CA2710768A1 - Method for making colloidal metal oxide particles - Google Patents
Method for making colloidal metal oxide particles Download PDFInfo
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- CA2710768A1 CA2710768A1 CA2710768A CA2710768A CA2710768A1 CA 2710768 A1 CA2710768 A1 CA 2710768A1 CA 2710768 A CA2710768 A CA 2710768A CA 2710768 A CA2710768 A CA 2710768A CA 2710768 A1 CA2710768 A1 CA 2710768A1
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- 239000002245 particle Substances 0.000 title claims abstract description 256
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 252
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 251
- 238000000034 method Methods 0.000 title claims abstract description 104
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 131
- 239000000377 silicon dioxide Substances 0.000 claims description 44
- 239000000376 reactant Substances 0.000 claims description 27
- 239000008119 colloidal silica Substances 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 230000006911 nucleation Effects 0.000 claims description 16
- 238000010899 nucleation Methods 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 15
- 238000013178 mathematical model Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003729 cation exchange resin Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 150000004760 silicates Chemical class 0.000 claims description 7
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 5
- 239000003456 ion exchange resin Substances 0.000 claims description 5
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims 4
- 239000007795 chemical reaction product Substances 0.000 claims 2
- 239000000203 mixture Substances 0.000 abstract description 14
- 238000007792 addition Methods 0.000 description 30
- 230000008569 process Effects 0.000 description 13
- 238000007796 conventional method Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 229910052681 coesite Inorganic materials 0.000 description 7
- 229910052906 cristobalite Inorganic materials 0.000 description 7
- 229910052682 stishovite Inorganic materials 0.000 description 7
- 229910052905 tridymite Inorganic materials 0.000 description 7
- 229940023913 cation exchange resins Drugs 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000013386 optimize process Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- 150000002738 metalloids Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000013387 non optimize process Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052699 polonium Inorganic materials 0.000 description 1
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0047—Preparation of sols containing a metal oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Colloid Chemistry (AREA)
- Silicon Compounds (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Methods of making colloidal metal oxide particles and compositions containing colloidal metal oxide particles are disclosed.
Description
METHOD FOR MAKING COLLOIDAL METAL OXIDE PARTICLES
FIELD OF THE INVENTION
[0001] The present invention is directed to methods of making colloidal metal oxide particles.
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
[0001] The present invention is directed to methods of making colloidal metal oxide particles.
BACKGROUND OF THE INVENTION
[0002] Efforts continue in the art to form colloidal metal oxide particles in an energy efficient manner.
[0003] There is a need in the art for improved processes of forming colloidal metal oxide particles in an energy efficient manner while optimizing apparatus utilization.
SUMMARY OF THE INVENTION
SUMMARY OF THE INVENTION
[0004] The present invention provides new methods of forming colloidal metal oxide particles. The disclosed methods of forming colloidal metal oxide particles enable the formation of colloidal metal oxide particles under near optimum process conditions so as to form the colloidal metal oxide particles in a very efficient manner.
Further, the disclosed methods of forming colloidal metal oxide particles enable optimum utilization of reaction vessels due to decreased reaction periods needed to form colloidal metal oxide particles.
Further, the disclosed methods of forming colloidal metal oxide particles enable optimum utilization of reaction vessels due to decreased reaction periods needed to form colloidal metal oxide particles.
[0005] The disclosed methods of forming colloidal metal oxide particles comprise a step of adding one or more reactants to a reaction vessel, wherein the step of adding one or more reactants takes into account various in situ reaction conditions including, but not limited to, at least one of (i) a particle nucleation rate within a reaction vessel, (ii) a metal oxide deposition rate onto existing metal oxide particles (e.g., seed metal oxide particles and/or nucleated metal oxide particles) within the reaction vessel, and/or (iii) growth of metal oxide particles (e.g., seed metal oxide particles and/or nucleated metal oxide particles) within the reaction vessel.
[0006] In one exemplary embodiment, a method of making colloidal metal oxide particles comprises the step of adding reactive metal oxide to a reaction vessel at a metal oxide mass addition rate that is based on a mathematical model that takes into account at least one of (i) a particle nucleation rate, (ii) a metal oxide deposition rate onto existing metal oxide particles, and/or (iii) growth of metal oxide particles in the reaction vessel, wherein the metal oxide mass addition rate increases as a function of reaction time. In a further embodiment the addition rate is greater than 10.0 grams of reactive metal oxide per 1000 square meters (m) of total particle surface area per hour (g/1000 m2-hr) during at least a portion of a reaction period. In an even further exemplary embodiment, a method of making colloidal metal oxide particles according to the present invention comprises the step of adding reactive metal oxide to a reaction vessel at a metal oxide mass addition rate according to a mathematical model that provides an optimum metal oxide mass addition rate, q, as represented by the formula'-.q = (3moGr/DP03)( Dpo +
Grt)2 wherein:
(a) mo represents a mass of metal oxide particles in the reaction vessel as measured in grams (g);
(b) Gr represents a metal oxide particle growth rate of the metal oxide particles in the reaction vessel as determined by an increase in particle diameter and as measured in nanometers per hour (nm/hr);
(c) Dpo represents an average metal oxide particle diameter as measured in nanometers (nm); and (d) t represents time in hours (hr).
Grt)2 wherein:
(a) mo represents a mass of metal oxide particles in the reaction vessel as measured in grams (g);
(b) Gr represents a metal oxide particle growth rate of the metal oxide particles in the reaction vessel as determined by an increase in particle diameter and as measured in nanometers per hour (nm/hr);
(c) Dpo represents an average metal oxide particle diameter as measured in nanometers (nm); and (d) t represents time in hours (hr).
