CA2129659A1 - Process for the production of a silica substance-containing material and materials produced therefrom - Google Patents
Process for the production of a silica substance-containing material and materials produced therefromInfo
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Abstract
ABSTRACT
The fundamental idea is based on the fact that the aim is not the crosslinking of the solid disperse phase in the dispersant, but instead the use of the solid disperse as an overmatrix, in order to incorporate macroparticles therein. The dispersant is finally chemically set, but so much setting agent is added in excess that with a subsequent dispersant addition the prelim-inary product can be finalized to the desired material.
For this purpose a matrix-like substance of filler-like macroparticles and sol oxide (crosslinking substance) and a buffer are brought together for assisting the formation of the overmatrix and are processed. This substance is pigmentable, so that a wide range of characteristics can be obtained. This is brought about by introducing a variation mixture into the substance. The substance directed at the desired aim is trans-formed in two following stages into the desired material, namely a hydration and balancing process stage and a subsequent setting and stabilizing process stage.
(No drawing)
The fundamental idea is based on the fact that the aim is not the crosslinking of the solid disperse phase in the dispersant, but instead the use of the solid disperse as an overmatrix, in order to incorporate macroparticles therein. The dispersant is finally chemically set, but so much setting agent is added in excess that with a subsequent dispersant addition the prelim-inary product can be finalized to the desired material.
For this purpose a matrix-like substance of filler-like macroparticles and sol oxide (crosslinking substance) and a buffer are brought together for assisting the formation of the overmatrix and are processed. This substance is pigmentable, so that a wide range of characteristics can be obtained. This is brought about by introducing a variation mixture into the substance. The substance directed at the desired aim is trans-formed in two following stages into the desired material, namely a hydration and balancing process stage and a subsequent setting and stabilizing process stage.
(No drawing)
Description
21 2~g;~9 PROCESS FOR THE PRODUCTION O~ A SILICA SUBSTANCE-CONTAINI~G
MATERIAL AND MATERIALS PRODUCED THEREFROM
The invention is in the field of mineral materials and relates to a composition based on fillers 9 SQl oxides, polysilicates and, if desired, pigmenting agents.
Numerous materials with which specific problems could be solved are known from colloid chemistry, particularly sol-gel tech-nology. The central point is that it is possible to produce from liquid components solid, crosslinked materials. Whereas as in the case of conventional dispersions, a sol, e.g. the disperse phase, is rela~ively freely movable, this is no longer the case in a gel, where the particles are interconnected in net-like manner and are therefore difficult to displace rela-tive to one another. Thus, the essence of sol-gal technology is the transition between free disperse and crosslinked dis-persed phase. As a rule the transition from sol to gel in mat-erials is irreversible, the dispersed, solid constituent being distributed in net or honeycomb-like manner in the dispersant 9 usually water, the dispersant being expelled by means of heat, in order to give a solid, crosslinked material.
What is problematical is the finalization of the gel to the material, i.e. the expulsion of the dispersant. It would be desirable to obviate this procedure, i.e. to essentially incor-porate the dispersant into the material. Advantageously this should take place without additional process stages and cert-ainly not by means of energy-intensive stages such as burning out, baking, etc.
The presently described process for the production of inorganic modified oxides by which hard and solid, crosslinked, layer-like, transparent or crystalline multicomponent semifinished products or materials can be produced at low temperature such as e.g. ambient temperature, constitutes a fur~her, enrichment of the prior art in this field.
21296~3 -~ - 2 -: .:
The invention defined in the claims shows how it is possible to arrive at semifinished products further processable to such materials. This leads to ur.iversally usable, inorganic mater-ials, which can be produced in large quantities.
The fundamental idea is based on the fact that the object is not merely the crosslinking of the solid disperse phase in the dispersant, bu~ also the use of the solid disperse phase as an overmatrix, in order to incorporate macroparticles into the same, the dispersant in the material being finally chemically bound, but sufficient binding agent is added in excess that with a subsequent dispersant addition the preliminary product can be finalized to the desired materialO This leads to a storable 9 but still reactive semifinished product which, mixed with the dispersant (generally water) and finally reacted leads to the end product.
For this purpose a matrix-like substance of filler-like macro-particles and sol oxide, polysilicate (crosslinking materials) and a buffer for assisting the formation of the overmatrix are brought together and processed. This substance is inter alia pigmentable, so that a considerable variety of characteristics is attainable. This is brought about by introducing a varia-tion mixture into the substance. The varied substance directed at the sought obJective is transformed in two following process stages into the desired semifinished product, namely a hydra-tion and balancing stage and a following setting and stabiliz~
ation stage. The still reacti~e, stabilized semifinished pro-duct can be reacted at a later time to a finished material by mlxing it with dispersant, so that the final reaction occurs.
This takes place at low temperatures (below 150C and most frequently below 100C).
Hereinafter by means of a first qualitative basic example the principle is discussed in greater detail and then by means of a i:,`
21296~9 ~uantitative basic example the principle can be implemented and subsequently in accordance with the above grouping substances are discussed which are suitable for producing such materials and in conclusion a few examples are giv~n based on actual experiments.
The quantitative basic example Component A: (filler part) comprises the fillers such as e.g.
glassmaking sand (cullet?, optionally mixed with tough fibres (carbon fibres, Kevlar, rock wool, glass fibres, etc.). As a function of the material to be obtained, these particles are of varying æize, but are clearly a multiple above the colloid limit of the dispersion used for the overmatrix.
Component B: (reaction part) includes an acid part, alone or together with the sol oxide, such as e.g. silica sol, aluminium sol, titanium sol, zirconium sol, etc., the sols having a maximum oxide content. In order to obtain a more reactive end product, solid aclds, e.g. boric acid are added. Concentrated o-phosphoric acid serves as the acid reaction medium and with a proportion of unsoled oxide, e.g. Si-oxide (fumed silica, Aerosil) is added to the silica sol, so as to increase the sol oxide content. The solling on acts as a gelling delay means (for better storage stability). Component B can also contain pigmenting or dyeing agents (component B'), particularly those consisting of two components, one being introduced here and the other into component V.
Component C: (buffer part) formed by a mixture of sol oxide and a polysilicate, e.g. in a ratio of 1:1, which is provided with~-lY of a metal oxide (Al, Ti, Zr, etc.) as an agglomeration or lumping preventing agent. Here a type of solling on is sought. The polysilicate is a highly alkaline acting component.
The filler (component A), reaction part (component B) and ..
21296~9 buffer part (component C) form the substance (ABC) for further variations of the end product. A variation mixture added to the substance is prepared in the following way:
Component V: (variation part) prepared from one or more of the premixes indicated below. It contains pigmenting agents in the form of metal salts such as aluminium, iron, copper, chromium salts, etc. This addition either takes place separately by a variation mixture to the substance or by additions to component B.
Premix Vl: e.g. a sol oxide-related substance, e.g. potassium silicate or trisilicate and a metal oxide, e.g. of Al, Si, Ti or Zr with boric acid. Hydroxides, preferably zirconium hydr-oxide, as well as calcium hydroxide or cements (and boric acid) can be used.
Premix V2: a further sol oxide is mixed with a mixture of phos-phoric acid and boric acid, e.g. a sol oxide of zirconium, aluminium, titanium, silicon, etc. (or a mixture of two or three of said oxides (variation) are separately mixed toge~her).
Variation mixture: The two premixes Vl and V2 are mixed together for preparing component V and (optionally once again a solid acid, e.g. boric acid is added), a hydroxide such as Zi-hydroxide, Ca-hydroxide, etc., in this case e.g. zirconium hydroxide is added and intimately mixed with one another and well homogenized. Thi.s gives a colourless, slightly coloured or coloured mixtures/ which can be introduced in~o the sub-stance for the sought objectives. The variation mixture is prepared as a function of the filler.
The three components A, B and C are mixed together in the foll-owing way to a substance and varied with component V.
21296~
~ - 5 -Formation of the Substance Component A is completely wetted with component B or B', so that a consistency of wet sand is obtained. In the case of additions for obtaining a pigmented component B, it is neces-sary to provide a residence time in which colourin~ takes place or the chemical reaction leading to the latter. Without the acid addition in B the colour reaction does not occur. ~ollow-ing the necessary residence time, where the wet sand consist-ency is retained, component C is added, being poured into the "wet sand" and intimately mixed. In order to avoid agglomera-tion or lump formation the mixture can be passed through a sieve or screen. The consistency remains similar to a wet powder, but tends to gel, i.e. to form the overmatrix, but is still free-flowing and should be further processed as rapidly as possible.
Variation_of the Substance The resulting wet, free-flowing substance is mixed with the variation mixture, so that an almost dry powder is obtained.
The variation mixture contains componen~s for binding in the dispersant. The resulting powder is preferably screened in order to comminute any lumps and homogenize the mixture. The resulting mixture is allowed to stand for roughly 1 to 5 hours/n.
The powder becomes ever drier through the binding in of dis-persant (water binding time, hydration). The resulting dry, pulverulent mixture with different particle sizes ~s still not stable in storage and should be further processed within a reas-onable time. The dispersant incorportion must be continued and finalized.
Hydration and Balancing The varied substance is "started" with a hydrating agent ,.. . .
` ~
~ 6 - 21296~9 .; ~ . ..
(starter substance), e.g. metasilicate (hydration). This takes place by intimate mixing, the mixture becoming detectably warm.
During mixing further sol oxide with polysilicate is poured in (balancing). The mixing process is continued until a dry pow-der is obtained. The heating level increases on pouring in the sol oxide and polysilicate. The metasilicate probably serves as a water binder (hydration). Following this process an ever drier powder is obtained, but it is still not stable in storage.
