FR2507591A1 - WATER-RESISTANT RIGID PHOSPHATE CERAMIC MATERIALS AND PROCESSES FOR THEIR PREPARATION - Google Patents

Abstract

TO PRODUCE THIS CERAMIC MATERIAL, A METAL OXIDE CONTAINING APPROX. 11-65 PARTS CALCULATED ON AN ANHYDROUS BASIS OF AT LEAST AL0, MGO, CAD, ZNO AND THEIR HYDRATES; A REACTION SOLUTION CONSISTING OF PART OF THE METAL OXIDE AND APPROX. 80-190 PARTS OF A SOLUTION OF PHOSPHORIC ACID A APPROX. 35-75 BY WEIGHT IN IN RELATION TO THE WEIGHT OF THE ACID SOLUTION, THE WATER OF HYDRATION OF SAID METAL OXIDE BEING INCLUDED IN CALCULATING THE PHOSPHORIC ANHYDRIDE CONTENT; A MIXTURE OF THE REST OF THE OXIDE AND APPROX. 100 PARTS OF CALCIUM SILICATE; THE TEMPERATURE OF THE SOLUTION IS SET TO A DESIRED VALUE; THE MIXTURE IS MIXED WITH THE SAID SOLUTION AND THE MIXED MATERIAL IS PLACED IN A DESIRED CONFIGURATION AND ITS CONSTITUENTS ARE REACTED, THE QUANTITY OF OXIDE TO PREPARE THE SAID SOLUTION AND THE TEMPERATURE OF THE SAME BEING SELECTED PREVIOUSLY OR FINISHED THEREFORE. MIXED MATERIAL BECOMES RIGID OF THE TIME THE WATER VAPORIZATION BEGINS. (PARTS SHOWN ARE WEIGHT PARTS).

Description

2507 891

  CERA <MIQUES WATER-RESISTANT RIGID PHOSPHATE MATERIALS

AND METHODS FOR THEIR PREPARATION.

  The present invention relates to

  water-resistant, rigid phosphates, and more particularly rigid, water-resistant phosphated ceramic materials which do not require hardening

subsequent thermal.

  Refractory metal phosphates are

  naked for a long time as useful materials in the construction

  tion and isolation Compositions comprising

  phosphoric acid, a metal oxide, and metal silicates.

  rates are known in the art; however,

  containing these constituents and having a resistance

  sufficient mechanics are extremely difficult to prepare

  For example, mixtures of aluminum oxide and 85% phosphoric acid are viscous and difficult to handle. If such mixtures are diluted with water, ease of handling is greatly improved;

  nevertheless, when adding a silicate, for example

  calcium, and that the resulting phosphate is hardened

  thermally to remove excess water, the man-

  refractory material obtained has a tensile strength

  comparatively mediocre. Alternatively, if all the

  are mixed together in one go without

  additional water, this results in a rapid reaction that does not allow handling under

normal manufacturing.

  It is found in the prior art various

  phosphatic compositions and methods for preparing

  For example, U.S. Patent 2,992,930 of July 18, 1961 to William Wheeler et al.

  compositions comprising oxides of zirconium or

  luminium powder, calcium silicate for stabilization

  foam, phosphoric acid, a soil binder

  silica and a blowing agent, the composition being preferably

  prepared by mixing the dry ingredients, adding the

  silica sol, stirring the mixture with phosphoric acid

  phoric and allowing the resulting foam to become

  The United States Patent 3,148,996 of September 15, 1964 to Mark Vukasovitch et al.

  compositions that take on a rigid mass without heating

  and which can be made porous by incorpora-

  These compositions consist of

  of water, an acid phosphate consisting of phosphoric anhydride

  calcium, aluminum or zirconium oxides, and finely divided calcium silicate.

  preparing a viscous solution of water, phosphorus

  Phoric and a suitable metal oxide, adding calcium silicate to the mixture and allowing it to partially cure. Foaming is then effected by adding an internal foaming agent or mechanically introducing gas bubbles. US Pat. No. 3,330 675 of July 11, 1967 in the name of Jules Magder discloses compositions comprising aluminum acid phosphate, magnesium carbonate, oxide, hydroxide or silicate or zirconium and organic or inorganic gas-producing materials In a similar manner, other patents describe phosphatic foams of the same kind in which a powdered metal is incorporated in the acid mixture, so as to produce a formation of

  foam by release of hydrogen gas.

  Although it is evident from these references that a great deal of effort has been devoted to the development of useful phosphate foams, many problems still exist. Most foams of the prior art have poor mechanical strength.

  rendering them unusable as building materials.

  Some are moisture sensitive, many require thermal cure for improved strength, and most contain other additives

  to avoid problems of low mechanical strength.

  In addition, most foams produced indus-

  trially contain blowing agents that can

  increase the cost of the product and sometimes contribute -

weak bonding.

  It is therefore an object of the present invention to provide mechanically resistant, moisture resistant, phosphated ceramic materials which can be prepared

  without the use of external heat.

  Another object of the present invention is to provide

  methods for the preparation of rigid phosphatic foams without the use of added blowing agents. Another object of the present invention is

  to provide processes for convenient and continuous production

  phosphate foam so that a slump of

the foam is avoided.

  Other aims and advantages of the invention result from

  will be further described below.

  The present invention relates to ceramics

  rigid phosphates, water-resistant, which can be prepared from constituents comprising an oxide

  of metal, calcium silicate and phosphoric acid.

  By reacting some of the metal oxide in advance with phosphoric acid and / or adjusting the temperature

  of the acid solution when it is co-oxidized with the

  ingredients, one can act on the character of the foam.

  to obtain a phosphatized ceramic material

foam or not.

  According to a preferred embodiment, the method of the present invention comprises the steps of

  (1) choose at least one metal oxide in the group

  by A 1203, g O, Ca O or Zn O or their hydrates, this metal oxide constituting a total of about 11 to about

  parts by weight calculated on an anhydrous basis; (2) pre-

  paring a reaction solution comprising a portion of the metal oxide and from about 80 to about 190 parts by weight;

  weight of a phosphoric acid solution comprising the equi-

  from about 35 to about 75% by weight of phosphorus

  phorique relative to the weight of the acid solution, the hydration water of said metal oxide being included during the

  calculation of phosphoric anhydride content; and (3) pre-

  admixing a mixture comprising the remainder of the metal oxide and about 100 parts by weight of calcium silicate. The temperature of this reaction solution is adjusted to a desired value and the mixture is proportionally mixed.

  with this reaction solution The resulting mixed material

  aunt is placed in a desired configuration and

  The amount of metal oxide used to prepare the reaction solution and the temperature of the reaction solution are selected to approximately predict the moment when the intermingled material becomes rigid with respect to the moment.

  o The vaporization of the water occurs.