[0007] The disclosed methods of making colloidal metal oxide particles may comprise a step of forming nucleated metal oxide particles and/or a step of growing metal oxide seed particles. In one exemplary embodiment, the method of making colloidal metal oxide particles comprises the step of adding one or more reactants to a reaction vessel (i) containing water and (ii) being substantially free of any seed metal oxide particles, wherein the one or more reactants are capable of forming nucleated metal oxide particles; forming nucleated metal oxide particles within the reaction vessel; and growing the nucleated metal oxide particles within the reaction vessel so as to form colloidal metal oxide particles, wherein the growing step comprises increasing a feed rate of the one or more reactants over a reaction period.
[0008] The disclosed methods of making colloidal metal oxide particles enable the production of colloidal metal oxide particles in an energy efficient manner with a reaction period significantly less than conventional reaction periods for forming colloidal metal oxide particles. In one exemplary embodiment, the method of making colloidal metal oxide particles comprises the step of adding reactive metal oxide to a reaction vessel at a metal oxide mass addition rate over a reaction period so as to form colloidal metal oxide particles having an average final particle diameter ranging from about 10 nm to about 200 nm, wherein the reaction period is as much as 50% shorter than a similar reaction period using conventional techniques (e.g., a constant reactive metal oxide feed rate). For example, using the present method, colloidal metal oxide particles having an average particle diameter in the range of 20-30 nm may be formed in a reaction period of about 21-28 minutes, while conventional methods of forming similarly sized colloidal metal oxide particles require reaction periods of at least 30 minutes, typically, from about 31 to minutes.
[0009] In another exemplary embodiment, the method of making colloidal metal oxide particles comprises the step of adding reactive metal oxide to a reaction vessel at a metal oxide mass addition rate over a reaction period so as to form colloidal metal oxide particles having an average final particle diameter ranges from about 20 nm to about 200 nm, the metal oxide mass addition rate increasing at least once during the reaction period. The increase in the metal oxide mass addition rate may, for example, be a single step increase or multiple step increases.
[0010] The present invention is further directed to methods of using colloidal metal oxide particles. In one exemplary method of using colloidal metal oxide particles, the method comprises applying a colloidal metal oxide particle composition onto a substrate; and drying the colloidal metal oxide particle composition so as to form a coating on the substrate.
[0011] These and other features and advantages of the present invention will become apparent after a review of the following detailed description of the disclosed embodiments and the appended claims.
BRIEF DESCRIPTION OF THE FIGURES
BRIEF DESCRIPTION OF THE FIGURES
[0012] FIG. 1 graphically depicts (i) nucleation rate of reactive metal oxide and (ii) deposition rate of reactive metal oxide onto existing particles as the concentration of reactive metal oxide changes;
[0013] FIG. 2 graphically depicts conditions that favor (i) deposition rate of reactive metal oxide onto existing particles, (ii) nucleation of new colloidal metal oxide particles and (iii) both (i) and (ii) as the concentration of reactive metal oxide changes;
[0014] FIG. 3 graphically depicts the reduction in reaction time needed to form colloidal metal oxide particles having an average particle diameter of 22 nm using (i) the optimized reactive metal oxide feed rate of the present invention and (ii) a constant reactive metal oxide feed rate used in conventional processes;
[0015] FIG. 4 graphically depicts step-wise addition of reactive metal oxide using optimized methods of the present invention so as to closely follow an optimal feed rate; and [0016] FIG. 5 graphically depicts particle size and surface area of colloidal silica particles formed via the optimized methods of the present invention versus colloidal silica particles formed via conventional methods (i.e., a constant reactive silica feed rate).
DETAILED DESCRIPTION OF THE INVENTION
DETAILED DESCRIPTION OF THE INVENTION
[0017] To promote an understanding of the principles of the present invention, descriptions of specific embodiments of the invention follow and specific language is used to describe the specific embodiments. It will nevertheless be understood that no limitation of the scope of the invention is intended by the use of specific language. Alterations, further modifications, and such further applications of the principles of the present invention discussed are contemplated as would normally occur to one ordinarily skilled in the art to which the invention pertains.
[0018] It must be noted that as used herein and in the appended claims, the singular forms "a", "and", and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "an oxide" includes a plurality of such oxides and reference to "oxide" includes reference to one or more oxides and equivalents thereof known to those skilled in the art, and so forth.
[0019] "About" modifying, for example, the quantity of an ingredient in a composition, concentrations, volumes, process temperatures, process times, recoveries or yields, flow rates, and like values, and ranges thereof, employed in describing the embodiments of the disclosure, refers to variation in the numerical quantity that may occur, for example, through typical measuring and handling procedures; through inadvertent error in these procedures; through differences in the ingredients used to carry out the methods; and like proximate considerations.
The term "about" also encompasses amounts that differ due to aging of a formulation with a particular initial concentration or mixture, and amounts that differ due to mixing or processing a formulation with a particular initial concentration or mixture.
Whether modified by. the term "about" the claims appended hereto include equivalents to these quantities.
The term "about" also encompasses amounts that differ due to aging of a formulation with a particular initial concentration or mixture, and amounts that differ due to mixing or processing a formulation with a particular initial concentration or mixture.
Whether modified by. the term "about" the claims appended hereto include equivalents to these quantities.
[0020] As used herein, "metal oxides" is defined as binary oxygen compounds where the metal is the cation and the oxide is the anion. The metals may also include metalloids. Metals include those elements on the left of the diagonal line drawn from boron to polonium on the periodic table. Metalloids or semi-metals include those elements that are on this line. Examples of metal oxides include silica, alumina, titania, zirconia, etc., and mixtures thereof.