Setting and Stabilization The aim is to produce a still reactive, stable product. The next stages initiate the stabilization phase. Thus, the resul-ting powder is further processed. The now dry powder contains residues of bound ~-ater, which is hydrated by mi~ing further metasilicate. On mixing in the metasilicate heat evolution occurs and the powder becomes increasingly moist and sticky.
Before it again acquires a dry, pulverulent consistency, addi-tion takes place of hdyroxylizing (setting, possibly catalyzing) substances, e.g. hydroxides of Ca, Al, Mg, Zr, etc. and vigor- -ous mixing occurs untll a uniform granular material is obtained.
Thus, the stable, reactive end product with a hydrating agent excess is obtained, which in a subsequent stage can be reacted to a corresponding material on adding dispersant. The final-izing stages could naturally ~ake place at this point, if thiæ
materlal is required. However, the aim is e.g. that a semi-finlshed product in granular form can e.g. be stirred with water, randomly applied and then cured at ambient temperature e.g. to a layer, block, calandered plates etc.
The quantitative basic example Component A: 300 g of glassmaking sand (cullet), optionally with tough fibres (carbon fibres, Kevlar, rock wool, glass fibres, etc.).
~ ' ~
- 7 - 21 29 6~g Component B: 25 g of a mixture of lO0 g of silica sol ~e.g.
Levasol 200/40~ from Bayer-Leverkusen) or a sol oxide such as Si-oxide sol, Al-oxide sol, Ti-oxide sol, Zi-oxide sol, etc.
(in part not commercially available), but in this case silica sol (Si-oxide sol) preferably 50~ or higher in the silica con-tent, are mixed with 5 g of concentrated o-phosphoric acid in a ratio of 100:30 g of boric acid. The boric acid is added for buffering and in part having a gelling accelerating action. It is also possible to use other buffers such as aluminium oxide, zirconium oxide (Degussa) or other oxides. Gelling delay takes place if no boric acid îs added.
Component C: 25 g of a mixture of sol oxide (in this case 40%
silica sol, 50% silica sol leading to a sedimentation of the mixture) with 40% lithium polysilicate (Van Baerle, Munchenstein BL, Switzerland) in a ratio of 1:1 and which can additionally be provided with 0.5 to 1% of an oxide (Al, Ti, Zr, etc.) as an agglomeration preventing agent.
Premix Vl: 100 g of potassium silicate or trisilicate and 5 g of Al~oxide, 10 g of boric acid (or Zi-hydroxide (MEL magnesium Electrode Ltd., Manchester, GB), Ca-hydroxide) are mixed together, optionally with the addition of pigment in the form of inorganic pigments (spinel, lapis lazuli, e.g. from Van Baerle, etc.) or metal salts of aluminium, iron, copper~ chrom-ium, cobalt, manganese, etc.
Premix V2: 50 g of 50% silica sol from a mixture of 100:5 g of o-phosphoric acid are mixed together in a ratio 100:30 g of boric acid.
Component V The two premixes V1 and V2 are mixed together, com-pletely dried and again intimately mixed and well homogenized and mixed with lO to 20 g of a carbonate, such as Ca-carbonate, zirconium carbonate (MEL), etc., or a hydroxide such as Ca-hydroxide, zirconium hydroxide, etc.) and once again well mixed.
8 2 ~ 2 9 6 ~ 9 The three component A, B and C are mixed together in t'ne Eoll-owing way to a substance.
300 g of component .~ are completely wetted with 25 g of com-ponent B or B', so as to give a consistency like wet sand.
With respect to co~ponent B a residence time must be respected, w'here colouring or the chemical reaction leading ~o this takes place. The colour reaction does not occur without acid addi-tion in B'. Follo-~ing the necessary residence time, when the wet sand consistency is maintained, 25 g of component C are added. It is poured into the "wet sand" and intimately mixed.
To avoid lump formation the mixture can be passed through a sieve or screen. ~he consistency remains similar to a wet powder, but has a gelling tendency, but still flows freely and must be further processed.
The resulting 350 g of wet, free-flowing mixture of A, B and C
are mixed with component V (80 g of dry powder), so that an almost dry powder is obtained. Preferably the resulting powder is screened in order to comminute any lumps and homogenize the mixture. The resulting 430 g of mixture are allowed to stand for approximately 1 to hours/n. The powder becomes ever drier (water binding ti~e, hydration). The resulting dry, pulveru-lent mixture with iifferent particle sizes is not stable in storage and must b~ further processed as soon as possible.
The 430 g of the above-prepared mixture are mixed with 20 g of powder-like Na-metasilicate and therefore reacted. This takes place by intimate mixing, the mixture becoming detectably warm.
During mixing successively 50 g of sol oxide polysilicate (lithium polysilicate) are poured in in a ratio of 3:1 (balan-cing agent). The mixing process is continued until a dry pow- -der is obtained. ~he heating level increases on pouring in the sol oxide. The metasilicate prob~bly serves as a water binder ~hydration). There are 500 g of a dry powder after this oper-- 9 - 21296a9 ation. In order to obtain a free-flowing particle mix~ure, the quantity obtained is again forced through a sieve before fur-ther processing.
The resulting 500 g of the mixture are further processed in the following way. The dry powder contains bound water, which is further hydrated by mixing in a further 20 g of metasilicate.
On mixing in the me~asilicate heat evolu~ion occurs and the powder becomes increasingly moist and sticky. Before it is again passed into a dry, pulverulent consistency, addition takes place of 50 to 60 g of a hydroxylizing substance, e.g.
hydroxides and/or carbonates or hydrocarbonates of Ca, Al, Mg, Zr, etc. or a combination of hydroxylizing substances with a cement, followed by vigorous mlxing until a uniform granular material is obtained. Thus, approximately 600 g of end product are obtained.
The end product is storable, but must be protected against mois-ture. As a function of pigmentation different coloured gran-ules are obtained and as a function of the basic substance, i.e.
quartz sand, glass powder, etc., they are either more glitter-ing or more dull. Said granules can be stirred with water.
As a function of the doughy to free-flowing consistency the substance can be spread onl spa~ula-applled, calandered, poured or sprayed. When applied to a surface such as glass, metal, ceramic, concrete or wood, the material adheres and reacts in air at ambient temperature to a dry, hard, mineral feeling layer. The completely reacted product is ~laterproof, tough, hard, resistant to most mechanical actions and can also be used as rock glue or as an inorganic adhesive. The range of uses is virtually unlimited.
The various additions of solid and liquid silica~es combined wlth metal oxides and hydroxides lead to different effects, e.g.:
2129~5~
Aluminium oxide: Tends to make layers brittle wlth a tendency shrinkage cracks~ crosslinking to conglomerates, coarse surface;
titanium oxide differs by a pigmentation and more homogeneous combination, leads to brittleness and hard layers, crosslinking to conglomerates and with an average coarse surface;
silicon dioxide: delays the reaction process, but leads to more homogeneous layers;
zirconium oxide: less shrinkage cracks and good balance between pH and crystallization, slight pigmentation.
The above phenomena were observed during variation experiments and are to be looked upon purely empirically.
The Groups Substance Components:
A Borosilicate glass, glassmaking sand, foundry sand, mineral sands, borosilicate, organic and inorganic fibrous material, quartz sand, aluminium oxide (white corundum) B Phosphoric acids, boric acid and optionally sol oxides such as silicon dioxide sol (silica sol), aluminium oxide sol, titanium oxide sol, zirconium oxide sol and their dry oxides for solling on, zirconium acetate, kaolin I
C Sol oxides and sol oxides dissolved in alkali metal hydroxides, polysilicates (soda water glass, potassium water glass) and lithium polysilicate.
21296~9 Yar_ation of the substance (with component V):
Sodium silicate, potassium silicate, Ca-hydrocarbonate, zircon-ium carbonate, titanium carbonate or their hydroxides and the oxides of silicon, aluminium, titanium, zirconium mixed together. For pigmenting inorganic or mineral pigments or pig-~enting agents such as metal salts, e.g. aluminium, iron, copper, chromium salts and sulphates, nitrates, hydroxides, etc.
Premixes (some examples):
Premix V1: 100 g of potassium silicate and 10 g of boric acid are mixed together -> dry premix.
Premix V2: In each case 5 g of an oxide of zirconium, alum-inium, titanium, silicon, etc., or in each case 2.5 to 5 g of two different oxides indicated above are mixed together and added to V1)-> dry premix.
Premix V3: 100 g of basic 40% silica sol (e.g. Levasil, Bayer-Leverkusen) mixed with 5 to 10 g of phosphoric and boric acid in à ratio 100:30. This mixture is less alkaline than V6 and is therefore suitable for fillers with a lower alkali resis-~ance such as e.g. glass sand ->wet and acid premix.
Premix V4: 100 g of basic 40% silica sol mixed with 5 g of phosphoric acid gives a combination in the acid range which is advantageous for delaying gelling -> wet and acid premix.
Premix V5: 50 g of a mixture of 3 parts of basic 40~ silica sol and 1 pat of lithium polysilicate (used as a buffer for the premix of V3 and V4) -> wet, basic premix.
Premix V6: 200 g of 40~ silica sol mixed with 5 g of Al-oxide and 10 g of Ca-hydrocarbonate, said mixture being alkaline and .
: . . :- . -. . :
.
- - 12 - 2~29~9 suitable for certain mineral fillers, but unsuitable for glass-making sand ->wet, basic premix.
Premix V7: 10 to 20 g of Ca-hydroxide (Zi-hydroxide) are added to the combinable premixes Vl to V5 in the dry state and intimately mixed ->dry premix.