  In a second embodiment, the method

  according to the present invention comprises the steps which

  attempt to (1) prepare a mixture comprising from about 11 to

  about 65 parts by weight calculated on an anhydrous basis of at least one metal oxide selected from A 1203, 1 g O, Ca O, Zn O

  and their hydrates, and about 100 parts by weight of silicone

  calcium carbonate; and (2) preparing a reaction solution comprising from about 80 to about 190 parts by weight of iune

  phosphoric acid solution comprising the equivalent of

  about 35 to about 75% by weight of phosphoric anhydride

  relative to the weight of the acid solution, the hydra-

  said metal oxide being included in the calculation

  the phosphoric anhydride content.

  of the reaction solution to a desired value and

  the solution is mixed proportionally with this mixture.

  The resulting mixed material is placed in a configu-

  The temperature of the reaction solution is chosen so as to approximately pre-determine the moment when the mixed material becomes rigid with respect to the moment.

  o The vaporization of the water occurs.

  In a third mode of implementation, the present

  the invention comprises the steps of (1) selecting at least one of A 1203, g O, Ca O, Zn O and

  their hydrates, the metal oxide constituting a total of

  11 to about 65 parts by weight calculated on an anhydrous basis; (2) preparing a reaction solution comprising a portion of the metal oxide and from about 80 to about parts by weight of a phosphoric acid soltuion comprising the equivalent of about 35 to about 75% by weight

  phosphoric anhydride in relation to the weight of the solu-

  acid, the water of hydration of said metal oxide being

  included in the calculation of the phosphoric anhydride content

  than; and (3) prepare a mixture comprising the remainder of

  the metal oxide and about 100 parts by weight of silica

  The mixture is proportionally mixed with the reaction solution and the resulting mixed material

  aunt is placed in a desired configuration where

  Its constituents react with each other The amount of metal oxide that is used to prepare the solution is

  chosen to predetermine the approximate

  where the mixed material becomes rigid with respect to

  when water vaporization occurs.

  In a fourth mode of implementation, the present

  the invention comprises a composition which can be used for

  a rigid phosphatized ceramic material resistant to

  water, this composition comprising (1) from about 11 to about

  about 65 parts by weight calculated on an anhydrous basis of at least one metal oxide selected from A 1203, NgO, CaO, ZnO and their hydrates (2) from about 80 to about 190 parts by weight.

  weight of a phosphoric acid solution comprising the equi-

  from about 35 to about 75% by weight of phosphorus

  phorique relative to the weight of the acid solution, the water of hydration of said oxy / metal being included during the

  calculation of phosphoric anhydrous content; and (3)

  100 parts by weight of calcium silicate -

  In a fifth mode of implementation, the pre-

  The invention comprises a rigid phosphate ceramic material resistant to water obtained by reacting (1)

  about 11 to about 65 parts by weight calculated on a basis of

  anhydrate of at least one metal oxide selected from A 1203,

  Mg O, CaO, ZnO and their hydrates; (2) from about 80 to about

  190 parts by weight of a phosphoric acid solution

  which comprises the equivalent of about 35 to about 75% by weight of phosphoric anhydride relative to the acid solution, the water of hydration of said metal oxide being

  included in the calculation of the phospho-

  America; and (3) about 100 parts by weight of calcium silicate. Constituents used for the implementation of

  The present invention is all available in the

  Calcium silicate (100 parts by weight) is preferably

  in the practice of the present invention, but

  other silicates can also give good results

  The calcium silicate exists in nature and is called wollastonite. Suitable foam products or not can be obtained when this material is used in a spray form as described below. For the formation of foams, particle size will preferably be small enough so that most of the silicate passes through a Tyler NO 200 screen (0.074 mm

mesh opening).

  A number of metal oxides, such as aluminum oxide, magnesium oxide, can be used.

  calcium oxide and zinc oxide to obtain a

  These oxides are used in the form of powder, particulate oxides

  quite thin, of the order of 0.044 mm or less giving

  Hydrated forms of the oxide can also be used and in many cases are preferred. In the case where a hydrate is used, the water of hydration must be taken into account so as not to provide water. excess water for the reaction This

  can be done conveniently by including hydrata-

  when calculating the phosphoric anhydride content

  of the phosphoric acid solution.

  It can be used from about 11 to about 65

  by weight of metal oxide calculated on an anhy-

  per 100 parts of calcium silicate in the practice of the present invention; however, amounts of about 13-26 parts of metal oxide and

  in particular about 15-20 parts The amount of oxy-

  of which is used will depend on whether it is in a

  me hydrated or not and / or its reactivity.

  Anhydrous magnesium oxide reacts much more

  quickly with phosphoric acid as aluminum oxide

  For example, the former will react in a few minutes while the second may require hours, depending on the temperature of the acid solution. If hydrated forms are used, however, the difference in reaction times is dramatically reduced. Hydrated magnesium oxide reacts faster than anhydrous magnesium oxide, and it also reacts faster than hydrated aluminum oxide Nevertheless, aluminum oxide

  hydrate is significantly more reactive than aluminum oxide

  because it reacts with the phosphoric acid solution

  phoric over a period of time in minutes rather than hours The implications of reaction times will be

  described more fully below.

  Appropriate products can be obtained by using

  any of the oxides listed, alone or in combination, but anhydrous magnesium oxide (calcined)

  and hydrated aluminum oxide are particularly preferred.

  SUMMARY OF THE INVENTION Magnesium oxide tends to increase the mechanical strength and moisture resistance of the final product while

  aluminum oxide tends to give

  higher levels of caking.

  Phosphoric acid is available at various

  the concentration of 85% being the most common

  for orthophosphoric acid Other composi-

  such as polyphosphoric acid, which will give

  phosphoric acid when diluted with water may

  The total water content of the reaction system is not too high. Too much water should be avoided because products which, although resistant to water, would have poor mechanical strength.

  too little water is harmful as well, not only

  because the mutual mixing of materials is difficult.

  but because, in the case of products in the form of foam, only

high density foams.

  In general, the phosphoric acid will be useful if it contains the equivalent of about 35 to about 75% by weight of phosphoric anhydride based on the weight of the acid solution. phosphoric acid will be around 40-70% and in particular

  approximately 45-65% The remaining portion of the acid solution

  of water, including, for calculations, any water of hydration derived from the metal oxide. From about 80 to about 190 parts by weight of the acid solution may be used in the setting of of the present invention, but preferably from about 90 to about 150 parts and in particular from about 100 to about

parts of acid.

  Although the constituents used in the practice of the present invention have long been used in the art, the benefits to be obtained when

  these constituents are combined as described here have never

  but has been pointed out It has been found that if one regulates the way in which the constituents are combined and avoids an excess

  water, a product that does not require hardening is

  thermal insulation and is water resistant.

  deresse does not wish to be limited by any theory

  As regards the nature of the reactions involved in the present invention, two separate but interrelated phenomena appear to occur, namely water vaporization and binding of materials.

  produced by the bodies in reaction vaporizes the water present

  te, so that the water vapor can play the role of agent

  foaming For about the same time, it occurs

  bonding or caking which results in the formation of

  of a rigid material of the ceramic type.

  nomenes will be referred to here as "vaporization" or "vapor stage"

  "caking" or "caking stage", respectively. To practice the present invention, a reaction solution is preferably prepared by adding

  a desired portion of the metal oxide to the solution of

  In addition, liquid additives such as surfactants can also be incorporated into the reaction solution. Then the remainder of the metal oxide is combined with the total calcium silicate and mixed with any additives. solid, such as

  reinforcing fibers, thickeners, a colored material

  The temperature of the reaction solution is preferably set to a desired value and the solution is mixed proportionately with the remaining dry ingredients. The mixed material is then put into a desired configuration and the components of the L 3 system react between The products that are obtained do not require thermal hardening and can be put in boiling water without any adverse effect.

  they are not sensitive to heat because samples are

  ions were heated to 8710 C without significant loss of

mechanical resistance.

