CA2010181A1 - Aqueous dispersion of micro silica having a delayed thixotropic reaction - Google Patents
Aqueous dispersion of micro silica having a delayed thixotropic reactionInfo
- Publication number
- CA2010181A1 CA2010181A1 CA002010181A CA2010181A CA2010181A1 CA 2010181 A1 CA2010181 A1 CA 2010181A1 CA 002010181 A CA002010181 A CA 002010181A CA 2010181 A CA2010181 A CA 2010181A CA 2010181 A1 CA2010181 A1 CA 2010181A1
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- CA
- Canada
- Prior art keywords
- aqueous dispersion
- micro silica
- silica
- micro
- delayed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Abstract
AN AQUEOUS DISPERSION OF MICRO
SILICA HAVING A DELAYED THIXOTROPIC REACTION
ABSTRACT OF THE DISCLOSURE
The thixotropic reaction that takes place in an aqueous dispersion of micro silica is delayed by the addition of a pre-determined amount of at least one chemical additive selected from the group consisting of amides, such as carbamide, or polyols, such as glycerol and propylene glycol.
SILICA HAVING A DELAYED THIXOTROPIC REACTION
ABSTRACT OF THE DISCLOSURE
The thixotropic reaction that takes place in an aqueous dispersion of micro silica is delayed by the addition of a pre-determined amount of at least one chemical additive selected from the group consisting of amides, such as carbamide, or polyols, such as glycerol and propylene glycol.
Description
AN AQUEOUS DISPERSION OF MICRO
SILICA HAVING A DELAYED THIXOTROPIC REACTION
TECHNICAL FIELD
The present invention relates generally to thixotropic reactions and more particularly to the addition of at least one chemical additive to an aqueous dispersion of micro silica to delay the thixotropic reaction which occurs therein.
BACKGROUND ART
Fumed silica can be manufactured by a process involving reacting evaporated silicon tetrachloride in an oxygen-hydrogen flame to produce silicon dioxide and hydrochloric acid. The resulting product is 99.8% pure silica, its pa~ticles are non-porous, extremely small in diameter (average 12 millimicrons), have a defined shape, and are loosely agglomerated. The surface of the particles contain siloxane and silanol groups. In terms of numbers, the siloxane groups within the resulting product predominate aausing the product to have a fully lnert character. The sila~ol groups wlthln the resulting product impart hydrophilic properties. However, with compounds that are especially reactive, such as organosilanes, chemical reactions with the silanol groups may be carried out, thus imparting hydrophobic properties. Areas of application for the resultlng product include paints and inks, and use as a suspension and/or and anti-blocking agent.
The manufacture of precipitated silica begins with the reaction of an alkaline silicate solution, usually sodium silicate (waterglass), with a mineral acid. The resultant white precipitate is pumped through filter presses which yiold cakes with higher solids content than could be .. . :. ~: : ,. . .: , X~V18~ ~
obtained through other filtration means. Salts that are formed during the precipitation process are washed out in the filtering equipment. The resulting solid content of the filtered cakes is generally in the range of 15 to 20%.
Drying is carried out through turbine, rotary, or spray drying. Since 80 to 85% of the water must be driven off during the drying process, this process is cost intensive.
Milling can generally be done after drying to reduce the size o agglomerates formed during the drying process. After milling has been completed, sizing classification separates :
the product from grit and other impurities. Purity of the resulting product is in the range of 98-100% silica. Areas i o application for precipitated silica include use as an 15 agent for any of the following functions: anti-blocking, ~;
anti-slip, defoaming, infiulation, thickening, polishing, carrier (liquids to powders), filler for inks, clarifier for liquid systems, etc.
The resulting products produced by both of the foregoing processes have a BET surface area in excess of 100 m2/g and a tamped density of approximately 100 g1l. In additlon, both of the~e products have a tendency to gel when ln a colloi~al di~pe~slon. In ~rder to prevent, to a certain degree, the gelllng behavior of a colloidal dispersion of precipitated silica, it has been proposed (Society of Petroleum Engineers Journal, July, 1969, page 42) that precipitated silica be reacted with dimethyldichlorosilane.
The precipitated silica produced by this reaction is more expensive because of the additional production step required.