Premi~ V8: 100 g of potassium trisilicate with 10 g of zirco-nium hydroxide, 50 g of basic 40% silica sol mixed with 5 g of o-phosphoric acid are intimately mixed and dried for 8 to 12 hours and to avoid lump formation pass through a fine sieve.
This powder is mixed with 100 g of water and up to 50 g powder ->dry premix. The aqueous dispersing solution is constituted by the premix V8 as a coating and film-forming pore sealer in materials produced from silica substances.
These premixes are used individually as component V or, as in the above-discussed example, used mixed together as a component V. These mixtures are used as a ~asis for the variation system of the still reactive preliminary product (granular material stirrable with dispersants) in order to give materials with desired characteristics, such as surface characteristics, hard-ness, colour9 etc. Among carbon dioxide forming agents impor-tance is attached to carbonat~s and hydrocarbonates e.g. of calcium or zirconium. In the case of carbonates carbon dioxide is released in the reaction with the premixes V3 and V4 and con-sequently a better ''crosslinking" is obtained. In place of basic silica sols it is also possible to use acid silica sols.
The basic silica sols used contain a higher Si-concentration (up to 50~ Si) than the acid silica sols (up to approxlmately 30% Si).
.. ' Premixes V5 and V6 are also used as balancing agents, which can be added to the mixture ABCV ~ith metasilicate (hydrating agent) after or during reaction.
MATERIAL AND MATERIALS PRODUCED THEREFROM
The invention is in the field of mineral materials and relates to a composition based on fillers 9 SQl oxides, polysilicates and, if desired, pigmenting agents.
Numerous materials with which specific problems could be solved are known from colloid chemistry, particularly sol-gel tech-nology. The central point is that it is possible to produce from liquid components solid, crosslinked materials. Whereas as in the case of conventional dispersions, a sol, e.g. the disperse phase, is rela~ively freely movable, this is no longer the case in a gel, where the particles are interconnected in net-like manner and are therefore difficult to displace rela-tive to one another. Thus, the essence of sol-gal technology is the transition between free disperse and crosslinked dis-persed phase. As a rule the transition from sol to gel in mat-erials is irreversible, the dispersed, solid constituent being distributed in net or honeycomb-like manner in the dispersant 9 usually water, the dispersant being expelled by means of heat, in order to give a solid, crosslinked material.
What is problematical is the finalization of the gel to the material, i.e. the expulsion of the dispersant. It would be desirable to obviate this procedure, i.e. to essentially incor-porate the dispersant into the material. Advantageously this should take place without additional process stages and cert-ainly not by means of energy-intensive stages such as burning out, baking, etc.
The presently described process for the production of inorganic modified oxides by which hard and solid, crosslinked, layer-like, transparent or crystalline multicomponent semifinished products or materials can be produced at low temperature such as e.g. ambient temperature, constitutes a fur~her, enrichment of the prior art in this field.
21296~3 -~ - 2 -: .:
The invention defined in the claims shows how it is possible to arrive at semifinished products further processable to such materials. This leads to ur.iversally usable, inorganic mater-ials, which can be produced in large quantities.
The fundamental idea is based on the fact that the object is not merely the crosslinking of the solid disperse phase in the dispersant, bu~ also the use of the solid disperse phase as an overmatrix, in order to incorporate macroparticles into the same, the dispersant in the material being finally chemically bound, but sufficient binding agent is added in excess that with a subsequent dispersant addition the preliminary product can be finalized to the desired materialO This leads to a storable 9 but still reactive semifinished product which, mixed with the dispersant (generally water) and finally reacted leads to the end product.
For this purpose a matrix-like substance of filler-like macro-particles and sol oxide, polysilicate (crosslinking materials) and a buffer for assisting the formation of the overmatrix are brought together and processed. This substance is inter alia pigmentable, so that a considerable variety of characteristics is attainable. This is brought about by introducing a varia-tion mixture into the substance. The varied substance directed at the sought obJective is transformed in two following process stages into the desired semifinished product, namely a hydra-tion and balancing stage and a following setting and stabiliz~
ation stage. The still reacti~e, stabilized semifinished pro-duct can be reacted at a later time to a finished material by mlxing it with dispersant, so that the final reaction occurs.
This takes place at low temperatures (below 150C and most frequently below 100C).
Hereinafter by means of a first qualitative basic example the principle is discussed in greater detail and then by means of a i:,`
21296~9 ~uantitative basic example the principle can be implemented and subsequently in accordance with the above grouping substances are discussed which are suitable for producing such materials and in conclusion a few examples are giv~n based on actual experiments.
The quantitative basic example Component A: (filler part) comprises the fillers such as e.g.
glassmaking sand (cullet?, optionally mixed with tough fibres (carbon fibres, Kevlar, rock wool, glass fibres, etc.). As a function of the material to be obtained, these particles are of varying æize, but are clearly a multiple above the colloid limit of the dispersion used for the overmatrix.
Component B: (reaction part) includes an acid part, alone or together with the sol oxide, such as e.g. silica sol, aluminium sol, titanium sol, zirconium sol, etc., the sols having a maximum oxide content. In order to obtain a more reactive end product, solid aclds, e.g. boric acid are added. Concentrated o-phosphoric acid serves as the acid reaction medium and with a proportion of unsoled oxide, e.g. Si-oxide (fumed silica, Aerosil) is added to the silica sol, so as to increase the sol oxide content. The solling on acts as a gelling delay means (for better storage stability). Component B can also contain pigmenting or dyeing agents (component B'), particularly those consisting of two components, one being introduced here and the other into component V.
Component C: (buffer part) formed by a mixture of sol oxide and a polysilicate, e.g. in a ratio of 1:1, which is provided with~-lY of a metal oxide (Al, Ti, Zr, etc.) as an agglomeration or lumping preventing agent. Here a type of solling on is sought. The polysilicate is a highly alkaline acting component.
The filler (component A), reaction part (component B) and ..
21296~9 buffer part (component C) form the substance (ABC) for further variations of the end product. A variation mixture added to the substance is prepared in the following way:
Component V: (variation part) prepared from one or more of the premixes indicated below. It contains pigmenting agents in the form of metal salts such as aluminium, iron, copper, chromium salts, etc. This addition either takes place separately by a variation mixture to the substance or by additions to component B.
Premix Vl: e.g. a sol oxide-related substance, e.g. potassium silicate or trisilicate and a metal oxide, e.g. of Al, Si, Ti or Zr with boric acid. Hydroxides, preferably zirconium hydr-oxide, as well as calcium hydroxide or cements (and boric acid) can be used.
Premix V2: a further sol oxide is mixed with a mixture of phos-phoric acid and boric acid, e.g. a sol oxide of zirconium, aluminium, titanium, silicon, etc. (or a mixture of two or three of said oxides (variation) are separately mixed toge~her).
Variation mixture: The two premixes Vl and V2 are mixed together for preparing component V and (optionally once again a solid acid, e.g. boric acid is added), a hydroxide such as Zi-hydroxide, Ca-hydroxide, etc., in this case e.g. zirconium hydroxide is added and intimately mixed with one another and well homogenized. Thi.s gives a colourless, slightly coloured or coloured mixtures/ which can be introduced in~o the sub-stance for the sought objectives. The variation mixture is prepared as a function of the filler.
The three components A, B and C are mixed together in the foll-owing way to a substance and varied with component V.
21296~
~ - 5 -Formation of the Substance Component A is completely wetted with component B or B', so that a consistency of wet sand is obtained. In the case of additions for obtaining a pigmented component B, it is neces-sary to provide a residence time in which colourin~ takes place or the chemical reaction leading to the latter. Without the acid addition in B the colour reaction does not occur. ~ollow-ing the necessary residence time, where the wet sand consist-ency is retained, component C is added, being poured into the "wet sand" and intimately mixed. In order to avoid agglomera-tion or lump formation the mixture can be passed through a sieve or screen. The consistency remains similar to a wet powder, but tends to gel, i.e. to form the overmatrix, but is still free-flowing and should be further processed as rapidly as possible.
Variation_of the Substance The resulting wet, free-flowing substance is mixed with the variation mixture, so that an almost dry powder is obtained.
The variation mixture contains componen~s for binding in the dispersant. The resulting powder is preferably screened in order to comminute any lumps and homogenize the mixture. The resulting mixture is allowed to stand for roughly 1 to 5 hours/n.
The powder becomes ever drier through the binding in of dis-persant (water binding time, hydration). The resulting dry, pulverulent mixture with different particle sizes ~s still not stable in storage and should be further processed within a reas-onable time. The dispersant incorportion must be continued and finalized.
Hydration and Balancing The varied substance is "started" with a hydrating agent ,.. . .
` ~
~ 6 - 21296~9 .; ~ . ..
(starter substance), e.g. metasilicate (hydration). This takes place by intimate mixing, the mixture becoming detectably warm.
During mixing further sol oxide with polysilicate is poured in (balancing). The mixing process is continued until a dry pow-der is obtained. The heating level increases on pouring in the sol oxide and polysilicate. The metasilicate probably serves as a water binder (hydration). Following this process an ever drier powder is obtained, but it is still not stable in storage.
Setting and Stabilization The aim is to produce a still reactive, stable product. The next stages initiate the stabilization phase. Thus, the resul-ting powder is further processed. The now dry powder contains residues of bound ~-ater, which is hydrated by mi~ing further metasilicate. On mixing in the metasilicate heat evolution occurs and the powder becomes increasingly moist and sticky.