  It has been found that the relative moments when vaporization and bulk take place determine the nature of the product that is obtained. For example, if the vaporization stage is reached before the caking stage, the water vapor Foams the mixture before the mass becomes rigid Conversely, if the bulk takes place first, the material is unable to

  foam and water vapor escapes through interspaces

  The implications of this last succession of

  events will be described in more detail below, but in each case, a product that requires

  no thermal hardening, and yet which is resistant

so much to the water.

  Two factors contributing to the events

  above are the amount of metal oxide which is reacted in advance with the phosphoric acid and the temperature of the reaction solution at the moment when it is

  combined with the remaining dry ingredients -If

  only one of these factors, one can still obtain a

  However, it is better to

  set both parameters to facilitate the handling of

  to obtain a superior product.

  We will indicate below how we can do

  In general, if a relatively small amount of the metal oxide is reacted in advance with phosphoric acid, there will be relatively

  more foam formation during the blending step

  before the material mass becomes rigid, as long as the temperature of the acid solution is not too low Conversely, if a relatively larger amount of the metal oxide is reacted in advance, phosphoric acid, there will be less foam formation Fo before the mass becomes rigid If we do

  react in advance enough metal oxide, there will be sen-

  no foam formation. This result is ob-

  held-apparently because the prior addition of the metal oxide tends to prolong the duration of the reaction

  or exothermic reactions that vaporize the water.

  The temperature of the reaction solution during

  the subsequent mixing step may also have an influence

  this important on the resulting product The higher the temperature

  of this solution is high, the more violent the

  water vapor and earlier vaporization occurs.

  duit when the reaction solution is mixed with the remaining dry ingredients So, if the temperature is

  too high, the probability is greater than we obtain

  hold mosses that contain cavities or that

  foam quickly and then collapse.

  this effect, however, by including an agent

  sio-active in the reaction solution.

  If the temperature is too low, the reaction

  exothermic can be suppressed, so that it does not

  In addition, too low a temperature can be harmful because the resulting material could

  have a relatively low binding strength

  The optimum temperature of the reaction solution may vary according to the reactants, but

  In general, it has been found that a range of temperatures

  from about 20 ° C. to about 270 ° C. will give satisfactory results.

  preferred temperature is about 3-7 OC, and in particular

  to a temperature of about 4.50 C, unless we add

  a wetting agent as described below.

  In practice, other factors must be taken into account besides the amount of material reacted in advance and the temperature of the acid solution.

  many of these other factors depending on the type of pro-

  to obtain When one produces foams, the goal is

  to ensure that the mass reaches a decent height

  at the moment when the setting in mass occurs Essentiel-

  In this case, the vaporization of the water which causes the formation of foam must be adjusted in time so that it gives a uniform cell size in a product having the correct height and density once the caking is complete. The size of the cells is influenced by the rate at which the water vapor is

* released and by the viscosity of the acid solution

  cosity, in turn, depends on the type of oxide or oxy-

  used, the particle size of the oxide and

  the temperature of the acid solution.

  Solutions with viscosities are obtained

  different when the various oxides are dissolved in the

  For example, when quantities increase

  magnesium oxide are added to an aliquot of a normal concentration

  (eg 85%), it is observed that the visco-

  range from about 50 c Po to 1000 c Po to 22,20 C All-

  Once, when comparable molar amounts of aluminum oxide are added to a second aliquot

  of the male solution of acid at 22.20 C, we observe

  Costs of about 50 c Po at only 400 c Po To produce higher foams, it is preferred that the viscosity

  of the acid solution at the moment of mixing with the

  remaining quantities do not exceed about 400 c Po Thus, it will be seen that a second limitation to the use of oxide

  magnesium, in addition to its tendency to cause

  violent foam, is the viscosity of the solution

  reaction that results when used.

  The higher the viscosity of the solution, the poorer the mixing operation and the poorer the foam quality of the product obtained. For this reason,

  it is often advantageous to use more than one oxide.

  Thus, an oxide could be used to prepare the

  reaction, and one could combine another with the calcium silicate Alternatively, the oxide could

  be used in the form of a mixture, both for

  Reaction solution only for mixing with calcium silicate Various possibilities exist; therefore, it is contemplated that all of these possibilities are included within the general scope of the present invention, and the present invention should not be construed as such.

limited to these two illustrations.

  The density of the final product will depend to a large extent on the amount of metal oxide

  is used to form the reaction solution; that is

  say that the more metal oxide there is, the more the mass

  In general, in the absence of added foaming agents, from about 0 to about 0.3 parts of metal oxide per portion of P 205 in the acid solution are used to form the solution. reaction, we will obtain foams with densities of about 0.64

  at about 0.24 g / cm 3 However, if more

  In the case of a metal oxide, it can be expected that a non-cellular ceramic material will be obtained. Nevertheless, practical considerations, such as viscosity, have an influence on the upper limit of the amount of material reacted to the metal. 'advanced; thus, usually, a proportion of

  not more than 50% of the metal oxide.

  Other considerations that influence

  on mosses are the particle size, the properties

  surface and reinforcing materials A granular

  Fine and uniform measurement is much preferred for the practice of the present invention because of the tendency of such a material to promote a fine cell structure. As previously indicated, metal oxides which pass through a Tyler NO screen 325 (0.044

  mm of mesh size) and calcium silicate which

  se through a Tyler N 200 sieve (0.074 mm aperture

mesh) are preferred.

  The size of the cells also depends on the

  surface properties of the material and it is often useful

  to include one or more surfactants that promote cell stability Virtually any surfactant

  which is not impaired by phosphoric acid may be used. A surfactant which has been found to be particularly satisfactory is

  dimethylocaine, which is sold by Armak under the name

  Aramox DMC It is important to take precautions in the

  manipulation of this material, however, because it is an irre-

ritant for skin and eyes.

  As the foams are of a porous nature, they

  tend to have lower tensile strength

  to those of materials that are not in the form of foam As a result, it is often recommended to add

  a reinforcing fibrous material for reinforcing the foam.

  Polyester, glass, polypropylene and nylon, among others, have been used successfully, but the conditions under which the final product will be used may have an influence on the choice of the fiber. For example, for a temperature application high fiber

  glass would be much more stable than organic fibers.

  Generally, lengths of fibers ranging from 3 mm to mm will be usable, fibers of about 13 mm being

specially usable.

  When preparing ceramic phospha-

  which are not in the form of foam, the factors

  such as particle size, viscosity, temperature,

  temperature and surface properties become much less

  because the cell structure is not important.