Micro silica is produced as a by-product in the manufacture o~ ferrosilicon or silicon metals through the use of electric arc furnaces. This by-product material contains ~; .
- - .. . - . ........... . :
~: - :. . - . .
:~ :: , . . .. . ; ... . . .
181.
high amounts of extremely fine spherical particles of silicon dioxide. The micro silica is captured from the escaping gasses of the arc furnaces by means of electrostatic precipitators. The collected material generally contains more than 7~ percent silicon dioxide. Other constituents are carbon, sulfur, and the oxides of iron, aluminum, calcium, magnesium, sodium and potassium. The chemical composition of this ~y-product varies depending upon the type of metal or 1~ alloy being produced. For example, the micro sllica produced from à furnace being used to manufacture errosilicon metal will generally contain more iron and magnesium oxide than from a furnace being used to manufacture silicon metal. Regardless of the type of charge within the furnace, the micro silica produced as a by-product typically has a BET surface area of approximately 20 m2/g, a bul~ density of approximately 200 g/l and a tamped density of approximately 600 g/l It has been found that the addition of micro silica to fresh concrete affects the pore size distribution and the hydration products formed during hydration, and thereby increases th~ strength and durability o~ the resulting aoncrete product~ The propertie~ of micro ~ilica and its use as an additive to cement, concrete and mortar have been thoroughly discussed in a technical paper entitled "Silica Fume" by ~. M. Malhotra and G. G. Garette in the May, 1982 issue of Concrete Construction, pages 443 to 446~ The technical information contained in the foregoing paper is ~ incorporated by reference in the description of the present ; 30 invention.
Since micro silica consists of very fine vitreous particles, most of which are smaller than one micron, it has been noted by the aforementioned authors that the use of this product presents handling problems and may pose a health : ; , ~ , .,; : ,; -,~ . . ~, . ., ~ . . ............................. ..
:-:, ,- :, ~
.: . .: .. : :. . ~ . . . :
hazard. These problems can be overcome by transporting and using micro silica in the form of an aqueous dispersion consisting, in general, of approximately 50% by weight of water, and the balance being micro silica. A problem, however, arises with the use of such aqueous dispersions of micro silica due to the fact that such dispersions have an af~inity to become thixotropic.
The a~finity to thixotropy may be desirable in certain applications, For example, this property is desirable and necessary in order to produce the coating of fumed silica or precipitated silica which is placed on cardboard to reduce warpage and to maintain the non-skid properties of same. In the concrete industry, however, the affinity of such dispersions to become thixotropic is undesirable and there has been considerable research with respect to techniques for delaying the thixotropic reaction which occurs in such dispersion~.
SUMMARY OF THE INVENTION
The present invention solves the problems associated with the prior art as well a~ other problem~ by providing an aqu~ous di~persion o~ micro sllica which ha~ a delayed affinity to becoming thlxotropic. This delayed affinity results from adding to the aqueous dispersion a pre-determined amount of at least one chemical additive selected from the group consisting of amides and polyols. These chemical additives have the ability to modi~y the rheology of the thixotropic reaction by breaking the physical bonding between the interstices of the submicroscopic crystalline particles of micro silica. The results obtained by the present invention indicate that an aqueous dispersion of ; micro silica to which is added a pre-determined amount of at . ..: : ... .,. : . . .
. . : f . :: : :
SILICA HAVING A DELAYED THIXOTROPIC REACTION
TECHNICAL FIELD
The present invention relates generally to thixotropic reactions and more particularly to the addition of at least one chemical additive to an aqueous dispersion of micro silica to delay the thixotropic reaction which occurs therein.
BACKGROUND ART
Fumed silica can be manufactured by a process involving reacting evaporated silicon tetrachloride in an oxygen-hydrogen flame to produce silicon dioxide and hydrochloric acid. The resulting product is 99.8% pure silica, its pa~ticles are non-porous, extremely small in diameter (average 12 millimicrons), have a defined shape, and are loosely agglomerated. The surface of the particles contain siloxane and silanol groups. In terms of numbers, the siloxane groups within the resulting product predominate aausing the product to have a fully lnert character. The sila~ol groups wlthln the resulting product impart hydrophilic properties. However, with compounds that are especially reactive, such as organosilanes, chemical reactions with the silanol groups may be carried out, thus imparting hydrophobic properties. Areas of application for the resultlng product include paints and inks, and use as a suspension and/or and anti-blocking agent.