[0021] The present invention is directed to methods of making colloidal metal oxide particles. The present invention is further directed to colloidal metal oxide particles, compositions comprising colloidal metal oxide particles, as well as methods of using colloidal metal oxide particles. A description of exemplary colloidal metal oxide particles, methods of making colloidal metal oxide particles, and methods of using colloidal metal oxide particles is provided below.
I. Methods of Making Colloidal Metal Oxide Particles [0022] The present invention is directed to methods of making colloidal metal oxide particles. Raw materials used to form the colloidal metal oxide particles of the present invention, as well as method steps for forming the colloidal metal oxide particles of the present invention are discussed below.
A. Raw Materials [0023] The disclosed methods of making colloidal metal oxide particles may utilize one or more of the following raw materials for making colloidal silica particles, but alternative raw materials may be utilized to form other types of colloidal metal oxide materials, such as colloidal alumina particles, colloidal titania particles, colloidal zirconia particles, etc., and combinations thereof.
1. Silicates [0024] The methods of making colloidal silica particles may utilize one or more silicon-containing raw materials. Suitable silicon-containing raw materials include, but are not limited to, silicates such as alkali metal silicates.
Desirably, one or more alkali metal silicates are used to form colloidal silica particles.
Suitable alkali metal silicates include, but are not limited to, sodium silicate, potassium silicate, calcium silicate, lithium silicate, magnesium silicate, and combinations thereof.
I. Methods of Making Colloidal Metal Oxide Particles [0022] The present invention is directed to methods of making colloidal metal oxide particles. Raw materials used to form the colloidal metal oxide particles of the present invention, as well as method steps for forming the colloidal metal oxide particles of the present invention are discussed below.
A. Raw Materials [0023] The disclosed methods of making colloidal metal oxide particles may utilize one or more of the following raw materials for making colloidal silica particles, but alternative raw materials may be utilized to form other types of colloidal metal oxide materials, such as colloidal alumina particles, colloidal titania particles, colloidal zirconia particles, etc., and combinations thereof.
1. Silicates [0024] The methods of making colloidal silica particles may utilize one or more silicon-containing raw materials. Suitable silicon-containing raw materials include, but are not limited to, silicates such as alkali metal silicates.
Desirably, one or more alkali metal silicates are used to form colloidal silica particles.
Suitable alkali metal silicates include, but are not limited to, sodium silicate, potassium silicate, calcium silicate, lithium silicate, magnesium silicate, and combinations thereof.
[0025] Suitable commercially available silicates include, but are not limited to, sodium and potassium silicates commercially available from a number of sources including PQ Corporation (Valley Forge, PA) and Zaclon, Inc. (Cleveland, OH).
2. Ion-Exchange Resins [0026] Any single silicate or combination of silicates may be reacted with one or more cation exchange resins to form colloidal silica particles in the disclosed methods. Suitable cation exchange resins for use in the present invention include, but are not limited to, strong acid cation (SAC) resins, weak acid cation (WAC) resins, and combinations thereof.
2. Ion-Exchange Resins [0026] Any single silicate or combination of silicates may be reacted with one or more cation exchange resins to form colloidal silica particles in the disclosed methods. Suitable cation exchange resins for use in the present invention include, but are not limited to, strong acid cation (SAC) resins, weak acid cation (WAC) resins, and combinations thereof.
[0027] Suitable commercially available cation exchange resins include, but are not limited to, cation exchange resins commercially available from a number of sources including Purolite Corporation (Bala Cynwyd, PA) such as those sold under the PUROLITE trade designation, and Dow Chemical (Midland, MI) such as those sold under the DOWEX trade designation.
[0028] Typically, one or more cation exchange resins are added to a reaction vessel at a resin addition rate so as to maintain the pH of the reaction vessel between about 8.0 and about 10.0, desirably, between about 9.2 and about 9.6.
3. Seed Metal Oxide Particles [0029] In some embodiments of the present invention, seed metal oxide particles are utilized as a starting raw material. In these embodiments, seed colloidal metal oxide particles from a number of suppliers may be used.
Suitable seed colloidal metal oxide particles for use in the present invention include, but are not limited to, seed colloidal metal oxide particles, such as colloidal silica particles commercially available from Nissan Chemical America Corporation (Houston, TX) and Eka Chemicals, Inc. (Marietta, GA).
B. Process Steps [0030] The disclosed methods of making colloidal metal oxide particles comprise a number of steps as discussed below.
1. Preparation of Reaction Vessel [0031] The disclosed methods of making colloidal metal oxide particles enable the production of colloidal metal oxide particles in an energy efficient manner with a reaction period significantly less than conventional reaction periods for forming colloidal metal oxide particles. In one exemplary embodiment, the method of making colloidal metal oxide particles comprises the step of adding one or more reactants to a reaction vessel (i) containing water and (ii) being substantially free of any seed metal oxide particles, wherein the one or more reactants are capable of forming nucleated metal oxide particles. In this embodiment, the step of preparing a reaction vessel simply comprises adding a desired amount of deionized (DI) water to the reaction vessel.
3. Seed Metal Oxide Particles [0029] In some embodiments of the present invention, seed metal oxide particles are utilized as a starting raw material. In these embodiments, seed colloidal metal oxide particles from a number of suppliers may be used.
Suitable seed colloidal metal oxide particles for use in the present invention include, but are not limited to, seed colloidal metal oxide particles, such as colloidal silica particles commercially available from Nissan Chemical America Corporation (Houston, TX) and Eka Chemicals, Inc. (Marietta, GA).
B. Process Steps [0030] The disclosed methods of making colloidal metal oxide particles comprise a number of steps as discussed below.