  Consequently, materials of coarser particle size and higher viscosity of the solution

  may be eligible, subject to the limitations

  mitations imposed by the maneuverability of the bodies in reaction.

  A much higher temperature can also be used for the reaction solution because the material which is not in the molded form will not sag. In addition, no surfactant will be required because

  there is no problem of cell stability.

  Apart from these considerations, the objective of preparing a ceramic material which is not in the form of foam is comparable to that consisting of

  to prepare a material in the form of foam, the difference

  major difference being that, with materials that are not in the form of foam, it is necessary to defer the vaporization stage until the mass has become

  rigid, thus preventing an expansion of phos-

  This is conveniently done by reacting to

  advance a greater amount of the metal oxide.

  However, care must be taken that water can escape from the non-foamed material.

  internal pressure becomes too great because of the pressure

  water, the rigid ceramic material will be cracked.

  For this reason, when preparing ceramics

  In the case of phosphates which are not in the form of foam, it is often advantageous to include porous fillers which provide passages through which water vapor can escape. Examples of satisfactory fillers

with vermiculite and perlite.

  Surprisingly, it has also been discovered that satisfactory foam materials can be produced by combining the techniques according to the present invention.

  invention with foaming agents taught by the tech-

  The prior art contains references relating to the use of carbon dioxide or materials producing carbon dioxide and hydrogen or hydrogen-producing materials.

  as well as other organic or inorganic materials

  gas producers, during the production of phosphoric

  Such agents can also be used

  in the production of water-resistant rigid phosphatic ceramic materials according to the present invention.

  Although we can use almost any

  which foaming agent of the prior art, the results that can be obtained are illustrated by

  The use of various carbonates is preferred.

  such as Mg CO 3, Ca CO 3, Zn CO 3, L 12 C 03 and carbonates

  of the same kind, or their mixtures, which produce phos-

  relatively insoluble phates; however, 14 g CO 3 is

  especially preferred because it typically produces a

  having relatively uniform cell sizes and a generally suitable density Other carbonates such as Na 2 C 03 and K 2003 which produce relatively soluble phosphoric acid salts can also be used when the leaching of phosphate from the resulting phosphated ceramic material when exposed to water will not be harmful. When dry foaming agents are used, it is usually advantageous to mix them with the other dry ingredients including calcium silicate and a part of the metal oxide; however, these foaming agents can also be added separately. foam obtained in the presence of such agents is not produced by the vaporization of water, it is undesirable that the release of heat occurs before

  For this reason, it is usual-

  necessary to react in advance a higher proportion of the metal oxide with the acid solution

  phosphoric Often this will cause an inde-

  the viscosity of the acid solution.

  quence, when using an added foaming agent, it may be necessary to dilute the acid solution a little

  in order to adjust the viscosity. However, we must take

  care should be taken to avoid the use of excess water as the combination of the use of additional water and the prior reaction of a larger quantity of the oxide

  metal tends to lower the temperature of the reaction

  eothermal, thus increasing the possibility of

  the production of a phosphatized ceramic material having

  unsatisfactory behavioral characteristics.

  As an additional consideration, the temperature

  The reaction solution, when mixing with the dry constituents, can often be higher when foaming using dry foaming agents, instead of using water spray, because It is often advantageous for the reaction solution to be in a preferred temperature range of about 10 to 167 ° C., when dry foaming agents are used.

  instead of the preferred range of about 3 to 70 C

  born above about the process of forming foam

by spraying water.

  Of course, it is also possible to use a liquid foaming agent such as a fluorinated hydrocarbon having a boiling point below the temperature at which the foaming of the foam occurs Examples of such hydrocarbons are those said Freon-11 or Freon-113 sold by Pont Hydrocarbons of this type can be added to the acid solution and mixed with it, or they can be added separately at the time of mixing with the solid ingredients. appropriate boiling point can be used too, but they are much less advantageous because of the inherent fire hazard associated with their use. The mode of addition of these foaming agents, wet or dry, may be a matter of choice for the operator, or it may depend on various factors such as the type of product desired and / or the type of equipment used In some cases, the technique of use

  can be determined by the nature of the foaming agent.

  For example, carbonates react chemically with

  the acid solution; thus, they can not be added

  to the acid solution too early in the sequence of

  Inversely, fluorinated hydrocarbons produced

  feel foam forming when moving from a liquid state

  in a gaseous state; thus, they can be maintained in

  with the acid solution if the temperature of the mixture remains sufficiently low In the latter case, however, it should be noted that fluorinated hydrocarbons form

  a two-phase system with the acid solution In

  sequence, care must be taken to ensure that the two-phase system is uniformly mixed before

  mix with the solid ingredients.

  As the technique describes a wide variety of materials that can be used in various ways to

  produce the phosphatic ceramic materials of the present

  In the invention, the term "foaming agents" as used herein should be understood to embrace all such materials,

  as long as they produce phosphor ceramics

  phatées having the characteristics specified above.

  The following examples, in which all parts are by weight, are presented by way of illustration to show the advantages of the present invention.

EXAMPLE 1

  A following constituent foam is prepared: phosphated from

  If we calculate these relationships by considering the oxy-

  of metal as anhydrous and including hydrata-

  As part of the acid solution, we obtain: Constituent Parts per 100 parts of Ca Si O 3

A 1203 23.56

H 3 P 04 to 75.9% 116.5

  (55% P 205) Ca Si O 3 100 surfactant 0.1 The reaction solution is prepared by adding

  1.04 parts of A 1203 3 H 20 to 104 parts of phosphoric acid

  that and stirring the mixture with moderate stirring during

  about 15 minutes until a clear solution is

  Weight Parts Constituting Podspour 100 parts (,) of Ca Si O 3 /

A 1203 3 H 30 14.42 36.04

H 3 PO 4 at 85% 41.58 104.0

  (61.6% P 205) Ca Si O 3 40.0 100 surfactant 0.04 0.1

  The surfactant (0.1 part) is added to the solution.

  reaction, which is then cooled to 4.5 ° C.

  remaining dry ingredients (100 parts calcium silicate

  cium and 35 parts of aluminum oxide trihydrate) are mixed together and fed into a Readco continuous processing apparatus. The reaction solution is also introduced into the Readco mixer through an orifice.

  different ingredients The ingredients are mixed together

  proportioned, unloaded on a walking belt covered with a light scrim, and

  foam starts in about 1.5 minutes and the mass of material

  This becomes a continuous block of material in the form of foam 2.5 cm thick and 12.7 cm wide. The material in the form of foam has a fine cellular structure. and

  a density of 0.288 g / cm 3 The compressive strength

  this material according to ASTM D 1621 is 41.19 N / m 2 (4.2 kg / cm 2). The modulus of rupture according to ASTM C 209 is 48.05 N / cm 2 (4, 9 kg / cm 2 No signs of cracking are detected when 20 g cubes of the product are placed in boiling water for 1/2 hour and left to dry or wetted with 50 g of water at room temperature and

left to dry.