Before it again acquires a dry, pulverulent consistency, addi-tion takes place of hdyroxylizing (setting, possibly catalyzing) substances, e.g. hydroxides of Ca, Al, Mg, Zr, etc. and vigor- -ous mixing occurs untll a uniform granular material is obtained.
Thus, the stable, reactive end product with a hydrating agent excess is obtained, which in a subsequent stage can be reacted to a corresponding material on adding dispersant. The final-izing stages could naturally ~ake place at this point, if thiæ
materlal is required. However, the aim is e.g. that a semi-finlshed product in granular form can e.g. be stirred with water, randomly applied and then cured at ambient temperature e.g. to a layer, block, calandered plates etc.
The quantitative basic example Component A: 300 g of glassmaking sand (cullet), optionally with tough fibres (carbon fibres, Kevlar, rock wool, glass fibres, etc.).
~ ' ~
- 7 - 21 29 6~g Component B: 25 g of a mixture of lO0 g of silica sol ~e.g.
Levasol 200/40~ from Bayer-Leverkusen) or a sol oxide such as Si-oxide sol, Al-oxide sol, Ti-oxide sol, Zi-oxide sol, etc.
(in part not commercially available), but in this case silica sol (Si-oxide sol) preferably 50~ or higher in the silica con-tent, are mixed with 5 g of concentrated o-phosphoric acid in a ratio of 100:30 g of boric acid. The boric acid is added for buffering and in part having a gelling accelerating action. It is also possible to use other buffers such as aluminium oxide, zirconium oxide (Degussa) or other oxides. Gelling delay takes place if no boric acid îs added.
Component C: 25 g of a mixture of sol oxide (in this case 40%
silica sol, 50% silica sol leading to a sedimentation of the mixture) with 40% lithium polysilicate (Van Baerle, Munchenstein BL, Switzerland) in a ratio of 1:1 and which can additionally be provided with 0.5 to 1% of an oxide (Al, Ti, Zr, etc.) as an agglomeration preventing agent.
Premix Vl: 100 g of potassium silicate or trisilicate and 5 g of Al~oxide, 10 g of boric acid (or Zi-hydroxide (MEL magnesium Electrode Ltd., Manchester, GB), Ca-hydroxide) are mixed together, optionally with the addition of pigment in the form of inorganic pigments (spinel, lapis lazuli, e.g. from Van Baerle, etc.) or metal salts of aluminium, iron, copper~ chrom-ium, cobalt, manganese, etc.
Premix V2: 50 g of 50% silica sol from a mixture of 100:5 g of o-phosphoric acid are mixed together in a ratio 100:30 g of boric acid.
Component V The two premixes V1 and V2 are mixed together, com-pletely dried and again intimately mixed and well homogenized and mixed with lO to 20 g of a carbonate, such as Ca-carbonate, zirconium carbonate (MEL), etc., or a hydroxide such as Ca-hydroxide, zirconium hydroxide, etc.) and once again well mixed.
8 2 ~ 2 9 6 ~ 9 The three component A, B and C are mixed together in t'ne Eoll-owing way to a substance.
300 g of component .~ are completely wetted with 25 g of com-ponent B or B', so as to give a consistency like wet sand.
With respect to co~ponent B a residence time must be respected, w'here colouring or the chemical reaction leading ~o this takes place. The colour reaction does not occur without acid addi-tion in B'. Follo-~ing the necessary residence time, when the wet sand consistency is maintained, 25 g of component C are added. It is poured into the "wet sand" and intimately mixed.
To avoid lump formation the mixture can be passed through a sieve or screen. ~he consistency remains similar to a wet powder, but has a gelling tendency, but still flows freely and must be further processed.
The resulting 350 g of wet, free-flowing mixture of A, B and C
are mixed with component V (80 g of dry powder), so that an almost dry powder is obtained. Preferably the resulting powder is screened in order to comminute any lumps and homogenize the mixture. The resulting 430 g of mixture are allowed to stand for approximately 1 to hours/n. The powder becomes ever drier (water binding ti~e, hydration). The resulting dry, pulveru-lent mixture with iifferent particle sizes is not stable in storage and must b~ further processed as soon as possible.
The 430 g of the above-prepared mixture are mixed with 20 g of powder-like Na-metasilicate and therefore reacted. This takes place by intimate mixing, the mixture becoming detectably warm.
During mixing successively 50 g of sol oxide polysilicate (lithium polysilicate) are poured in in a ratio of 3:1 (balan-cing agent). The mixing process is continued until a dry pow- -der is obtained. ~he heating level increases on pouring in the sol oxide. The metasilicate prob~bly serves as a water binder ~hydration). There are 500 g of a dry powder after this oper-- 9 - 21296a9 ation. In order to obtain a free-flowing particle mix~ure, the quantity obtained is again forced through a sieve before fur-ther processing.
The resulting 500 g of the mixture are further processed in the following way. The dry powder contains bound water, which is further hydrated by mixing in a further 20 g of metasilicate.
On mixing in the me~asilicate heat evolu~ion occurs and the powder becomes increasingly moist and sticky. Before it is again passed into a dry, pulverulent consistency, addition takes place of 50 to 60 g of a hydroxylizing substance, e.g.
hydroxides and/or carbonates or hydrocarbonates of Ca, Al, Mg, Zr, etc. or a combination of hydroxylizing substances with a cement, followed by vigorous mlxing until a uniform granular material is obtained. Thus, approximately 600 g of end product are obtained.
The end product is storable, but must be protected against mois-ture. As a function of pigmentation different coloured gran-ules are obtained and as a function of the basic substance, i.e.
quartz sand, glass powder, etc., they are either more glitter-ing or more dull. Said granules can be stirred with water.
As a function of the doughy to free-flowing consistency the substance can be spread onl spa~ula-applled, calandered, poured or sprayed. When applied to a surface such as glass, metal, ceramic, concrete or wood, the material adheres and reacts in air at ambient temperature to a dry, hard, mineral feeling layer. The completely reacted product is ~laterproof, tough, hard, resistant to most mechanical actions and can also be used as rock glue or as an inorganic adhesive. The range of uses is virtually unlimited.
The various additions of solid and liquid silica~es combined wlth metal oxides and hydroxides lead to different effects, e.g.:
2129~5~
Aluminium oxide: Tends to make layers brittle wlth a tendency shrinkage cracks~ crosslinking to conglomerates, coarse surface;
titanium oxide differs by a pigmentation and more homogeneous combination, leads to brittleness and hard layers, crosslinking to conglomerates and with an average coarse surface;
silicon dioxide: delays the reaction process, but leads to more homogeneous layers;
zirconium oxide: less shrinkage cracks and good balance between pH and crystallization, slight pigmentation.
The above phenomena were observed during variation experiments and are to be looked upon purely empirically.
The Groups Substance Components:
A Borosilicate glass, glassmaking sand, foundry sand, mineral sands, borosilicate, organic and inorganic fibrous material, quartz sand, aluminium oxide (white corundum) B Phosphoric acids, boric acid and optionally sol oxides such as silicon dioxide sol (silica sol), aluminium oxide sol, titanium oxide sol, zirconium oxide sol and their dry oxides for solling on, zirconium acetate, kaolin I
C Sol oxides and sol oxides dissolved in alkali metal hydroxides, polysilicates (soda water glass, potassium water glass) and lithium polysilicate.
21296~9 Yar_ation of the substance (with component V):
Sodium silicate, potassium silicate, Ca-hydrocarbonate, zircon-ium carbonate, titanium carbonate or their hydroxides and the oxides of silicon, aluminium, titanium, zirconium mixed together. For pigmenting inorganic or mineral pigments or pig-~enting agents such as metal salts, e.g. aluminium, iron, copper, chromium salts and sulphates, nitrates, hydroxides, etc.
Premixes (some examples):
Premix V1: 100 g of potassium silicate and 10 g of boric acid are mixed together -> dry premix.
Premix V2: In each case 5 g of an oxide of zirconium, alum-inium, titanium, silicon, etc., or in each case 2.5 to 5 g of two different oxides indicated above are mixed together and added to V1)-> dry premix.
Premix V3: 100 g of basic 40% silica sol (e.g. Levasil, Bayer-Leverkusen) mixed with 5 to 10 g of phosphoric and boric acid in à ratio 100:30. This mixture is less alkaline than V6 and is therefore suitable for fillers with a lower alkali resis-~ance such as e.g. glass sand ->wet and acid premix.
Premix V4: 100 g of basic 40% silica sol mixed with 5 g of phosphoric acid gives a combination in the acid range which is advantageous for delaying gelling -> wet and acid premix.
Premix V5: 50 g of a mixture of 3 parts of basic 40~ silica sol and 1 pat of lithium polysilicate (used as a buffer for the premix of V3 and V4) -> wet, basic premix.
Premix V6: 200 g of 40~ silica sol mixed with 5 g of Al-oxide and 10 g of Ca-hydrocarbonate, said mixture being alkaline and .
: . . :- . -. . :
.
- - 12 - 2~29~9 suitable for certain mineral fillers, but unsuitable for glass-making sand ->wet, basic premix.
Premix V7: 10 to 20 g of Ca-hydroxide (Zi-hydroxide) are added to the combinable premixes Vl to V5 in the dry state and intimately mixed ->dry premix.
Premi~ V8: 100 g of potassium trisilicate with 10 g of zirco-nium hydroxide, 50 g of basic 40% silica sol mixed with 5 g of o-phosphoric acid are intimately mixed and dried for 8 to 12 hours and to avoid lump formation pass through a fine sieve.
This powder is mixed with 100 g of water and up to 50 g powder ->dry premix. The aqueous dispersing solution is constituted by the premix V8 as a coating and film-forming pore sealer in materials produced from silica substances.