1. Preparation of Reaction Vessel [0031] The disclosed methods of making colloidal metal oxide particles enable the production of colloidal metal oxide particles in an energy efficient manner with a reaction period significantly less than conventional reaction periods for forming colloidal metal oxide particles. In one exemplary embodiment, the method of making colloidal metal oxide particles comprises the step of adding one or more reactants to a reaction vessel (i) containing water and (ii) being substantially free of any seed metal oxide particles, wherein the one or more reactants are capable of forming nucleated metal oxide particles. In this embodiment, the step of preparing a reaction vessel simply comprises adding a desired amount of deionized (DI) water to the reaction vessel.
[0032] In other embodiments, the method of making colloidal metal oxide particles comprises the step of adding one or more reactants to a reaction vessel containing (i) deionized (DI) water and (ii) seed metal oxide particles, wherein the one or more reactants are capable of forming nucleated metal oxide particles and/or growing the seed metal oxide particles. In this embodiment, the step of preparing a reaction vessel comprises adding (i) a desired amount of deionized (DI) water and (ii) a desired amount of seed metal oxide particles to the reaction vessel.
When utilized, the seed metal oxide particles typically have an initial average particle size (i.e., largest dimension) ranging from about 5 nm to about 15 nm.
2. Addition of Reactive Metal oxide [0033] The disclosed methods of forming colloidal metal oxide particles comprise a step of adding one or more of the above-described reactants to a reaction vessel, wherein the step of adding the one or more reactants takes into account various in situ reaction conditions including, but not limited to, at least one of (i) a particle nucleation rate within the reaction vessel, (ii) a metal oxide deposition rate onto existing metal oxide particles (e.g., seed metal oxide particles and/or nucleated metal oxide particles) within the reaction vessel, and/or (iii) growth of metal oxide particles (e.g., seed metal oxide particles and/or nucleated metal oxide particles) within the reaction vessel. The disclosed methods of forming colloidal metal oxide particles balance the feed rate of reactants against the deposition rate of reactive metal oxide onto existing metal oxide particles so as to control the extent of supersaturation of reactive metal oxide in the solution phase.
When utilized, the seed metal oxide particles typically have an initial average particle size (i.e., largest dimension) ranging from about 5 nm to about 15 nm.
2. Addition of Reactive Metal oxide [0033] The disclosed methods of forming colloidal metal oxide particles comprise a step of adding one or more of the above-described reactants to a reaction vessel, wherein the step of adding the one or more reactants takes into account various in situ reaction conditions including, but not limited to, at least one of (i) a particle nucleation rate within the reaction vessel, (ii) a metal oxide deposition rate onto existing metal oxide particles (e.g., seed metal oxide particles and/or nucleated metal oxide particles) within the reaction vessel, and/or (iii) growth of metal oxide particles (e.g., seed metal oxide particles and/or nucleated metal oxide particles) within the reaction vessel. The disclosed methods of forming colloidal metal oxide particles balance the feed rate of reactants against the deposition rate of reactive metal oxide onto existing metal oxide particles so as to control the extent of supersaturation of reactive metal oxide in the solution phase.
[0034] In one exemplary embodiment, a method of making colloidal metal oxide particles comprises the step of adding reactive metal oxide to a reaction vessel at a metal oxide mass addition rate that is based on a mathematical model that takes into account at least one of (i) a particle nucleation rate, (ii) a metal oxide deposition rate onto existing metal oxide particles, and/or (iii) growth of metal oxide particles in the reaction vessel, wherein the metal oxide mass addition rate increases as a function of reaction time. In a further embodiment, the addition rate is greater than 10.0 grams of reactive metal oxide per 1000 square meters (m) of total particle surface area per hour (g/1000 m2-hr) during at least a portion of a reaction period. In an even further exemplary embodiment, a method of making colloidal metal oxide particles according to the present invention comprises the step of adding reactive metal oxide to a reaction vessel at a metal oxide mass addition rate according to a mathematical model that provides an optimum metal oxide mass addition rate, q, as represented by the formula:q = (3moGr/DP 3)( Dpo + Grt)2 wherein:
(a) m0 represents a mass of metal oxide particles in the reaction vessel as measured in grams (g);
(b) Gr represents a metal oxide particle growth rate of the metal oxide particles in the reaction vessel as determined by an increase in particle diameter and as measured in nanometers per hour (nm/hr);
(c) Dp0 represents an average metal oxide particle diameter as measured in nanometers (nm); and (d) t represents time in hours (hr).
(a) m0 represents a mass of metal oxide particles in the reaction vessel as measured in grams (g);
(b) Gr represents a metal oxide particle growth rate of the metal oxide particles in the reaction vessel as determined by an increase in particle diameter and as measured in nanometers per hour (nm/hr);
(c) Dp0 represents an average metal oxide particle diameter as measured in nanometers (nm); and (d) t represents time in hours (hr).
[0035] In some embodiments, Gr ranges from about 10 to about 50 nm/hr, and q ranges from about 10.6 to about 52.8 g/1000 m2-hr during at least a portion of the reaction period. In other embodiments, Gr ranges from about 20 to about 40 nm/hr, and q ranges from about 21.1 to about 42.3 g/1000 m2-hr during at least a portion of the reaction period.
[0036] FIG. 1 graphically depicts a plot of (i) nucleation rate, RN, of reactive metal oxide and (ii) deposition rate, DR, of reactive metal oxide onto existing particles as the concentration of reactive metal oxide changes. As shown in FIG. 1, nucleation does not take place until (i) the concentration of reactive metal oxide exceeds a concentration at saturation, CS, and (ii) reaches a critical level of supersaturation identified as Cc. At this point, nucleation proceeds at an exponential rate, while the deposition rate continues along a linear path as the concentration of reactive metal oxide increases.