EXAMPLE 2

  Phosphate foam is prepared from the metals

  my ingredients as in Example 1.

  reaction by adding 1.04 parts of A 1203 3 H to 104 parts of phosphoric acid and stirring the mixture with moderate stirring for about 15 minutes until a clear solution is obtained. (0.1 part) to the reaction solution.

  remaining dry ingredients (100 parts calcium silicate

  and 35 parts of aluminum oxide trihydrate) are

  mixed together and introduced into a trans-

  Readco Continuous Formation The reaction solution at room temperature, 22 C, is also introduced into the Readco mixer through a different addition port.

  ingredients are mixed in a proportionate way,

  loaded on a walking belt covered with a canvas

  The formation of the foam begins in about 42 seconds and the mass of material becomes rigid in about a second. In this way, a continuous block of material is obtained in the form of foam 2.5 cm thick and 12.7 mm thick. cm of width The material in the form

  of foam has a coarse, irregular cellular structure

  re, and a density of 0.272 g / cm 3 The compressive strength of this material according to ASTM D 1621 is 34.32 Nkm 2 (3.5 kg / c_ 2) The breaking modulus according to ASTM standard C 209 is 34.32 N / cm 2 (3.5 kg / cm 2) No detects

  sign of Cracking when cubes of 20 g of the product are

  in boiling water for 1/2 hour and then

  allowed to dry, or are wetted with 50 g of water at

  ambient and allow them to dry.

EXAMPLE 3

  Phosphate foam is prepared from the following constituents: Weight Parts Constituent (g) per 100 parts of Ca Si O 3

A 1203 3 H 20 11.44 30.1

Mg O (calcined) 3.0 7.9

H 3 P 04 to 80% 43.56 114.63

  (58.0% P 205) Ca Si O 3 38 100 Taisko-actf agent 0.3 0.79 Polyester fiber 1.27 cm 0.2 0.53

  If we calculate these relationships by considering the oxy-

  of anhydrous metal and including hydrate water.

  As part of the acid solution, we obtain: 2 'The reaction solution is prepared by adding

  1.15 parts of A 1203 3 H 20 to 114.63 parts of phosphoric acid

  and stirring the mixture with moderate agitation during

  about 15 minutes until a clear solution is obtained. The surfactant (0.79 part) is added to the

  reaction solution, which is then cooled to 4.5 C.

  The remaining dry ingredients (100 parts of calcium silicate, 28.95 parts of aluminum oxide trihydrate, 7.9 parts of magnesium oxide and 0.53 parts of polyester fiber) are mixed together and introduced into a Readco continuous processing unit The reaction solution is also introduced into the Readco mixer via a different addition port The ingredients are there

  proportionately mixed, unloaded on a cour-

  The foam formation begins in about 57 seconds and the mass of material becomes rigid in about 1 minute and 51 seconds. In this way, a continuous block of material in the form of foam is obtained. 2.5 cm thick and 12.7 cm wide The material in the form of foam has a fine cell structure and a density of 0.304 g / em 3 Lung resistance in this manner according to ASTMD 1621 is d & 68.64 Ncm 2 (7 kg / cm 2) The modulus of rupture according to ASTM C 209 is <1; 54, 85 / cn 2 (5, / c) m There is no evidence of cracking when cubes constituting parts per 100 parts of Ca Si O

A 1203 19.7

  Mg O (calcined) 7.9 H 3 P 04 to 73, T / o 125.05 (53.2% P 205) Ca Si O 100 Surfactant 0.79 Polyester fiber 1.27 cm 0 , 53 of 20 g of the product are placed in water for 1/2 hour and allowed to dry with 50 g of water at room temperature

let it dry.

EXAMPLE 4

  A phosphate foam is prepared with the following constituents: boiling

or are wet

and let them go from

  If we calculate these relationships by considering the oxy-

  of anhydrous metal and including hydrata-

  As part of the acid solution, the following is obtained: The reaction solution is prepared by adding 100 parts of 120% to 100 parts of phosphoric acid and stirring the mixture with moderate stirring.

  about 15 minutes until a clear solution is

  The surfactant (0.1 part) is added to the solution.

  reaction, which is then cooled to 4.5 ° C.

  remaining dry ingredients (100 parts calcium silicate

  and 35 parts of aluminum oxide trihydrate) are weight parts constituting Pds for 100 arties of Ca Si O 3

A 1203 3 H 20 16.0 40.0

H 3 PO 4 at 85% 40.0 100.0

  (61.6% P 205) Ca Si O 3 40.0 100.0 Tasio-active agent 0.04 0.1 Constituent Parts per 100 parts of Ca Si O 3

A 1203 26.15

H 3 P 04 to 74.7% 113.85

  (54.1% of P 205) Ca Si O 3 100 surfactant 0.1 2 i 07591

  mixed together and introduced into a trans-

  Readco Continuous Formation The reaction solution is also introduced into the Readco mixer through a different addition port. The ingredients are proportionately mixed, discharged onto a moving belt covered with a light scrim, and smoothed. Foam formation begins in about 1 minute and 45 seconds and the mass of material becomes rigid in about 2 minutes

  and 5 seconds in this way we obtain a continuous block

  naked material in the form of foam 2.5 cm thick

  12.7 cm wide The material in the form of

  has a fine cell structure and a density of

  0.464 g / cm 3 The compressive strength of this material is -

from 8, 3 7 / c 2 2

  AST 14 D 1621 is 82.371 / cm 2 (8.4 kg / cm 2).

  The breaking point according to ASTM C 209 is 82.37 N / cm 2 (8.4 k-cm 2). No evidence of cracking is detected when 20 g cubes of the product are placed in boiling water.

  for 1/2 hour and let them dry or are wet

  50 g of water at room temperature and that they are

let it dry.

EXAMPLE 5

  A phosphatized ceramic material that is not

  in the form of foam is prepared from the

  following components: Parts Constituent weight per 100 parts of Ca Si O 3

A 1203 3 H 20 18.4 40.89

H 3 P 04 to 85% 39.6 88.0

  (61.6% P 205) Ca Si O 3 45.0 100

  If we calculate these relationships by considering the oxy-

  of metal as anhydrous and including hydrata-

  As part of the acid solution, we obtain: The reaction solution is prepared by adding

  9.78 parts of A 1203 3 H 20 to 88 parts of phosphoric acid

  that and stirring the mixture with moderate stirring during

  about 15 minutes until a clear solution is obtained.

  The remaining dry ingredients (100 parts of calcium silicate and 31.1 parts of aluminum oxide trihydrate) are mixed together and fed to a Readco continuous processing apparatus. The reaction solution at room temperature is also introduced into the Readco mixer through a different addition port

  ingredients are mixed in a proportionate way,

  loaded on a walking belt covered with a canvas

  ger, and flattened Foam formation does not occur and the mixture becomes a solid mass in 2 minutes and 10 seconds Hard matter resembling a material

  ceramic has a density of 0.96 g / cm 3.