These premixes are used individually as component V or, as in the above-discussed example, used mixed together as a component V. These mixtures are used as a ~asis for the variation system of the still reactive preliminary product (granular material stirrable with dispersants) in order to give materials with desired characteristics, such as surface characteristics, hard-ness, colour9 etc. Among carbon dioxide forming agents impor-tance is attached to carbonat~s and hydrocarbonates e.g. of calcium or zirconium. In the case of carbonates carbon dioxide is released in the reaction with the premixes V3 and V4 and con-sequently a better ''crosslinking" is obtained. In place of basic silica sols it is also possible to use acid silica sols.
The basic silica sols used contain a higher Si-concentration (up to 50~ Si) than the acid silica sols (up to approxlmately 30% Si).
.. ' Premixes V5 and V6 are also used as balancing agents, which can be added to the mixture ABCV ~ith metasilicate (hydrating agent) after or during reaction.
2~296~9 ~ - 13 -~ydration and Balancing Metasilicates such as e.g. potassium metasilicate, sodium meta-silicate as hydrating agents and premixes V5 or V6 or the like (see examples) as balancing agents.
Settin~ and Stabilizin~
Metasilicates (as above), hydrocarbonates or hydroxide such as calcium hydroxide, magnesium hydroxide, aluminium hydroxide, titanium hydroxide, zirconium hydroxide, further hydrating products such as white cement, Portland cement, or a combina-tion of cements and hydroxides or novel hydrating products, which are specifically modified in view of the desired mineral composition, e.g. with a combination of clinker minerals.
Quantitative variations for the basic examples Example I: hydroxide example.
Component A: 300 g of borosilicate glassmaking sand (Berger &
Bachmann, Buchs AG, 5witzerland) Component B: 5 g of a mixture of 100 g of 40% silica sol (Levasil) with 5 g of o-phosphoric acid in a ratio of 100:10 g of boric acid.
Component C: 25 g of a mixture of 100 g of 40% silica sol in a ratio of 1:1 with 40% lithium polysilicate (Van Baerle, Munchenstein, BL, Switzerland).
Premix: formed from premixes Vl, V2 and V3 comprising 75 g of a powder mix of 100 g of potassium trisilicate (Van Baerle), 5 g of zirconium oxide (MEL) and 10 g of boric acid, as well as 50 g of a mixture of 100 g of 40% silica sol with 5 g of a mixture of phosphoric acid 100:10 g with boric acid (compo-.. , ~ .. . . . . ~ . . . . . . . . . . . . . . .
14 - 212 9 g~9 nent B) and dried for approximately 8 to 12 hours at ambient temperature.
Premix V7: 10 to 20 g with in each case 10 g of Ca-hydroxide (10 g zirconium hydroxide - MEL) are mixed with the above premix (V1, V2 and V3).
Component V: 70 to 80 g of the t~o premixes V1-V3 and V7 are mixed together and well homogenize~ (e.g. through a hair sleve).
Components A, B and C are mixed together in the following way:
300 g of component A are comple~ely wetted with S g of compo-nent B, so that a wet sand consist~ncy is obtained. 25 g of component C is poured into the "wet sand" and intimately ~ixed.
Following the mixing process the product has a gelling tendency and consequently becomes free-flo~-ing9 but still remains moist.
The resulting 330 g of the moist, free-flowing mixture ABC are mixed with component V (80 g of dry powder), so that an almost dry powder is obtained. In order to homogenize the mix~ure and comminute any lumps, the product is forced through a sieve.
The resulting 410 g of mixture are allowed to stand for between 1 and 2 hours. The powder is hydrated by the water binding time to a granular powder mixture, which is further processed (not storage-stable).
The 410 g of the above-prepared mixture are mixed with 20 g of Na-metasilicate. This takes place by intimate mixing, the mix-ture becoming somewhat sticky and ~oist. During mixing succ-essive pouring in takes place of 50 g of a mixture of 200 g of 40% silica sol and 5 g of aluminiu~ oxide and 10 g of Ca-hydrocarbonate (V6 as the balancir.~ agent). During the pouring in of the sol oxide the metasilicate reacts as a water binder and hydrates the 480 g slowly for approximately 1 to 5 hours so - 15 - 21296~9 ; i as to give a granular sand with different part-icle sizes. If at the end of the setting time the mixture has a lump formation tendency and a tendency to produce free-flowing granules, the product is again passed through a sieve.
The resulting 480 g of mixture are further processed in the following way. The dry granular product contains bound water, which is further hydrated by mixing in a further 20 g of Na-metasilicate. This gives a moist and ~acky sta~e and addition takes place of a hydroxylizing (catalyzing) substance. Substi-tute for new hydration products, with the following proportions:
Tricalcium silicate [(3 CaO, SiO2 (C3S)], dicalcium silicate [(2 CaO, SiO2 (C2S)]~ tricalcium aluminate [(3 CaO, Al203 (C3A)], tetracalcium aluminate ferrite [(4 CaO, Al203, Fe203)], calcium sulphate hydrate [(CaS04 2H20 (C 4AF)] and calcium oxide (CaO) formulated for specific material modifications, can be added in place of 50 to 70 g of white cement combined with Ca-carbonates, Ca-hydroxides, kaolin, etc. and vigorous mixing then leads to a uniform granular product of approximately 570 g.
The end product is a chemically modified mixture, which is step-wise prevented from reacting and is subsequently transformed stepwise into difeerent aggregate states as a basic material until an irreversible chemical process mechanlsm is ended. As a basic material and starting substance prior to processing, the end product can be stored, but must be protected against moisture. As a function of the pigmentation, the granules have different colours and as a function of the basic substance (i.e.
quartz sand, glassmaking or other mineral sands) they are more bri.lliant or dull. These granules can be stirred or mixed with water. As a function of the doughy to free-flowing consistency the substance can be calandered, spatula-applied, poured or sprayed. When poured or otherwise applied to a surface such as glass, metal, ceramic, concrete, wood or plastic, the material adheres and reacts with the atmospheric carbon dioxide and the -` 21296~9 substrate by silification, during which a more or less pron-ounced crystalline structure is obtained. The completely reacted product is waterproof, tough, hard, resistant to most mechanical actions and can also be used as a rock glue or inor-ganic adhesive. The range of uses is virtually unlimited.
Example II (formulation only): (carbonate example) Component A: 300 g of glassmaking sand (Berger & Bachmann Component B: 5 g of 40~ silica sol with 5 g of phosphoric acid in the ratio 100:10 g of boric acid Component C: 25 g of 40% silica sol 1:1 lithium polysilicate (Van Baerle) Component V: 80 to 90 g of 100 g potassium trisilicate wi~h 2.5 g aluminium oxide and 10 g of boric acid mixed with 10 to 20 g of Ca-hydrocarbonate (corresponding to a mixture of pre-mixes V1-V3 and V7) -Mixtures A,B,C,V: To the 410 g obtained are added 20 g of Na-metasilicate (hydrating agent - ~an Baerle) and 50 g of a mix-ture of 50 g of 40% silica sol in the ratio 3:1 lithium poly-silicate (Van Baerle - V5 as balancing agen~) Stabilization: To the 460 g are added 20 g of Na-metasilicate and 60 to 80 g white cement (Dickenhoff, Germany). The combin-ation of Ca-carbonate in component V with the cement as the reactant for the hydration, has an effect on the homogenization during the subsequent processing of the finished granular material to a product (i.e. on stirring the finished granules with dispersant, here water). The result is a granular mater-ial, which can be stored and mixe~ with water Rives a solid material.
~`` - 17 - 2~296~9 -, The addition and mixing in the case of example II are substan-tially the same as in example I. The following exemplified formulations are processed in the same way.
Example III (formulation only): (kaolin example) Component A: 300 g of quartz sand (Zimmerli Mineralstoffe, Zurich, Switzerland) Component B: 5 g of a mixture of 50 g of o-phosphoric acid with 5 g of aluminium oxide Component C: 50 g of a mixture of water 1:1 potassium trisllicate Component V: 85 g of a mixture of 100 g of potassium trisili- ~ :
cate with 5 g of Ti-oxide (Degussa), 10 g of boric acid, 50 g of 40~ silica sol with 5 g of phosphoric acid in ratio lOOg:lOg of boric acid, dried for 1 to 5 hours, as well as 10 to 20 g of kaolin (Siegfried, Zofingen, Switzerland) added to the dry powder.
Mixture A,B,C,V: 20 g of Na-metasilicate to the 480 g of mix-ture, as hydrating agent for the further addition of 50 g of 40% silica sol in the ratio 3:1 lithium polysilicate on the basis of 50 g of component C (V5 as balancing agent) Stabilization: 20 g of Na-metasilicate for further wetting and crosslinking with 75 g of a mixture of 60 g white cement and 15 g Ca-hydroxide Granular material: 600 g as end product.
Example IV (formulatlon only) Component A: 500 g of white corundum (e.g. for implantation : :.: . : -2~29~
: - 18 -medicine~ Berger & Bachmann) (same volume as 300 g due to spec-ific weight) Component B: 5 g of o-phosphoric acid lOOg:5g of aluminium oxide Component C: 50 g of tricalcium sllicate and water (in mixing ratio 1:1) Component V: 135 g of a mixture of 75 g potassium trisilica~e (Van Baerle) and 5 g of Al-oxide, 20 g of borosilicate glass powder, 10 g of boric acid, 10 g of Ca-carbonate, 15 g of Zi-hydroxide, and 20 g of sodium metasilicate Mixture A,B,C,V: 710 g of filler and powder proportion wet~ed with 50 g of a mixture of 200 g of 40% silica sol and 5 g of Zi-oxide, 5 g of titanium oxide, 5 g of boric acid, and ~ :
5 g of kaolin and dried in air Stabilization: 15 g of Na-metasilicate for further wetting and crosslinking with 75 g of white cement Granular material: 850 g as end product.