[0037] FIG. 2 graphically depicts process conditions that favor (i)...deposition rate of reactive metal oxide onto existing particles (i.e., at concentrations of reactive metal oxide less than Cc), (ii) nucleation of new colloidal metal oxide particles (i.e., at concentrations of reactive metal oxide above Cc) and (iii) both (i) and (ii) (i.e., at concentrations of reactive metal oxide above Cc and below a concentration CN
shown in FIG. 2) as the concentration of reactive metal oxide increases. When the concentration of reactive metal oxide increases above CN shown in FIG. 2, process conditions significantly favor nucleation of new metal oxide particles over deposition of metal oxide onto existing particles.
3. Completion of Particle Formation Step [0038] Once a desired metal oxide particle size has been reached, the addition of reactants to the reaction vessel is stopped, and an amount of deionized water is added to the reaction vessel in order to quench the reaction.
4. Filtering Step [0039] Following the quenching step, a filtering step (e.g., an ultrafiltration step) may be employed to remove unwanted salts resulting from the reaction of one or more cation exchange resins with one or more metal oxide raw materials.
C. Process Benefits [0040] The disclosed methods of making colloidal metal oxide particles enable the production of colloidal metal oxide particles while optimizing the utilization of reactor time and energy. In some exemplary embodiments, the method of making colloidal metal oxide particles enables the production of colloidal metal oxide particles having an average final particle diameter ranging from about 30 nm to about 200 nm in a reaction period that represents a 50% reduction in reaction period needed for making the same colloidal metal oxide particles using conventional methods.
shown in FIG. 2) as the concentration of reactive metal oxide increases. When the concentration of reactive metal oxide increases above CN shown in FIG. 2, process conditions significantly favor nucleation of new metal oxide particles over deposition of metal oxide onto existing particles.
3. Completion of Particle Formation Step [0038] Once a desired metal oxide particle size has been reached, the addition of reactants to the reaction vessel is stopped, and an amount of deionized water is added to the reaction vessel in order to quench the reaction.
4. Filtering Step [0039] Following the quenching step, a filtering step (e.g., an ultrafiltration step) may be employed to remove unwanted salts resulting from the reaction of one or more cation exchange resins with one or more metal oxide raw materials.
C. Process Benefits [0040] The disclosed methods of making colloidal metal oxide particles enable the production of colloidal metal oxide particles while optimizing the utilization of reactor time and energy. In some exemplary embodiments, the method of making colloidal metal oxide particles enables the production of colloidal metal oxide particles having an average final particle diameter ranging from about 30 nm to about 200 nm in a reaction period that represents a 50% reduction in reaction period needed for making the same colloidal metal oxide particles using conventional methods.
[0041] FIG. 3 graphically depicts the reduction in reaction time needed to form colloidal silica particles having an average particle diameter of 22 nm using (i) the optimized reactive silica feed rate of the present invention, and (ii) a constant reactive silica feed rate used in conventional processes.
[0042] FIG. 4 graphically depicts step-wise addition of reactive silica using optimized methods of the present invention so as to closely follow an optimal feed rate. As shown in FIG. 4, the disclosed methods of making colloidal silica particles may comprise one or more stepwise increases in the reactive silica feed rate during a given reaction period. Although only two-step or three-step methods:are shown in FIG....4,- any number of step increases in the reactive silica feed. rate may be= used in the present invention to closely follow an optimal feed rate depicted by the "optimal"
line shown in FIG. 4.
ll. Resulting Colloidal Metal Oxide Particles [0043] The colloidal metal oxide particles formed in the above-described methods of the present invention have a physical structure and properties similar to colloidal metal oxide particles formed in conventional methods of forming colloidal metal oxide particles as described below.
A. Metal Oxide Particle Dimensions [0044] The colloidal metal oxide particles of the present invention have a spherical particle shape with an average largest particle dimension (i.e., a largest diameter dimension). Typically, the colloidal metal oxide particles of the present invention have an average largest particle dimension of less than about 700 pm, more typically, less than about 100 pm. In one desired embodiment of the present invention, the colloidal metal oxide particles have an average largest particle dimension of from about 10.0 to about 100 pm, more desirably, from about 10.0 to about 30 pm.
line shown in FIG. 4.
ll. Resulting Colloidal Metal Oxide Particles [0043] The colloidal metal oxide particles formed in the above-described methods of the present invention have a physical structure and properties similar to colloidal metal oxide particles formed in conventional methods of forming colloidal metal oxide particles as described below.
A. Metal Oxide Particle Dimensions [0044] The colloidal metal oxide particles of the present invention have a spherical particle shape with an average largest particle dimension (i.e., a largest diameter dimension). Typically, the colloidal metal oxide particles of the present invention have an average largest particle dimension of less than about 700 pm, more typically, less than about 100 pm. In one desired embodiment of the present invention, the colloidal metal oxide particles have an average largest particle dimension of from about 10.0 to about 100 pm, more desirably, from about 10.0 to about 30 pm.
[0045] The colloidal metal oxide particles of the present invention typically have an aspect ratio of less than about 1.4 as measured, for example, using Transmission Electron Microscopy (TEM) techniques. As used herein, the term "aspect ratio" is used to describe the ratio between (i) the average largest particle dimension of the colloidal metal oxide particles and (ii) the average largest cross-sectional particle dimension of the colloidal metal oxide particles, wherein the cross-sectional particle dimension is substantially perpendicular to the largest particle dimension of the colloidal metal oxide particle. In some embodiments of the present invention, the colloidal metal oxide particles have an aspect ratio of less than about 1.3 (or less than about 1.2, or less than about 1.1, or less than about 1.05).