The manufacture of precipitated silica begins with the reaction of an alkaline silicate solution, usually sodium silicate (waterglass), with a mineral acid. The resultant white precipitate is pumped through filter presses which yiold cakes with higher solids content than could be .. . :. ~: : ,. . .: , X~V18~ ~
obtained through other filtration means. Salts that are formed during the precipitation process are washed out in the filtering equipment. The resulting solid content of the filtered cakes is generally in the range of 15 to 20%.
Drying is carried out through turbine, rotary, or spray drying. Since 80 to 85% of the water must be driven off during the drying process, this process is cost intensive.
Milling can generally be done after drying to reduce the size o agglomerates formed during the drying process. After milling has been completed, sizing classification separates :
the product from grit and other impurities. Purity of the resulting product is in the range of 98-100% silica. Areas i o application for precipitated silica include use as an 15 agent for any of the following functions: anti-blocking, ~;
anti-slip, defoaming, infiulation, thickening, polishing, carrier (liquids to powders), filler for inks, clarifier for liquid systems, etc.
The resulting products produced by both of the foregoing processes have a BET surface area in excess of 100 m2/g and a tamped density of approximately 100 g1l. In additlon, both of the~e products have a tendency to gel when ln a colloi~al di~pe~slon. In ~rder to prevent, to a certain degree, the gelllng behavior of a colloidal dispersion of precipitated silica, it has been proposed (Society of Petroleum Engineers Journal, July, 1969, page 42) that precipitated silica be reacted with dimethyldichlorosilane.
The precipitated silica produced by this reaction is more expensive because of the additional production step required.
Micro silica is produced as a by-product in the manufacture o~ ferrosilicon or silicon metals through the use of electric arc furnaces. This by-product material contains ~; .
- - .. . - . ........... . :
~: - :. . - . .
:~ :: , . . .. . ; ... . . .
181.
high amounts of extremely fine spherical particles of silicon dioxide. The micro silica is captured from the escaping gasses of the arc furnaces by means of electrostatic precipitators. The collected material generally contains more than 7~ percent silicon dioxide. Other constituents are carbon, sulfur, and the oxides of iron, aluminum, calcium, magnesium, sodium and potassium. The chemical composition of this ~y-product varies depending upon the type of metal or 1~ alloy being produced. For example, the micro sllica produced from à furnace being used to manufacture errosilicon metal will generally contain more iron and magnesium oxide than from a furnace being used to manufacture silicon metal. Regardless of the type of charge within the furnace, the micro silica produced as a by-product typically has a BET surface area of approximately 20 m2/g, a bul~ density of approximately 200 g/l and a tamped density of approximately 600 g/l It has been found that the addition of micro silica to fresh concrete affects the pore size distribution and the hydration products formed during hydration, and thereby increases th~ strength and durability o~ the resulting aoncrete product~ The propertie~ of micro ~ilica and its use as an additive to cement, concrete and mortar have been thoroughly discussed in a technical paper entitled "Silica Fume" by ~. M. Malhotra and G. G. Garette in the May, 1982 issue of Concrete Construction, pages 443 to 446~ The technical information contained in the foregoing paper is ~ incorporated by reference in the description of the present ; 30 invention.
Since micro silica consists of very fine vitreous particles, most of which are smaller than one micron, it has been noted by the aforementioned authors that the use of this product presents handling problems and may pose a health : ; , ~ , .,; : ,; -,~ . . ~, . ., ~ . . ............................. ..
:-:, ,- :, ~
.: . .: .. : :. . ~ . . . :
hazard. These problems can be overcome by transporting and using micro silica in the form of an aqueous dispersion consisting, in general, of approximately 50% by weight of water, and the balance being micro silica. A problem, however, arises with the use of such aqueous dispersions of micro silica due to the fact that such dispersions have an af~inity to become thixotropic.
The a~finity to thixotropy may be desirable in certain applications, For example, this property is desirable and necessary in order to produce the coating of fumed silica or precipitated silica which is placed on cardboard to reduce warpage and to maintain the non-skid properties of same. In the concrete industry, however, the affinity of such dispersions to become thixotropic is undesirable and there has been considerable research with respect to techniques for delaying the thixotropic reaction which occurs in such dispersion~.