Pigmentation to basic examples Example V:
Component A: 300 g of borosilicate glassmaking sand ..Component B': 5 g of copper hydroxide carbonate..(pigmenting agent, Siegfried, Zofingen~ Switzerland) Component B: 25 g of a mixture of 100 g of 40~ silica sol with 5 g of o-phosphoric acid in the ratio lOO:lOg of boric acid .. . . . .. ,. . , j, . " ., , . . . . . - ....... . - ~ , . .. . .-. .:, ., . - . . ~ .
21296~9 . - 19 -Compon~nt C: 25 g of a mixture of 100 g of 40% silica sol in a ratio 1:1 with 40% potassium water glass and 10% water additisn as possible diluent Premix V: 85 g of a powder mixture of lO0 g of potassium tri-silica.e with 5 g of zirconium oxide, lO g of boric acid, 50 g of 40% silica sol with 2.5 g of o-phosphoric acid in the ratio 100:10 g of boric acid, which is dried for approximately 8 to 12 hou-s and subsequently intimately mixed with 10 g of hydro-carbonate (formed from premixes Vl-V3 and V7).
Components A,B',B and C are mixed together in the following way.
300 g cf component A are thoroughly mixed with 5 g of component B' and subsequently completely wetted with 25 g of component B7 -so tha~ apart from a consistency like wet sand there is an opti-mum pi~mentation and thorough colouring during the reaction phase ~ith the aid and hydroxide carbonate. Following the mixing process 25 g of component C is poured into the wet, thorou3hly coloured sand and agaln intimately mixed. The pro-duct has a gelling tendency and consequently becomes free-f lowin3 ~ but remains moist.
The resulting 390 g of moist, free-flowing mixture AB'BC are mixed ~ith 85 g of dry powder component V, so that an almost dry po~der i~ obtained. To homogenize the mixture and commi-nute a-~y lumps, the product is passed through a fine sieve.
The resulting 475 g of mixture are allowed to stand for approx-imatel~ 1 to 2 hours. The powder is hydrated by the water bind-ing ti-e to a granular powder mixt~re, which is further proc-essed 'not storage-stable).
The 47~ g of the above mixture are mixed with 2 g of Na-meta--silica-e. This takes place by intimate mixing, so that the mixtur~ becomes sticky and moist. During mixing successively `
212 9 6 .~ ~
50 g of 100 g of 50% silica sol with a ratio of 100:30 g of lithium polysilicate (V5) are added. During the pouring in of the sol oxide polysilicate the metasilicate reacts as a water binder and hydrates the 545 g of product slowly for approxim-ately 1 to 2 nours so as to give a granular sand with different particle sizes. After the setting time the mixture tends to agglomerate and must therefore be passed through a sieve again in order to produce free-flowing granules. The resulting 545 g of mixture are further processed in the following way. The dry granular product contains bound water, which is further hydra-ted by mixing a further 20 g of Na~metasilicate. This gives a moist, tacky state, to which are added 70 to 80 g of a mixture of white cement 100:10 g of kaolin. Accompanied by vigorous mixing and possibly again passing through a sieve, approxim-ately 650 g of a uniform granular product are obtained.
Example VI (formulation only):
Component A: 300 g of cristobalite sand (Berger, Mineralien-handel, Zurich, Switzerland) Component B: 5 g of o-phosphoric acid and aluminium oxide with a mixing ratio of lOOg:5g Component C: 25 g oE 40% silica sol in a ratio of 1:1 to 40%
potassium water glass Component V: 80 to 90 g of 100 g potassium trisilicate with 5 g of inorganic pigment (e.g. spinel, Bayer-Leverkusen). with 5 g of zirconium oxide and 10 g of boric acid as Vl and V2 combined with V4, namely 50 g of 40% silica sol in a ratio of 100:5 g of o-phosphoric acid with mixing and drying. Mixing also takes place with 10 g of Ca-carbonate according to V7 Mixt,ure A,B,C,V: To the 430 g obtained are added 20 g of ~` - 21 - 21296~9 Na-metasilicate and V5 or 50 g of a mixture of 40% silica sol 100:30 g lithium polysilicate (V5) Stabilization: To the 500 g obtained are added 20 g of Na-metasilicate and a mixture of 70 to 80 g of white cement in a ratio of 100:10 g of calcium hydroxide. The combination of Ca-hydroxide with the cemen~ as the reactant for the hydration, has an effect on the homogenization during the subsequent pro-cessing of the finished granules to a material.
Thiq leads to 600 g of granular material, which is storable and when stirred with water is compressed to a solid.
Example VII (formulation only):
Component A: 500 g of aluminium oxide twhite corrundum) Component B: 10 g of a mixture of phosphoric acid, zirconium acetate, titanium oxide, zirconium oxide (mixing ratio 100:10:5:5 g) Component C: 50 g of a mixture of 40% s-llica sol, potassium silicate, borosilicate glass powder and zirconium carbonate tmixing ratio 100:50:20:10 g) which in gel-powder form solidi-fies rapidly, so that when mixing corresponding precautions must be taken (see hereinafter) Component V: 160 g of a mixture of potassium trisilicate, boro-silicate glass powder, Ca-carbor.ate, boric acid, zirconium hydroxide (mixing ratio 100:25:10:10:15 g) Mixture A,B~C,V: To the 720 g of mixture obtained are added for hydration and balancing purposes 20 g of Na-metasilicate and 50 g of a mixture of 40% silica sol, component B (see above) borosilicate glass powder 9 titanium oxide, zirconium oxide (mixing ratio 100:10:25:5:5 g) ~ 22 - 2 1 2 9 6 ~ 9 Stabilization: To the 790 g of mixture obtained are added 15 g of Na-metasilicate and 75 g of white cement.
880 g of granular product are obtained, which can be stored and i6 processed by adding dispersant to the finished silica substance.
Example VIII (formulation only):
Component A: 500 g of aluminium oxide (white corrundum) Component B: 5 g of a mixture of phosphoric acid and aluminium oxide ~mixing ratio 50:5 g) .
Component C: 50 g of a mixture of water, potassium trisilicate, aluminium oxide, borosilicate glass powder (mixing ratio 100:100:5:20 g), said gel-powder mixture solidifying rapidly, so that when mixing corresponding precautions must be taken (see hereinafter) Component V: 175 g of a mixture of potassium trisilicate, aluminium oxide, Ca-hydrocarbonate, boric acid and zirconium hydroxide (mixing ratio 75:5:10:10:15 g) Mixture A,B,C,V: The 730 g of mixture obtained are mixed for hydration and balancing purposes with 20 g of sodium metasili-cate and 50 g of a mixture of 40% silica sol, component B (see above), boric acid, titanium oxide, zirconium oxide and kaolin (mixing ratio 100:5:5:5:5 g) Stabilization: The 750 g of mixture obtained are mixed with 15 g of sodium metasilicate and 75 g of white cement.
890 g of storable granular material are obtained and this is processed to the finished silica substance by adding dispersant.
As intimated hereinbefore, part of the mixtures to be mixed is , . .. ... .
- 23 - 21296~9 solidified during the mixing process, so that special mixing precautions must be taken. It is recommended that the mixtures be mixed rapidly and forced through a sieve in the not com-pletely solidified state. It is also possible to use static mixers.
Carbonates reacting with acids bring about the gassing out of carbon dioxide in the mixture. The carbon dioxide from the ambient air and that in the mixture bring about the desired silification. Without carbon dioxide there is no good silific-ation or crosslinking. There is optimum pigmentation in the case of low dosage and use of pigments. A complete thorough dyeing is obtained when glass fillers are used. The chemical composition also permits colouring such as in the case of gems, e.g. lapis lazuli, turquoise, malachite and rhodonite. Thus, compared with the hitherto known mineral silicate materials particular significance must be attached to the value increase obtained setting new criteria as a refining and improving process.
Settin~ and Stabilizin~
Metasilicates (as above), hydrocarbonates or hydroxide such as calcium hydroxide, magnesium hydroxide, aluminium hydroxide, titanium hydroxide, zirconium hydroxide, further hydrating products such as white cement, Portland cement, or a combina-tion of cements and hydroxides or novel hydrating products, which are specifically modified in view of the desired mineral composition, e.g. with a combination of clinker minerals.
Quantitative variations for the basic examples Example I: hydroxide example.
Component A: 300 g of borosilicate glassmaking sand (Berger &
Bachmann, Buchs AG, 5witzerland) Component B: 5 g of a mixture of 100 g of 40% silica sol (Levasil) with 5 g of o-phosphoric acid in a ratio of 100:10 g of boric acid.
Component C: 25 g of a mixture of 100 g of 40% silica sol in a ratio of 1:1 with 40% lithium polysilicate (Van Baerle, Munchenstein, BL, Switzerland).
Premix: formed from premixes Vl, V2 and V3 comprising 75 g of a powder mix of 100 g of potassium trisilicate (Van Baerle), 5 g of zirconium oxide (MEL) and 10 g of boric acid, as well as 50 g of a mixture of 100 g of 40% silica sol with 5 g of a mixture of phosphoric acid 100:10 g with boric acid (compo-.. , ~ .. . . . . ~ . . . . . . . . . . . . . . .
14 - 212 9 g~9 nent B) and dried for approximately 8 to 12 hours at ambient temperature.