Typically, the colloidal metal oxide particles have an aspect ratio of from about 1.0 to about 1.2.
B. Metal Oxide Particle Surface Area [0046] The colloidal metal oxide particles of the present invention have an average surface area similar to colloidal metal oxide particles formed from conventional methods. Typically, the colloidal metal oxide particles of the present invention have an average surface area ranging from about 90 m2/g to about 180 m2/g. Desirably, the colloidal metal oxide particles of the present invention have an average surface area ranging from about 100 m2/g to about 160 m2/g, more desirably, from about 110 m2/g to about 150 m2/g.
Typically, the colloidal metal oxide particles have an aspect ratio of from about 1.0 to about 1.2.
B. Metal Oxide Particle Surface Area [0046] The colloidal metal oxide particles of the present invention have an average surface area similar to colloidal metal oxide particles formed from conventional methods. Typically, the colloidal metal oxide particles of the present invention have an average surface area ranging from about 90 m2/g to about 180 m2/g. Desirably, the colloidal metal oxide particles of the present invention have an average surface area ranging from about 100 m2/g to about 160 m2/g, more desirably, from about 110 m2/g to about 150 m2/g.
[0047] FIG. 5 graphically compares colloidal metal oxide particles, in this case colloidal silica particles, formed by the optimized process of the present invention with colloidal silica particles formed from conventional methods (i.e., a non-optimized process, namely, a constant metal oxide raw material feed rate). As shown in FIG.
5, colloidal silica particles formed from conventional methods had an average particle size of about 27.6 nm and an average particle surface area of about m2/g, while colloidal silica particles formed by the optimized process of the present invention had an average particle size of about 28.7 nm and an average particle surface area of about 142 m2/g.
5, colloidal silica particles formed from conventional methods had an average particle size of about 27.6 nm and an average particle surface area of about m2/g, while colloidal silica particles formed by the optimized process of the present invention had an average particle size of about 28.7 nm and an average particle surface area of about 142 m2/g.
[0048] As shown in FIG. 5, colloidal metal oxide (e.g., silica) particles formed by the optimized process of the present invention can produce substantially-similar colloidal metal oxide particles as formed from conventional methods. However, as discussed above, the colloidal metal oxide particles formed by the optimized process of the present invention can be produced in a much more efficient manner utilizing up to 50% less reactor time and process energy.
lll. Methods of Using Metal oxide Particles [0049] The present invention is further directed to methods of using the colloidal metal oxide particles formed in the above-described methods. In one exemplary method of using colloidal metal oxide particles, the method comprises applying a colloidal metal oxide particle composition onto a substrate; and drying the colloidal metal oxide particle composition so as to form a coating on the substrate.
Suitable substrates include, but are not limited to, paper, polymeric film, polymeric foam, glass, metal, ceramics, and fabrics.
lll. Methods of Using Metal oxide Particles [0049] The present invention is further directed to methods of using the colloidal metal oxide particles formed in the above-described methods. In one exemplary method of using colloidal metal oxide particles, the method comprises applying a colloidal metal oxide particle composition onto a substrate; and drying the colloidal metal oxide particle composition so as to form a coating on the substrate.
Suitable substrates include, but are not limited to, paper, polymeric film, polymeric foam, glass, metal, ceramics, and fabrics.
[0050] In other exemplary embodiments, the method of using colloidal metal oxide particles comprises utilizing the colloidal metal oxide particles as an abrasive/polishing composition for micro-electronics or other articles. In other exemplary embodiments, the method of using colloidal metal oxide particles comprises utilizing the colloidal metal oxide particles as an additive in paints to improve the mechanical properties of a dried paint film.
EXAMPLES
EXAMPLES
[0051] The present invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations upon the scope thereof. On the contrary, it is to be clearly understood that resort may be had to various other -embodiments, modifications, and equivalents thereof which, after reading-the description herein, may suggest themselves to those skilled in the art without departing from the spirit of the present invention and/or the scope of the appended claims.
Preparation of Colloidal Silica Particles Using Seed Silica Particles and an Optimized Silicate Addition Rate [0052] 28.4 kilograms (kg) (62.6 pounds (lb)) of deionized (DI) water were added to a 113.5 liter (I) (30 gallon (gal)) heated, agitated vessel to which 4.9 kg (10.9 lb) of a 40 wt% solids suspension of 12 nm colloidal silica material were added as a seed material. While agitating, the mixture was heated and maintained within the temperature range of 90-96 C. -Sodium silicate (29 wt% Si02, 9 wt% Na20) and .
a strong acid ion-exchange resin were then simultaneously added to the vessel at an initial silicate addition rate equivalent to 167.8 grams (g) SiO2/min (0.37 lb SiO2/min).
After 10 minutes, the silicate addition rate was increased to 317.5 g SiO2/min (0.70 lb SiO2/min) and maintained at this higher rate for an additional 11 minutes.
Preparation of Colloidal Silica Particles Using Seed Silica Particles and an Optimized Silicate Addition Rate [0052] 28.4 kilograms (kg) (62.6 pounds (lb)) of deionized (DI) water were added to a 113.5 liter (I) (30 gallon (gal)) heated, agitated vessel to which 4.9 kg (10.9 lb) of a 40 wt% solids suspension of 12 nm colloidal silica material were added as a seed material. While agitating, the mixture was heated and maintained within the temperature range of 90-96 C. -Sodium silicate (29 wt% Si02, 9 wt% Na20) and .
a strong acid ion-exchange resin were then simultaneously added to the vessel at an initial silicate addition rate equivalent to 167.8 grams (g) SiO2/min (0.37 lb SiO2/min).