SUMMARY OF THE INVENTION
The present invention solves the problems associated with the prior art as well a~ other problem~ by providing an aqu~ous di~persion o~ micro sllica which ha~ a delayed affinity to becoming thlxotropic. This delayed affinity results from adding to the aqueous dispersion a pre-determined amount of at least one chemical additive selected from the group consisting of amides and polyols. These chemical additives have the ability to modi~y the rheology of the thixotropic reaction by breaking the physical bonding between the interstices of the submicroscopic crystalline particles of micro silica. The results obtained by the present invention indicate that an aqueous dispersion of ; micro silica to which is added a pre-determined amount of at . ..: : ... .,. : . . .
. . : f . :: : :
2 ~
least one of the foregoing additives substantially delays the gelling of same.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
According to a preferred embodiment of the present invention, the addition of at least one chemical additive selected from the group consisting of amides and polyols to an aqueous disperslon of micro silica containing from 40 to 55% by weight of micro silica and from 1 to 5% by weight of the additive, the remainder being water, results in the aqueous dispersion having a delayed affinity to becoming thixotropic. The micro silica utilized is produced as a by-product in the manufacture of ferrosilicon or silicon metals through electric arc furnaces and is typically comprised of extremely ~ine,~ amorphous silica particles having a surface area of approximately 20 m2/g and a tamped density of approximately 600 g/l. The pH of the resulting dispersion is 7.
The amides which can be added to the aqueous dl~per~ion o micro silica must have a solubility co~P~i¢ient i~ water ~u~iclent to be aompletely dissolved or mixed in tha aqueous dlsper~lon. Examples of amide~ which may be used lnclude carbamide, biuret, formamide, acetamlde, and carbamic acid, with carbamide being preferred. In particular, it has been found that 1 to 2%
carbamide in a 50% aqueous dispersion of micro silica effectively delays the aqueous dispersion from becoming thixotropic and allows for much easier handling of same in industrial situations. In effect, the thixotropic reaction is delayed and a liquid phase is maintained for a conslderable number of days.
, , ~; . . .................. ~. - , :
... , ..... - ,. . . .. - . . . . . : .. - ~.: .. .
.. ., . . . ., :.: - , -, ... .
- `, ' , ' .. . ~ ., . . . , ' , The polyols which can be added to the aqueous dispersion of micro silica must also be completely soluble or mixable in this solution. Polyols which can be used include diols and triols, such as ethylene glycol, propylene glycol, butylene glycol, and glycerol, with glycerol and propylene glycol being preferred.
The invention will be described further in conjunction with the following examples which are not intended to limit the invention described herein. These examples illustrate te~t results at different temperatures of aqueous dispersions of micro silica (50% solids) with and without various additives thereto.
Example I
Propylene Glycerine 38F Plain Carbamide~2% Glycol-5% 5%
Time inter~al beor0 gel 18 hrs. 14 days 5 days 6 days occurred , (very 1uid) 18 days ~very fluid) 21 days ~very little signs of setting or gelling) 28 days (gelled-but very ~oft gel~
., .
i , .,, . . - , .
.. . , . ~ .- ~ . - .
- .
.. . .
.. . . . .
~G~ 8~
Example II
Propylene Glycerine 72F Plain Carbamide-2~ Glycol-5% 5 Time interval before 12 hrs. 11 days 24 hrs. 36 hrs.
gel (slight occurred increase in viscosity) 14 days ~maintained same viscosity) 18 days (approx. 1/2 has ~ begun to gel-soft gel) 21 days (approx. 3/4 has begun to gel-so~t gel) ,.
25 days (gelled-~oft gel-no lump~) .
~ ~ .
:
i, ~'. . ' .' i : ., '. ' . . . ': . ' ' , ' ': ' ' ' . .' ' . ' , ' . . :
2~1S~ ;
:
--8-- , Example III
Propylene Glycerine 102F Plain Carbamide-2% G1YCO1-5% 5%
Time interval before 12 hrs. 9 days 2 days 2 days gel (slight occurrèd increase in viscosity) 12 days (approx. 1/2 gelled but very soft gel-no lumps) 14 days (approx. 3/4 gelled still soft gel-no lumps) " 18 days (gelled-but very soft gel-no lumps) The results shown in Examples I, II and III are of particular interest since they illustrate that a thlxotropic reaatlon can be delayed with the addition of the proper additlve to. the aqueous disperslon of micro silica. The addition of the proper additive delays the thixotropic reaction that takes place when no additive is used.