EXAMPLE 6

  A phosphated ceramic material is prepared from the following ingredients: Constituent Weight (g) Parts per 100 parts of Ca Slo 3

A 1203 3 H 20 17.44 38.76

H 3 P 04 to 72% 40.56 90.13

  (52.18% P 205) Ca Si O 3 45 100 Vermiculite (approx O, lg / cm) 4 8.89 Constituent Parts per 100 parts Ca Si O 3

A 1203 26.73

H 3 PO 4 at 73.2% 102.16

(53.1% P 205) Ca Si O 3 100

* If we calculate these relationships by considering the oxy-

  of metal as anhydrous and including hydrata

  As part of the acid solution, we obtain: The reaction solution is prepared by adding

  7.65 parts of A 1203 3 H 20 to 90.13 parts of phosphoric acid

  and stirring the mixture with moderate agitation until

  than to obtain a clear solution Dry ingredients

  remaining parts (100 parts calcium silicate, 31.11 parts

  of aluminum oxide trihydrate and 8.89 parts of vermiculite) are mixed together and fed into a Readco continuous processing apparatus. The reaction solution at room temperature (22 C) is also introduced into the Readco mixer by an addition orifice

  different The ingredients are mixed in a pro

  Portioned, unloaded on a walking belt covered with a light scrim, and flattened No foam formation occurs

  product and the mixture becomes a solid mass in 2

  nute and 30 seconds Hard material resurfacing at a

  ceramic material has a density of 0.944 g / cm 3.

EXEM PLE 7

  This example illustrates the use of a foaming agent of the prior art in combination with the

  the present invention to produce a phosphor ceramic material

  Phosphatic foam is prepared from

  Components per 100 Parts of Ca Si O 3

A 1203 25.34

H 3 PO 4 at 63% 103.55

  (45.4% P 205) Ca Si O 3 100 Vermiculite 8.89 Constituent

A 1203 3 H 20

  3 p O 4 to 68% (49.3% P 205) Ca Si O 3 Mg CO 3 Mg O (calcined) Talc load Weight (g) 8.97 56.03, 00 2.0 7.0, 0 Parts per 100 parts of Ca Si O 3 17.94

112.06

, 0 4.0 14.0, 0

  If we calculate these relationships by considering the oxy-

  of metal as anhydrous and including hydrata-

  As part of the acid solution, we obtain: Constituent Parts per 100 parts of Ca Si O 3

A 1203 11.72

H 3 P 04 to 64.4%

  (46.7% P 205) 118.27 Ca Si O 3 100.0 Ng C 03 4.0 Mg O O (calcined) 14, 0 Talc load 20.0

  The reaction solution is prepared at room temperature.

  room temperature by adding 17.94 parts of A 1203 3 H 20,

  by stirring with 112.06 parts of phosphoric acid solution

  The resulting clear solution is cooled to 13 C.

  The remaining dry ingredients (100 parts calcium silicates, 4.0 parts magnesium carbonate, 14.0 parts magnesium oxide and 20.0 parts filler) are mixed together and fed to a continuous process apparatus. Readco The reaction solution at 13 ° C. is also introduced into the Readco mixer via a different addition orifice. The ingredients are there

  proportionately mixed and unloaded on a cour-

  mobile site covered with a light scrim Because of the presence of the acid in the mixture, a formation of

  happens when the material leaves the mixer The material

  During the formation of foam is flattened and it solidifies in about 1 minute and 30 seconds, an exothermic reaction occurring about 30 seconds later as indicated by the release of water vapor The material in the form of rigid foam has a fine cell structure and a density of 0.192 g / cm 3 The compressive strength of this material according to ASTM D 1621 is 61.78 N / km 2 (6.3 kg / cm 2) and the modulus of rupture according to standard

  ASTM C 209 is 27.45 N / cm 2 (2.8 kg / cm 2) This material is

  when placed in the water, indicating that the water

  can not easily penetrate into the foam matrix.

EXAMPLE 8

  This example illustrates the use of a prior art liquid foaming agent to produce

  the phosphated ceramic material according to the present invention.

  A phosphated ceramic material is prepared from the following constituents: Weight Component per 100 parts (g) or 10 parts of Ca Si O 3

A 1203 3 H 20 9.0 18.0

H 3 P 04 to 80.2%

  (58.2% P 205) 53.0 106.0 Ca Si O 3 50.0 100.0 Freon-11 4.0 8.0 8.0 Mg O (calcined) 5.0 10.0 Talc load 10, 0 20.0

  If we calculate these relationships by considering the oxy-

  of metal as anhydrous and including the water of hydration as part of the acid solution, we obtain: Constituent Parts per 100 parts of Ca Si O

A 1203 11.8

H 3 P 04 to 75.8%

  (55% P 205) 112.2 Ca Si O 3 100.0 Freon-ll 8.0 Mg O (calcine) 10.0 Talc load 20.0

  The reaction solution is prepared at room temperature.

  room temperature by mixing 10 parts of A 1203 3 H 20, with stirring, with 106.0 parts of phosphoric acid solution,

  after which the reaction solution is cooled to 13 C.

  The remaining dry ingredients (100 parts of calcium silicate, 8.0 parts of aluminum oxide trihydrate, 10.0 parts of magnesium oxide and 20.0 parts of filler) are mixed together and introduced into an apparatus. The Ingredients are mixed proportionately, Freon-ll being added by a separate in-line mixer so that a good dispersion is obtained Mixed material leaves the mixer

  and foam formation occurs slowly in a period of time.

  3 minutes Solidification occurs in 4 minutes.

  and the exothermic reaction occurs in 4.5 minutes.

  The resulting coarse-cell foam has a mass of

light of 0.304 g / cm 3.

  It is obvious that the invention is not limited

  the modes of implementation described and that can be

ter all variants.

Claims (70)