After 10 minutes, the silicate addition rate was increased to 317.5 g SiO2/min (0.70 lb SiO2/min) and maintained at this higher rate for an additional 11 minutes.
[0053] Throughout the process, the resin addition rate was controlled to maintain the pH of the vessel between 9.2 and 9.6. After 21 minutes of silicate addition, both additions were stopped and the reaction quenched by the addition of DI water.
[0054] The resulting product was determined to have a particle size of 22+2 nm with minimal indication of additional nucleation of small particles.
Preparation of Colloidal Silica Particles Using Seed Silica Particles and a Constant Silicate Feed Rate [0055] The procedure in Example 1 was repeated except the silicate addition rate equivalent to 167.8 grams (g) SiO2/min (0.37 lb SiO2/min) was maintained throughout the process. The resin addition rate was controlled to maintain the pH of' the vessel between 9.2 and 9.6. This process was continued for 31 minutes after which additions of silicate and ion-exchange resin were stopped and the growth reaction was quenched by addition of DI water.
Preparation of Colloidal Silica Particles Using Seed Silica Particles and a Constant Silicate Feed Rate [0055] The procedure in Example 1 was repeated except the silicate addition rate equivalent to 167.8 grams (g) SiO2/min (0.37 lb SiO2/min) was maintained throughout the process. The resin addition rate was controlled to maintain the pH of' the vessel between 9.2 and 9.6. This process was continued for 31 minutes after which additions of silicate and ion-exchange resin were stopped and the growth reaction was quenched by addition of DI water.
[0056] The resulting product was determined to have a particle size of 22+2 nm.
[0057] While the invention has been described with a limited number of embodiments, these specific embodiments are not intended to limit the scope of the invention as otherwise described and claimed herein. It may be evident to -those of ordinary .-..skill in the= art upon review of the exemplary embodiments-herein;.-that further modifications, equivalents, and variations are possible. All parts and percentages in the examples, as well as in the remainder of the specification, are by weight unless otherwise specified. Further, any range of numbers recited in the specification or claims, such as that representing a particular set of properties, units of measure, conditions, physical states or percentages, is intended to literally incorporate expressly herein by reference or otherwise, any number falling within such range, including any subset of numbers within any range so recited. For example, whenever a numerical range with a lower limit, RL, and an upper limit Ru, is disclosed, any number R falling within the range is specifically disclosed. In particular, the following numbers R within the range are specifically disclosed: R = RL
+ k(Ru -RL), where k is a variable ranging from 1% to 100% with a 1%
increment, e.g., k is 1%, 2%, 3%, 4%, 5%.... 50%, 51%, 52%.... 95%, 96%, 97%, 98%, 99%, or 100%. Moreover, any numerical range represented by any two values of R, as calculated above is also specifically disclosed. Any modifications of the invention, in addition to those shown and described herein, will become apparent to those skilled in the art from the foregoing description and accompanying drawings. Such modifications are intended to fall within the scope of the appended claims.
All publications cited herein are incorporated by reference in their entirety.
+ k(Ru -RL), where k is a variable ranging from 1% to 100% with a 1%
increment, e.g., k is 1%, 2%, 3%, 4%, 5%.... 50%, 51%, 52%.... 95%, 96%, 97%, 98%, 99%, or 100%. Moreover, any numerical range represented by any two values of R, as calculated above is also specifically disclosed. Any modifications of the invention, in addition to those shown and described herein, will become apparent to those skilled in the art from the foregoing description and accompanying drawings. Such modifications are intended to fall within the scope of the appended claims.
All publications cited herein are incorporated by reference in their entirety.
Claims (42)
1. A method of making colloidal metal oxide particles, said method comprising the step of:
(a) adding reactive metal oxide to a reaction vessel at a metal oxide mass addition rate that is based on a mathematical model that takes into account (i) a particle nucleation rate, (ii) a metal oxide deposition rate onto existing metal oxide particles, and (iii) growth of metal oxide particles in the reaction vessel, the metal oxide mass addition rate increasing as a function of reaction time.
(a) adding reactive metal oxide to a reaction vessel at a metal oxide mass addition rate that is based on a mathematical model that takes into account (i) a particle nucleation rate, (ii) a metal oxide deposition rate onto existing metal oxide particles, and (iii) growth of metal oxide particles in the reaction vessel, the metal oxide mass addition rate increasing as a function of reaction time.
2. The method of Claim 1, wherein the mathematical model provides that an optimum metal oxide mass addition rate, q, is represented by the formula:
q = (3m o G r/D po3)( D po + G r t)2 wherein:
(a) m o represents a mass of metal oxide particles in the reaction vessel as measured in grams (g);
(b) G r represents metal oxide particle growth rate of the silica particles in the reaction vessel as determined by an increase in particle diameter and as measured in nanometers per hour (nm/hr);
(c) D po represents an average silica particle diameter as measured in nanometers (nm); and (d) t represents time in hours (hr).
q = (3m o G r/D po3)( D po + G r t)2 wherein:
(a) m o represents a mass of metal oxide particles in the reaction vessel as measured in grams (g);
(b) G r represents metal oxide particle growth rate of the silica particles in the reaction vessel as determined by an increase in particle diameter and as measured in nanometers per hour (nm/hr);
(c) D po represents an average silica particle diameter as measured in nanometers (nm); and (d) t represents time in hours (hr).
3. The method of Claim 2, wherein G r ranges from about 10 to about 50 nm/hr, and q ranges from about 10.6 to about 52.8 g/1000 m2-hr during at least a portion of the reaction period.