Premix V7: 10 to 20 g with in each case 10 g of Ca-hydroxide (10 g zirconium hydroxide - MEL) are mixed with the above premix (V1, V2 and V3).
Component V: 70 to 80 g of the t~o premixes V1-V3 and V7 are mixed together and well homogenize~ (e.g. through a hair sleve).
Components A, B and C are mixed together in the following way:
300 g of component A are comple~ely wetted with S g of compo-nent B, so that a wet sand consist~ncy is obtained. 25 g of component C is poured into the "wet sand" and intimately ~ixed.
Following the mixing process the product has a gelling tendency and consequently becomes free-flo~-ing9 but still remains moist.
The resulting 330 g of the moist, free-flowing mixture ABC are mixed with component V (80 g of dry powder), so that an almost dry powder is obtained. In order to homogenize the mix~ure and comminute any lumps, the product is forced through a sieve.
The resulting 410 g of mixture are allowed to stand for between 1 and 2 hours. The powder is hydrated by the water binding time to a granular powder mixture, which is further processed (not storage-stable).
The 410 g of the above-prepared mixture are mixed with 20 g of Na-metasilicate. This takes place by intimate mixing, the mix-ture becoming somewhat sticky and ~oist. During mixing succ-essive pouring in takes place of 50 g of a mixture of 200 g of 40% silica sol and 5 g of aluminiu~ oxide and 10 g of Ca-hydrocarbonate (V6 as the balancir.~ agent). During the pouring in of the sol oxide the metasilicate reacts as a water binder and hydrates the 480 g slowly for approximately 1 to 5 hours so - 15 - 21296~9 ; i as to give a granular sand with different part-icle sizes. If at the end of the setting time the mixture has a lump formation tendency and a tendency to produce free-flowing granules, the product is again passed through a sieve.
The resulting 480 g of mixture are further processed in the following way. The dry granular product contains bound water, which is further hydrated by mixing in a further 20 g of Na-metasilicate. This gives a moist and ~acky sta~e and addition takes place of a hydroxylizing (catalyzing) substance. Substi-tute for new hydration products, with the following proportions:
Tricalcium silicate [(3 CaO, SiO2 (C3S)], dicalcium silicate [(2 CaO, SiO2 (C2S)]~ tricalcium aluminate [(3 CaO, Al203 (C3A)], tetracalcium aluminate ferrite [(4 CaO, Al203, Fe203)], calcium sulphate hydrate [(CaS04 2H20 (C 4AF)] and calcium oxide (CaO) formulated for specific material modifications, can be added in place of 50 to 70 g of white cement combined with Ca-carbonates, Ca-hydroxides, kaolin, etc. and vigorous mixing then leads to a uniform granular product of approximately 570 g.
The end product is a chemically modified mixture, which is step-wise prevented from reacting and is subsequently transformed stepwise into difeerent aggregate states as a basic material until an irreversible chemical process mechanlsm is ended. As a basic material and starting substance prior to processing, the end product can be stored, but must be protected against moisture. As a function of the pigmentation, the granules have different colours and as a function of the basic substance (i.e.
quartz sand, glassmaking or other mineral sands) they are more bri.lliant or dull. These granules can be stirred or mixed with water. As a function of the doughy to free-flowing consistency the substance can be calandered, spatula-applied, poured or sprayed. When poured or otherwise applied to a surface such as glass, metal, ceramic, concrete, wood or plastic, the material adheres and reacts with the atmospheric carbon dioxide and the -` 21296~9 substrate by silification, during which a more or less pron-ounced crystalline structure is obtained. The completely reacted product is waterproof, tough, hard, resistant to most mechanical actions and can also be used as a rock glue or inor-ganic adhesive. The range of uses is virtually unlimited.
Example II (formulation only): (carbonate example) Component A: 300 g of glassmaking sand (Berger & Bachmann Component B: 5 g of 40~ silica sol with 5 g of phosphoric acid in the ratio 100:10 g of boric acid Component C: 25 g of 40% silica sol 1:1 lithium polysilicate (Van Baerle) Component V: 80 to 90 g of 100 g potassium trisilicate wi~h 2.5 g aluminium oxide and 10 g of boric acid mixed with 10 to 20 g of Ca-hydrocarbonate (corresponding to a mixture of pre-mixes V1-V3 and V7) -Mixtures A,B,C,V: To the 410 g obtained are added 20 g of Na-metasilicate (hydrating agent - ~an Baerle) and 50 g of a mix-ture of 50 g of 40% silica sol in the ratio 3:1 lithium poly-silicate (Van Baerle - V5 as balancing agen~) Stabilization: To the 460 g are added 20 g of Na-metasilicate and 60 to 80 g white cement (Dickenhoff, Germany). The combin-ation of Ca-carbonate in component V with the cement as the reactant for the hydration, has an effect on the homogenization during the subsequent processing of the finished granular material to a product (i.e. on stirring the finished granules with dispersant, here water). The result is a granular mater-ial, which can be stored and mixe~ with water Rives a solid material.
~`` - 17 - 2~296~9 -, The addition and mixing in the case of example II are substan-tially the same as in example I. The following exemplified formulations are processed in the same way.
Example III (formulation only): (kaolin example) Component A: 300 g of quartz sand (Zimmerli Mineralstoffe, Zurich, Switzerland) Component B: 5 g of a mixture of 50 g of o-phosphoric acid with 5 g of aluminium oxide Component C: 50 g of a mixture of water 1:1 potassium trisllicate Component V: 85 g of a mixture of 100 g of potassium trisili- ~ :
cate with 5 g of Ti-oxide (Degussa), 10 g of boric acid, 50 g of 40~ silica sol with 5 g of phosphoric acid in ratio lOOg:lOg of boric acid, dried for 1 to 5 hours, as well as 10 to 20 g of kaolin (Siegfried, Zofingen, Switzerland) added to the dry powder.
Mixture A,B,C,V: 20 g of Na-metasilicate to the 480 g of mix-ture, as hydrating agent for the further addition of 50 g of 40% silica sol in the ratio 3:1 lithium polysilicate on the basis of 50 g of component C (V5 as balancing agent) Stabilization: 20 g of Na-metasilicate for further wetting and crosslinking with 75 g of a mixture of 60 g white cement and 15 g Ca-hydroxide Granular material: 600 g as end product.
Example IV (formulatlon only) Component A: 500 g of white corundum (e.g. for implantation : :.: . : -2~29~
: - 18 -medicine~ Berger & Bachmann) (same volume as 300 g due to spec-ific weight) Component B: 5 g of o-phosphoric acid lOOg:5g of aluminium oxide Component C: 50 g of tricalcium sllicate and water (in mixing ratio 1:1) Component V: 135 g of a mixture of 75 g potassium trisilica~e (Van Baerle) and 5 g of Al-oxide, 20 g of borosilicate glass powder, 10 g of boric acid, 10 g of Ca-carbonate, 15 g of Zi-hydroxide, and 20 g of sodium metasilicate Mixture A,B,C,V: 710 g of filler and powder proportion wet~ed with 50 g of a mixture of 200 g of 40% silica sol and 5 g of Zi-oxide, 5 g of titanium oxide, 5 g of boric acid, and ~ :
5 g of kaolin and dried in air Stabilization: 15 g of Na-metasilicate for further wetting and crosslinking with 75 g of white cement Granular material: 850 g as end product.
Pigmentation to basic examples Example V:
Component A: 300 g of borosilicate glassmaking sand ..Component B': 5 g of copper hydroxide carbonate..(pigmenting agent, Siegfried, Zofingen~ Switzerland) Component B: 25 g of a mixture of 100 g of 40~ silica sol with 5 g of o-phosphoric acid in the ratio lOO:lOg of boric acid .. . . . .. ,. . , j, . " ., , . . . . . - ....... . - ~ , . .. . .-. .:, ., . - . . ~ .
21296~9 . - 19 -Compon~nt C: 25 g of a mixture of 100 g of 40% silica sol in a ratio 1:1 with 40% potassium water glass and 10% water additisn as possible diluent Premix V: 85 g of a powder mixture of lO0 g of potassium tri-silica.e with 5 g of zirconium oxide, lO g of boric acid, 50 g of 40% silica sol with 2.5 g of o-phosphoric acid in the ratio 100:10 g of boric acid, which is dried for approximately 8 to 12 hou-s and subsequently intimately mixed with 10 g of hydro-carbonate (formed from premixes Vl-V3 and V7).
Components A,B',B and C are mixed together in the following way.
300 g cf component A are thoroughly mixed with 5 g of component B' and subsequently completely wetted with 25 g of component B7 -so tha~ apart from a consistency like wet sand there is an opti-mum pi~mentation and thorough colouring during the reaction phase ~ith the aid and hydroxide carbonate. Following the mixing process 25 g of component C is poured into the wet, thorou3hly coloured sand and agaln intimately mixed. The pro-duct has a gelling tendency and consequently becomes free-f lowin3 ~ but remains moist.
The resulting 390 g of moist, free-flowing mixture AB'BC are mixed ~ith 85 g of dry powder component V, so that an almost dry po~der i~ obtained. To homogenize the mixture and commi-nute a-~y lumps, the product is passed through a fine sieve.
The resulting 475 g of mixture are allowed to stand for approx-imatel~ 1 to 2 hours. The powder is hydrated by the water bind-ing ti-e to a granular powder mixt~re, which is further proc-essed 'not storage-stable).
