Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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
- 3 -
~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
- 4 -
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~
-- 10 --
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
-- 1 1 --
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
- 16 -
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.