  1 Process for producing a phosphoric ceramic material   rigid water-resistant phateate, characterized in that it comprises the steps of: preparing a metal oxide comprising from about 11 to about 65 parts by weight calculated on an anhydrous base of at least one oxide of metal selected from A 1203, MgO, CaO, ZnO and their hydrates, a reaction solution comprising a   part of the metal oxide and from about 80 to about 190   by weight of a phosphoric acid solution comprising the equivalent of about 35 to about 75% by weight of phosphoric anhydride based on the weight of the acid solution, the water of hydration of said metal oxide When a mixture comprising the remainder of the metal oxide and about 100 parts by weight of calcium silicate is included in the calculation of the phosphoric anhydride content, the temperature of the reaction solution is adjusted to a desired value. said mixture is proportionately mixed with the reaction solution, and   the resulting mixed material is placed in a confluence   t desired and allows its constituents to react with each other,   the amount of metal oxide used to prepare the solution   the reaction solution and the temperature of the reaction solution being selected to approximately pre-determine the moment when the mixed material becomes rigid relative to   at the moment when the water vaporization conr ence.   Process according to claim 1, characterized in that from about 13 to about 26 parts of metal oxide, about 100 parts of calcium silicate are used, and   from about 90 to about 150 parts of phosphoric acid solution.   phoric comprising the equivalent of about 40 to about 70% of phosphoric anhydride.   Process according to Claim 1, characterized in that from about 15 to about 22 parts are used.   of metal oxide, about 100 parts of calcium silicate   and about 0.1 to about 130 parts of phosphoric acid solution comprising the equivalent of about 45   about 65% phosphoric anhydride.   4 Process according to one of claims 1 to 3,   characterized by the fact that the temperature of the solution   the reaction temperature is from about 2 to about 27 ° C.   Method according to one of claims 1 to 3,   characterized by the fact that the temperature of the solution   of reaction is between 3 and 70 C approximately.   Process according to one of Claims 1 to 3,   characterized in that the temperature of the reaction solution is about 4.50 C.   Method according to one of claims 1 to 3,   characterized by the fact that the particle size   metal oxide is not greater than that of parti-   cules passing through a Tyler N O 325 sieve (0.044 mm   mesh size) and the particle size of the   Calcium is not greater than that of particulate   passing them through a No. 200 Tyler sieve (0.074 mm mesh size).   Process according to one of Claims 1 to 3,   characterized by the fact that the metal oxide is trihyde aluminum oxide drate.   Process according to one of Claims 1 to 3,   characterized by the fact that the metal oxide is oxy- of magnesium.   Method according to one of claims 1 to   3, characterized in that the metal oxide comprises a mixture of aluminum oxide trioxide and oxide magnesium.   The water-resistant phosphatized ceramic material obtained as a product of the process according to one of the Claims 1 to 3.   Products according to claim 11, characterized   rised by the fact that they have a foam structure.   Products according to claim 11, characterized   rised by the fact that they do not have a foam structure.   Products according to claim 13, characterized   terized by the fact that they include a charge.   Method according to one of claims 1 to   3, characterized in that the reaction solution comprises a surfactant.   Method according to one of claims 1 to   3, characterized in that the mixture comprises a reinforcing fiber.   Method according to one of claims 1 to   3, characterized in that the mixed material comprises a foaming agent.   18. Process according to claim 17, characterized   rised by the fact that the foaming agent is a carbonate   selected from Mg 3 CO 3, Ca C 03, Zn CO 3 and Li 2 CO 3 O 3.   19. Process according to claim 17, characterized   rised by the fact that the foaming agent is a hydrocarbon   fluorinated having a boiling point lower than the   erature to which the mixed material becomes rigid.   Process for producing a ceramic material   rigid phosphate water resistant, characterized in that it comprises the steps according to which:   has prepared a melane comprising from about 11 to   65 parts by weight calculated on an anhydrous basis of at least   a metal aid of 1203, Mg O, Ca O, Zn O and their hydra-   and about 100 parts by weight of calcium silicate, a reaction solution comprising from about 80 to about 190 parts by weight of a phosphoric acid solution comprising about 35 to about 75% by weight of phosphoric acid is prepared. phosphoric anhydride relative to the weight of the acid solutk, the water of hydration of said metal oxide being included in the calculation of the phosphoric anhydride content,   the temperature of the reaction solution is to a desired value,   the said material is proportionately mixed   mixed with the reaction solution, and the resulting mixed material is placed in   a desired configuration, and the compounds are left   between them, the temperature of the reaction solution being chosen to approximately predict the moment when the mixed material becomes rigid with respect to the moment   o The vaporization of the water occurs.   Method according to claim 20, characterized   due to the use of from about 13 to about 26 parts of metal oxide, about 100 parts of silicate   calcium and from about 90 to about 150 parts of   phosphoric acid comprising the equivalent of about   about 70% phosphoric anhydride.   Process according to claim 20, characterized   due to the fact that about 15 to about 22 parts of metal oxide are used, about 100 parts of silicate   calcium, and from about 100 to about 130 parts of   phosphoric acid comprising the equivalent of approximately   45 to about 65% phosphoric anhydride.   Method according to one of the claims 20   22, characterized in that the temperature of the   The reaction rate is from about 2 to about 270 ° C.   Method according to one of the claims 20   22, characterized in that the temperature of the   the reaction rate is between about 3 and 70 ° C.   Method according to one of the claims 20   22, characterized in that the temperature of the   The reaction rate is about 4.50 C.   Method according to one of claims 20 to   22, characterized by the fact that the particle size   metal oxide is not greater than that of parti-   by means of a Tyler N O 325 sieve (0.044 mm mesh aperture) and the particle size of the   Calcium silicate is not greater than that of   particles passing through a Tyler N O 200 sieve (0.074 mm mesh opening).   Method according to one of claims 20 to   22, characterized in that the metal oxide is aluminum oxide trihydrate.   Method according to one of claims 20 to   22, characterized in that the metal oxide is magnesium oxide.   Method according to one of claims 20 to   22, characterized in that the metal oxide comprises a mixture of aluminum oxide trihydrate and oxide magnesium.   The phosphatic ceramic material resistant to   the water obtained as a product of the process according to one of the sales 20 to -22.   Products according to claim 30, characterized   rised by the fact that they have a foam structure.   Products according to claim 30, characterized   laughed at the fact that they do not have a foam structure.   Products according to claim 32, characterized   rised by the fact that they include a charge.   Process according to one of claims 20 to   22, characterized in that the reaction solution comprises a surfactant.   Method according to one of claims 20 to   22, characterized in that the mixture comprises a reinforcing fiber.   Method according to one of claims 20 to   22, characterized in that the mixed material take a foaming agent.   37. The method of claim 36, characterized   rised by the fact that the foaming agent is a carbonate   selected from Mg C 03, Ca C 03, Zn CO 3 and Li 2 C 03.   The method of claim 36, characterized   rised by the fact that the foaming agent is a hydrocarbon   fluorinated product having a lower boiling point than the   erature to which the mixed material becomes rigid.   39 Process for producing a ceramic material   rigid phosphate water resistant, characterized in that it comprises the steps according to which:   a metal oxide comprising   11 to about 65 parts by weight calculated on a basis   An anhydride of at least one inert oxide selected from A 1203, MgO, CaO, ZnO and hydrates thereof is prepared, a reaction solution comprising a portion of the metal oxide and from about 80 to about by weight of a phosphoric acid solution comprising the equivalent of about 35 to about 75% by weight   phosphoric anhydride in relation to the weight of the solu-   acid, the water of hydration of said metal oxide state comprioelors the calculation of the phosphoric anhydride content, is prepared a mixture comprising the rest of   the metal oxide and about 100 parts by weight of silicon calcium carbonate,   the said material is proportionately mixed   mixed with the reaction solution, and the resulting mixed material is placed in a desired configuration and its components are allowed to react with each other,   the amount of metal oxide used to prepare the   the reaction rate being chosen so as to predetermine   approximately the moment when the mixed material   comes rigid with respect to when the vaporization of water occurs.   