While the invention has been described with reference to certain preferred embodiments, those skilled in the art will appreciate that various modifications and substitutions can be made wi~hout departing from the spirit of the invention. In particular, the aqueous dispersion of micro silica with proper additives ,mày have added thereto small amounts of compatible chelating agents containing alkaline earth cations, such as magnesium or calcium, which normally ~1 , :. . . .. . .. ... . ...
.
.; .: . . . , ~ :
1', ' , ~ '~ , ~ ; . , 2~
occur in ordinary water and would also tend to precipitate surface active agents, without substantially effecting the delaying of the thixotropic reaction. Furthermore, small amounts of compatible cosmetic coloring agents or the like may be added to the aqueous dispersion without any significant effect.
Certain modifications and improvements will occur to those skilled in the art upon reading the foregoing. It should be understood that all such modifications and improvements have been deleted herein for the sake of conclseness and readability, but are properly with the scope ~ the following claims.
; - ~ .... ; .,: -. . ,: . . , . ................... .. . -.
:: - ' . : . .
least one of the foregoing additives substantially delays the gelling of same.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
According to a preferred embodiment of the present invention, the addition of at least one chemical additive selected from the group consisting of amides and polyols to an aqueous disperslon of micro silica containing from 40 to 55% by weight of micro silica and from 1 to 5% by weight of the additive, the remainder being water, results in the aqueous dispersion having a delayed affinity to becoming thixotropic. The micro silica utilized is produced as a by-product in the manufacture of ferrosilicon or silicon metals through electric arc furnaces and is typically comprised of extremely ~ine,~ amorphous silica particles having a surface area of approximately 20 m2/g and a tamped density of approximately 600 g/l. The pH of the resulting dispersion is 7.
The amides which can be added to the aqueous dl~per~ion o micro silica must have a solubility co~P~i¢ient i~ water ~u~iclent to be aompletely dissolved or mixed in tha aqueous dlsper~lon. Examples of amide~ which may be used lnclude carbamide, biuret, formamide, acetamlde, and carbamic acid, with carbamide being preferred. In particular, it has been found that 1 to 2%
carbamide in a 50% aqueous dispersion of micro silica effectively delays the aqueous dispersion from becoming thixotropic and allows for much easier handling of same in industrial situations. In effect, the thixotropic reaction is delayed and a liquid phase is maintained for a conslderable number of days.
, , ~; . . .................. ~. - , :
... , ..... - ,. . . .. - . . . . . : .. - ~.: .. .
.. ., . . . ., :.: - , -, ... .
- `, ' , ' .. . ~ ., . . . , ' , The polyols which can be added to the aqueous dispersion of micro silica must also be completely soluble or mixable in this solution. Polyols which can be used include diols and triols, such as ethylene glycol, propylene glycol, butylene glycol, and glycerol, with glycerol and propylene glycol being preferred.
The invention will be described further in conjunction with the following examples which are not intended to limit the invention described herein. These examples illustrate te~t results at different temperatures of aqueous dispersions of micro silica (50% solids) with and without various additives thereto.
Example I
Propylene Glycerine 38F Plain Carbamide~2% Glycol-5% 5%
Time inter~al beor0 gel 18 hrs. 14 days 5 days 6 days occurred , (very 1uid) 18 days ~very fluid) 21 days ~very little signs of setting or gelling) 28 days (gelled-but very ~oft gel~
., .
i , .,, . . - , .
.. . , . ~ .- ~ . - .
- .
.. . .
.. . . . .
~G~ 8~
Example II
Propylene Glycerine 72F Plain Carbamide-2~ Glycol-5% 5 Time interval before 12 hrs. 11 days 24 hrs. 36 hrs.
gel (slight occurred increase in viscosity) 14 days ~maintained same viscosity) 18 days (approx. 1/2 has ~ begun to gel-soft gel) 21 days (approx. 3/4 has begun to gel-so~t gel) ,.