The 47~ g of the above mixture are mixed with 2 g of Na-meta--silica-e. This takes place by intimate mixing, so that the mixtur~ becomes sticky and moist. During mixing successively `
212 9 6 .~ ~
50 g of 100 g of 50% silica sol with a ratio of 100:30 g of lithium polysilicate (V5) are added. During the pouring in of the sol oxide polysilicate the metasilicate reacts as a water binder and hydrates the 545 g of product slowly for approxim-ately 1 to 2 nours so as to give a granular sand with different particle sizes. After the setting time the mixture tends to agglomerate and must therefore be passed through a sieve again in order to produce free-flowing granules. The resulting 545 g of mixture are further processed in the following way. The dry granular product contains bound water, which is further hydra-ted by mixing a further 20 g of Na~metasilicate. This gives a moist, tacky state, to which are added 70 to 80 g of a mixture of white cement 100:10 g of kaolin. Accompanied by vigorous mixing and possibly again passing through a sieve, approxim-ately 650 g of a uniform granular product are obtained.
Example VI (formulation only):
Component A: 300 g of cristobalite sand (Berger, Mineralien-handel, Zurich, Switzerland) Component B: 5 g of o-phosphoric acid and aluminium oxide with a mixing ratio of lOOg:5g Component C: 25 g oE 40% silica sol in a ratio of 1:1 to 40%
potassium water glass Component V: 80 to 90 g of 100 g potassium trisilicate with 5 g of inorganic pigment (e.g. spinel, Bayer-Leverkusen). with 5 g of zirconium oxide and 10 g of boric acid as Vl and V2 combined with V4, namely 50 g of 40% silica sol in a ratio of 100:5 g of o-phosphoric acid with mixing and drying. Mixing also takes place with 10 g of Ca-carbonate according to V7 Mixt,ure A,B,C,V: To the 430 g obtained are added 20 g of ~` - 21 - 21296~9 Na-metasilicate and V5 or 50 g of a mixture of 40% silica sol 100:30 g lithium polysilicate (V5) Stabilization: To the 500 g obtained are added 20 g of Na-metasilicate and a mixture of 70 to 80 g of white cement in a ratio of 100:10 g of calcium hydroxide. The combination of Ca-hydroxide with the cemen~ as the reactant for the hydration, has an effect on the homogenization during the subsequent pro-cessing of the finished granules to a material.
Thiq leads to 600 g of granular material, which is storable and when stirred with water is compressed to a solid.
Example VII (formulation only):
Component A: 500 g of aluminium oxide twhite corrundum) Component B: 10 g of a mixture of phosphoric acid, zirconium acetate, titanium oxide, zirconium oxide (mixing ratio 100:10:5:5 g) Component C: 50 g of a mixture of 40% s-llica sol, potassium silicate, borosilicate glass powder and zirconium carbonate tmixing ratio 100:50:20:10 g) which in gel-powder form solidi-fies rapidly, so that when mixing corresponding precautions must be taken (see hereinafter) Component V: 160 g of a mixture of potassium trisilicate, boro-silicate glass powder, Ca-carbor.ate, boric acid, zirconium hydroxide (mixing ratio 100:25:10:10:15 g) Mixture A,B~C,V: To the 720 g of mixture obtained are added for hydration and balancing purposes 20 g of Na-metasilicate and 50 g of a mixture of 40% silica sol, component B (see above) borosilicate glass powder 9 titanium oxide, zirconium oxide (mixing ratio 100:10:25:5:5 g) ~ 22 - 2 1 2 9 6 ~ 9 Stabilization: To the 790 g of mixture obtained are added 15 g of Na-metasilicate and 75 g of white cement.
880 g of granular product are obtained, which can be stored and i6 processed by adding dispersant to the finished silica substance.
Example VIII (formulation only):
Component A: 500 g of aluminium oxide (white corrundum) Component B: 5 g of a mixture of phosphoric acid and aluminium oxide ~mixing ratio 50:5 g) .
Component C: 50 g of a mixture of water, potassium trisilicate, aluminium oxide, borosilicate glass powder (mixing ratio 100:100:5:20 g), said gel-powder mixture solidifying rapidly, so that when mixing corresponding precautions must be taken (see hereinafter) Component V: 175 g of a mixture of potassium trisilicate, aluminium oxide, Ca-hydrocarbonate, boric acid and zirconium hydroxide (mixing ratio 75:5:10:10:15 g) Mixture A,B,C,V: The 730 g of mixture obtained are mixed for hydration and balancing purposes with 20 g of sodium metasili-cate and 50 g of a mixture of 40% silica sol, component B (see above), boric acid, titanium oxide, zirconium oxide and kaolin (mixing ratio 100:5:5:5:5 g) Stabilization: The 750 g of mixture obtained are mixed with 15 g of sodium metasilicate and 75 g of white cement.
890 g of storable granular material are obtained and this is processed to the finished silica substance by adding dispersant.
As intimated hereinbefore, part of the mixtures to be mixed is , . .. ... .
- 23 - 21296~9 solidified during the mixing process, so that special mixing precautions must be taken. It is recommended that the mixtures be mixed rapidly and forced through a sieve in the not com-pletely solidified state. It is also possible to use static mixers.
Carbonates reacting with acids bring about the gassing out of carbon dioxide in the mixture. The carbon dioxide from the ambient air and that in the mixture bring about the desired silification. Without carbon dioxide there is no good silific-ation or crosslinking. There is optimum pigmentation in the case of low dosage and use of pigments. A complete thorough dyeing is obtained when glass fillers are used. The chemical composition also permits colouring such as in the case of gems, e.g. lapis lazuli, turquoise, malachite and rhodonite. Thus, compared with the hitherto known mineral silicate materials particular significance must be attached to the value increase obtained setting new criteria as a refining and improving process.
Claims (19)
1. Process for the production of solid mineral materials or semifinished products based on sol oxides, polysilicates and fillers, in which apart from the crosslinking of the solid dis-perse phase in the dispersants the solid disperse phase is used as an overmatrix, in order to incorporate therein macroparticles in the form of fillers, the dispersant being set in substoichio-metric quantity, so that the product is still reactive, but storage-stable and can be completely reacted by adding further dispersant quantities in order to obtain the solid mineral material.
2. Process according to claim 1, characterized in that a matrix-like substance of filler-like macroparticles and sol oxide (crosslinking substance) and a buffer are brought toge-ther and processed for assisting the formation of the over-matrix and if there is to be a variation of the material char-acteristics a variation mixture is introduced into the subs-tance and subsequently the substance is transformed into the desired reactive preliminary stage of the material in further stages for hydration, balancing, setting and stabilizing.
3. Process according to claim 2, characterized in that the variation mixture for varying the substance is prepared from one or more premixes.
4. Process according to claim 3, characterized in that the premixes have an acid or basic component such as phosphoric acid or boric acid of hydroxides or carbonates or are admixed to premixes with acid or basic components.
S. Process according to one of the claims 2, 3 or 4, charac-terized in that the sol oxide content is increased by adding a proportion of unsolled oxide, e.g. S-oxide (fumed silica, Aerosil) to the silica sol and a gelling delay is brought about by solling on.
6. Process according to one of the claims 2 to 5, character-ized in that during additions for obtaining a pigmented compo-nent of the substance an acid is added, which brings about a colouring of the component after a residence time.
7. Process according to one of the claims 2 to 6, character-ized in that in the substance provided with the variation mix-ture dispersants are set by adding hydrating agents.
8. Process according to claim 7, characterized in that to the mixture with the set dispersant are added further hydrating agents and hydroxides or carbonates, so that it becomes reac-tive and storage-stable.
9. Process according to claim 7 and/or 8, characterized in that the hydrating agent is a metasilicate (K or Na-metasili-cate) or a cement such as white or Portland cement.
10. Process according to claim 8, characterized in that the carbonates Ca-carbonate, Mg-carbonate, Al-carbonate, Ti-carbonate, Zi-carbonate or their hydrocarbonates are used alone or in mixture.
11. Process according to claim 8, characterized in that the hydroxide Ca-hydroxide, Mg-hydroxide, Al-hydroxide, Ti-hydroxide, Zi-hydroxide are used alone or in mixture.
12. Process according to one of the claims 1 to 11, character-ized in that variation mixtures are added to the premixes or metal pigmenting salts to the substance.
13. Process according to one of the claims 1 to 11, character-ized in that variation mixtures are added to the premixes or mineral pigmenting substances to the substance.
14. Process according to claim 12, characterized in that the metal salts are Al, Fe, Cu, Cr or Co-salts, which are used as sulphates, nitrates, hydroxides, etc.
15. Process according to claim 13, characterized in that the mineral substances are spinel, lapis lazuli, malachite, rhodo-nite and turquoise, which are preferably used in the finely ground state.
16. Process according to claims 1, 2 or 3, characterized in that the filler proportion comprises borosilicate glass, quartz glass or glassmaking or foundry sand or mineral sands or aluminium oxide or an organic or inorganic fibrous material or a mixture of two or more of said fillers.
17. Products produced according to one of the processes of claims 1 to 16.
18. Product according to claim 17, characterized in that it is a semifinished product, which can be processed to a cured mat-erial by mixing in dispersant.
19. Product according to claim 18, characterized in that it is a cured material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH3763/92-0 | 1992-12-09 | ||
| PCT/CH1993/000269 WO1994013597A1 (en) | 1992-12-09 | 1993-11-26 | Process for producing siliceous materials and siliceous materials thus produced |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2129659A1 true CA2129659A1 (en) | 1994-06-23 |
Family
ID=4548706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2129659 Abandoned CA2129659A1 (en) | 1992-12-09 | 1993-11-26 | Process for the production of a silica substance-containing material and materials produced therefrom |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2129659A1 (en) |
-
1993
- 1993-11-26 CA CA 2129659 patent/CA2129659A1/en not_active Abandoned
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