Method according to claim 39, characterized   due to the fact that about 13 to about 26 parts of metal oxide are used, about 100 parts of silicate   calcium and from about 90 to about 150 parts of   phosphoric acid comprising the equivalent of about   At about 70% phosphoric anhydride.   41. The method according to claim 39, characterized   wherein from about 15 to about 22 parts of metal oxide, about 100 parts of calcium silicate and from about 100 to about 130 parts of phosphoric acid solution comprising the equivalent of about 45   about 65% phosphoric anhydride.   42 Method according to one of claims 39 to   41, characterized in that the particle size   metal oxide is not greater than that of parti-   cules passing through a Tyler N O 325 sieve (0.044 mm   mesh size) and the particle size of the   calcium licate is not superior to that of particles   passing through a No. 200 Tyler sieve (0.074 mm opening mesh size).   43 Method according to one of claims 39   at 41, characterized in that the metal oxide is aluminum oxide trihydrate.   44 Method according to one of claims 39   at 41, characterized in that the metal oxide is magnesium oxide.   Method according to one of Claims 39 to   41, characterized in that the metal oxide comprises a mixture of aluminum oxide trihydrate and magnesium oxide. 46 Phosphatic ceramic material resistant to   the water obtained as a product of the process according to one of the sales 39 to 41.   47 Products according to claim 46, characterized   rised by the fact that they have a foam structure.   48 Products according to claim 46, characterized   laughed at the fact that they do not have a foam structure.   49 Products according to claim 48, characterized   rised by the fact that they include a charge.   Method according to one of Claims 39 to   41, characterized in that the reaction solution comprises a surfactant.   Method according to one of claims 39 to   41, characterized in that the mixture comprises a reinforcing fiber.   Method according to one of claims 39 to   41, characterized in that the mixed material comprises a foaming agent.   The process according to claim 52, characterized   in that the foaming agent is a selected carbonate   from Mg C 03, Ga Ca 3, Zn CO 3 and Li 2 CO 3.   The method of claim 52, characterized   rised by the fact that the foaming agent is a hydrocarbon   fluorinated having a boiling point lower than the temperature   to which the mixed material becomes rigid.   55 Composition usable to produce a maize   rigid phosphatized ceramics resistant to water,   characterized by the fact that it includes   from about 1 to about 65 parts by weight   on an anhydrous basis of at least one metal oxide selected from A 1203, MgO, CaO, ZnO and their hydrates; from about 80 to about 190 parts by weight of phosphoric acid solution comprising the equivalent of about 35 to about 75% by weight of phoshoric anhydride based on the weight of the   acid soluticn, the water of hydrtatazn of said metal oxcyde being   take oom the calculation of the phosphoric anhydride content; and   about 100 parts by weight of calcium silicate.   56 Composition according to claim 55, characterized   characterized by the fact that it comprises from about 13 to about   26 parts of metal oxide, about 100 parts of silica   calcium and from about 90 to about 150 parts of   phosphoric acid solution comprising the equivalent of about   40 to about 70% phosphoric anhydride.   57. The composition of claim 55, wherein   it consists of about 15 to about   22 parts of metal oxide, about 100 parts of   calcium and about 100 to about 105 parts of   phosphoric acid solution comprising the equivalent of   55 to about 65% phosphoric anhydride.   58 Composition according to one of the claims   57, characterized by the fact that the size of the   metal oxide is no greater than that of particles passing through a No. 325 Tyler sieve (0.044 mm mesh aperture) and the particle size   calcium silicate is not greater than that of   particles passing through a Tyler N 200 screen (0.074 mm mesh opening).   59 Composition according to one of the claims   55 to 57, characterized by the fact that the metal oxide   is aluminum oxide trihydrate.   Composition according to one of the claims   at 57, characterized by the fact that the metal oxide is magnesium oxide.   61 Composition according to one of the claims   at 57, characterized in that it comprises a mixture   age of aluminum oxide and magnesium oxide trihydrate sium.   62 Composition according to one of the claims   at 57, characterized in that it comprises a surfactant.   63 Composition according to one of the claims   55 to 57, characterized in that it comprises a reinforcing fiber.   64 Composition according to one of the claims   at 57, characterized in that it comprises a foaming agent.   65. The composition according to claim 64, wherein * controlled by the fact that the foaming agent is a carbonate   selected from Mg C 03, Ca C 03, Zn CO 3 and Li 2 C 03.   Composition according to Claim 64,   characterized in that the foaming agent is a hydro-   fluorinated carbide having a boiling point lower than the   temperature at which the mixed material becomes rigid.   A rigid water-resistant phosphated ceramic material, characterized in that it is obtained by reacting: (1) from about 11 to about 65 parts by weight calculated on an anhydrous base of at least one metal oxide selected from A 1203, EgO, CaO, ZnO and their hydrates; (2) from about 80 to about 190 parts by weight of a phosphoric acid solution comprising the equivalent   from about 35 to about 75% by weight of phosphoric anhydride.   With respect to the weight of the acid solution, the water of hydration must include the metal oxide When calculating the phosphoric anhydride content; and   (3) about 100 parts by weight of calcium silicate.   Product according to claim 67, characterized   rised by the fact that it comprises from about 13 to about 26 parts of metal oxide, about 100 parts of silicate   calcium and from about 90 to about 150 parts of   phosphoric acid comprising the equivalent of about   40 to about 70% phosphoric anhydride.   The product of claim 67, characterized   in that it comprises from about 15 to about 22 parts of metal oxide, about 100 parts of silicate   of calcium and from about 100 to about 130 parts of sol-   phosphoric acid including the equivalent of about 45 to   about 65% phosphoric anhydride.   Product according to one of claims 67   at 69, characterized in that the ceramic material is obtained by reacting a reaction solution and   a mixture of constituents, the reaction solution   taking the phosphoric acid solution and at least a part of the metal oxide and the mixture of constituents   comprising calcium silicate and the remainder of the metal oxy.   71 Product according to one of claims 67 to   69, characterized in that the amount of metal oxide   used to prepare the reaction solution and the temperature   of the reaction solution are chosen so as to approximately pre-determine the moment when the material   mixed becomes rigid with respect to the moment when sation of the water begins.   72 Product according to claim 71, characterized   because the particle size of the oxy-   of metal is not greater than that of particles   passing through a Tyler N O 325 sieve (0.044 mm opening   mesh size) and the size of the silicate particles   of calcium is not greater than that of   through a Tyler N O 200 sieve (0.074 mm aperture mesh).   73 Product according to claim 71, characterized   in that the metal oxide is trihydrate of aluminum oxide.   The product of claim 71, characterized   rised by the fact that the metal oxide is the oxide of sium.   Product according to claim 71, characterized   in that the metal oxide comprises a mixture of   Aluminum oxide trihydrate and magnesium oxide.   76 Product according to claim 71, characterized   in that the ceramic material comprises a surfactant.   77 Product according to claim 71, characterized   in that the ceramic material comprises a material Z 507591 fibrous reinforcement.   Product according to claim 71, characterized   rised by the fact that it comprises a foaming agent.   79 Product according to claim 78, characterized   rised by the fact that the foaming agent is a carbonate   selected from Mg C 03, Ca C 03, Zn CO 3 and Li 2 CO 3.   Product according to claim 78, characterized   rised by the fact that the foaming agent is a hydrocarbon   fluorinated having a boiling point lower than the   erature to which the mixed material becomes rigid.