25 days (gelled-~oft gel-no lump~) .
~ ~ .
:
i, ~'. . ' .' i : ., '. ' . . . ': . ' ' , ' ': ' ' ' . .' ' . ' , ' . . :
2~1S~ ;
:
--8-- , Example III
Propylene Glycerine 102F Plain Carbamide-2% G1YCO1-5% 5%
Time interval before 12 hrs. 9 days 2 days 2 days gel (slight occurrèd increase in viscosity) 12 days (approx. 1/2 gelled but very soft gel-no lumps) 14 days (approx. 3/4 gelled still soft gel-no lumps) " 18 days (gelled-but very soft gel-no lumps) The results shown in Examples I, II and III are of particular interest since they illustrate that a thlxotropic reaatlon can be delayed with the addition of the proper additlve to. the aqueous disperslon of micro silica. The addition of the proper additive delays the thixotropic reaction that takes place when no additive is used.
While the invention has been described with reference to certain preferred embodiments, those skilled in the art will appreciate that various modifications and substitutions can be made wi~hout departing from the spirit of the invention. In particular, the aqueous dispersion of micro silica with proper additives ,mày have added thereto small amounts of compatible chelating agents containing alkaline earth cations, such as magnesium or calcium, which normally ~1 , :. . . .. . .. ... . ...
.
.; .: . . . , ~ :
1', ' , ~ '~ , ~ ; . , 2~
occur in ordinary water and would also tend to precipitate surface active agents, without substantially effecting the delaying of the thixotropic reaction. Furthermore, small amounts of compatible cosmetic coloring agents or the like may be added to the aqueous dispersion without any significant effect.
Certain modifications and improvements will occur to those skilled in the art upon reading the foregoing. It should be understood that all such modifications and improvements have been deleted herein for the sake of conclseness and readability, but are properly with the scope ~ the following claims.
; - ~ .... ; .,: -. . ,: . . , . ................... .. . -.
:: - ' . : . .
Claims (9)
1. An aqueous dispersion of micro silica having a delayed affinity to becoming thixotropic comprising a mixture of about 40 to 55% by weight of micro silica, 1 to 5% by weight of at least one additive selected from the group comprising amides and polyols, and the remainder being water.
2. The aqueous dispersion as defined in claim 1 wherein said additive is carbamide.
3. The aqueous dispersion as defined in claim 1 wherein said additive is glycerol.
4. The aqueous dispersion as defined in claim 1 wherein said additive is propylene glycol.
5. The aqueous dispersion as defined in claim 1 wherein the amount of said micro silica in said mixture is about 50%
by weight, and the amount of said additive is about 1 to 2%
by weight and is selected from the group comprising amides.
by weight, and the amount of said additive is about 1 to 2%
by weight and is selected from the group comprising amides.
6. The aqueous dispersion as defined in claim 1 wherein the amount of said micro silica in said mixture is about 50%
by weight, and the amount of said additive is about 5% by weight and is selected from the group comprising polyols.
by weight, and the amount of said additive is about 5% by weight and is selected from the group comprising polyols.
7. The aqueous dispersion as defined in claim 1 wherein said micro silica has a pH of about 7.
8. The aqueous dispersion as defined in claim 1 wherein said micro silica has a BET surface area of about 20 m2/g.
9. The aqueous dispersion as defined in claim 1 wherein said micro silica has a tamped density of about 600 g/l.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002010181A CA2010181A1 (en) | 1988-04-11 | 1990-02-15 | Aqueous dispersion of micro silica having a delayed thixotropic reaction |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17997788A | 1988-04-11 | 1988-04-11 | |
| CA002010181A CA2010181A1 (en) | 1988-04-11 | 1990-02-15 | Aqueous dispersion of micro silica having a delayed thixotropic reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2010181A1 true CA2010181A1 (en) | 1991-08-15 |
Family
ID=25673957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002010181A Abandoned CA2010181A1 (en) | 1988-04-11 | 1990-02-15 | Aqueous dispersion of micro silica having a delayed thixotropic reaction |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2010181A1 (en) |
-
1990
- 1990-02-15 CA CA002010181A patent/CA2010181A1/en not_active Abandoned
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |