, MgO, CaO or ZnO or their hydrates, (2) about 80 to about 190 parts by weight of a 20 phosphoric acid solution, corresponding to the equivalent of about 35 to about 75 parts by weight of phosphorus pentoxide, based on the weight of the acid solution, the water of hydration of said metal oxide being in the calculation of the phosphorus pentoxide content is included, 25 and (3) approximately 100 parts by weight of calcium silicate. 68. Composition according to claim 67, characterized. to contain about 13 to about 26 parts metal oxide, about 100 parts calcium silicate and about 90 to about 150 parts phosphoric acid solution, equivalent to about 40 to about 70% phosphorus pentoxide. 35 » 69. Composition according to claim 67, characterized in that it contains approximately 15 * - »·· - φ M 1 to approximately 22 parts of metal oxide, approximately 100 parts of calcium silicate and approximately 100 to approximately 130 parts of a phosphoric acid solution, corresponding to the equivalent of approximately 45 to contains about 65% phosphorus pentoxide. % 70. Composition according to one of claims 67, 68 or 69, characterized in that the ceramic material is obtained by reacting “10 ren a reaction solution and a component mixture, the i-reaction solution said phosphoric acid solution and at least part of said metal oxide, and that said component mixture calcium silicate and .The remaining metalloixd 15 contains. 71. Composition according to one of claims 67, 68 or 69, characterized in that the amount of the metal oxide used to prepare the reaction solution mentioned and the temperature of the reaction solution are selected such that the time at which this material hardened Mix can be roughly predetermined with respect to the time of the evaporation of water. 25th 72. The composition according to claim 71, characterized in that the particle size of the metal oxide mentioned is not greater than 0.043 mm and the particle size of the calcium silicate is not greater than 30 o 0.074 mm. 73. Composition according to claim 71, characterized in that said metal oxide is aluminum oxide trihydrate. 35 74. Composition according to claim 71, characterized in that said metal. i .JT * oxide is magnesium oxide. v_ • ^ * 1 75) Composition according to claim 71, characterized in that the said metal oxide is a mixture of aluminum oxide trihydrate and magnesium oxide. 5 » 76. Composition according to claim 71, characterized in that said - ceramic material contains a surfactant. 10 77) Composition according to claim 71, characterized in that said ceramic material contains a fibrous reinforcing material. 15 78) Composition according to claim 71, characterized in that it contains a foaming agent. 79. Composition according to claim 78, thereby! 20 characterized that this foam picture! ner from the group MgCO ^, CaCO ^, ZnCO ^ or Li ^ CO- I. l 80) composition according to claim 78, characterized i j 25 characterized in that the said. j Foaming agent is a fluorinated hydrocarbon with a boiling point below the temperature at ! which hardens the mixture of materials mentioned. j / - --- ¾ I 30 x ε l 5 «:» ΐ i