4. The method of Claim 2, wherein G r ranges from about 20 to about 40 nm/hr, and q ranges from about 21.1 to about 42.3 g/1000 m2-hr during at least a portion of the reaction period.
5. The method of Claim 1, wherein the metal oxide mass addition rate is greater than 10.0 grams of reactive metal oxide per 1000 square meters (m2) of total particle surface area per hour (g/1000 m2-hr) during at least a portion of a reaction period.
6. The method of Claim 1, wherein the step of adding reactive metal oxide comprises one or more stepwise increases in the metal oxide mass addition rate during the reaction period.
7. The method of Claim 1, further comprising the step of:
(a) introducing seed metal oxide particles into the reaction vessel prior to the step of adding reactive metal oxide.
(a) introducing seed metal oxide particles into the reaction vessel prior to the step of adding reactive metal oxide.
8. The method of Claim 7, wherein the seed metal oxide particles have an initial average particle size ranging from about 5 nm to about 15 nm.
9. The method of Claim 1, further comprising the step of:
(a) forming nucleated metal oxide particles in the reaction vessel as a result of the step of adding reactive metal oxide to the reaction vessel.
(a) forming nucleated metal oxide particles in the reaction vessel as a result of the step of adding reactive metal oxide to the reaction vessel.
10. The method of Claim 9, further comprising the step of:
(a) initially adding an aqueous solution to the reaction vessel prior to the step of adding reactive metal oxide, the aqueous solution being substantially free of metal oxide.
(a) initially adding an aqueous solution to the reaction vessel prior to the step of adding reactive metal oxide, the aqueous solution being substantially free of metal oxide.
11. The method of Claim 1, wherein the metal oxide comprises silica and the reactive metal oxide comprises a reaction product of a cationic ion exchange resin and an alkali metal silicate.
12. The method of Claim 11, further comprising one or more of the following steps:
(a) quenching a reaction between one or more silicates and one or more ion exchange resins with a sufficient amount of water.
(a) quenching a reaction between one or more silicates and one or more ion exchange resins with a sufficient amount of water.
13. The method of Claim 1, wherein the reactive period represents at least a 50%
reduction in reaction time when compared to a method of forming metal oxide particles in which the metal oxide mass addition rate is constant and below 10.0 g/1000 m2-hr.
reduction in reaction time when compared to a method of forming metal oxide particles in which the metal oxide mass addition rate is constant and below 10.0 g/1000 m2-hr.
14. A method of making colloidal metal oxide particles, said method comprising the step of:
(a) adding one or more reactants to a reaction vessel containing water and being substantially free of any seed metal oxide particles, said one or more reactants being capable of forming nucleated metal oxide particles;
(b) forming nucleated metal oxide particles within the reaction vessel; and (c) growing the nucleated metal oxide particles within the reaction vessel so as to form colloidal metal oxide particles, said growing step comprising increasing a feed rate of said one or more reactants over a reaction period.
(a) adding one or more reactants to a reaction vessel containing water and being substantially free of any seed metal oxide particles, said one or more reactants being capable of forming nucleated metal oxide particles;
(b) forming nucleated metal oxide particles within the reaction vessel; and (c) growing the nucleated metal oxide particles within the reaction vessel so as to form colloidal metal oxide particles, said growing step comprising increasing a feed rate of said one or more reactants over a reaction period.
15. The method of Claim 14, wherein the feed rate of said one or more reactants is a function of reaction time and is greater than 10.0 grams of reactive metal oxide per 1000 square meters (m2) of total particle surface area per hour (g/1000 m2-hr) during at least a portion of the reaction period.
16. The method of Claim 14, wherein the step of adding one or more reactants comprises one or more stepwise increases in the feed rate of the one or more reactants during the reaction period, the one or more stepwise increases being based on a mathematical model that provides an optimum metal oxide mass addition rate, q, represented by the formula:
q = (3m o G r/D po3)( D po + G r t)2 wherein:
(a) m o represents a mass of metal oxide particles in the reaction vessel as measured in grams (g);
(b) G r represents a metal oxide particle growth rate of the metal oxide particles in the reaction vessel as determined by an increase in particle diameter and as measured in nanometers per hour (nm/hr);
(c) D po represents an average metal oxide particle diameter as measured in nanometers (nm); and (d) t represents time in hours (hr).
q = (3m o G r/D po3)( D po + G r t)2 wherein:
(a) m o represents a mass of metal oxide particles in the reaction vessel as measured in grams (g);
(b) G r represents a metal oxide particle growth rate of the metal oxide particles in the reaction vessel as determined by an increase in particle diameter and as measured in nanometers per hour (nm/hr);
(c) D po represents an average metal oxide particle diameter as measured in nanometers (nm); and (d) t represents time in hours (hr).
17. The method of Claim 14, wherein the metal oxide comprises silica and the one or more reactants comprise a cationic ion exchange resin and a silicate.
18. A method of making colloidal metal oxide particles, said method comprising the step of:
(a) adding reactive metal oxide to a reaction vessel at a metal oxide mass addition rate over a reaction period so as to form colloidal metal oxide particles having an average final particle diameter ranges from about 20 nm to about 200 nm, the metal oxide mass addition rate increasing at least once during the reaction period.
(a) adding reactive metal oxide to a reaction vessel at a metal oxide mass addition rate over a reaction period so as to form colloidal metal oxide particles having an average final particle diameter ranges from about 20 nm to about 200 nm, the metal oxide mass addition rate increasing at least once during the reaction period.
19. The method of Claim 18, wherein the metal oxide mass addition rate is based on a mathematical model that takes into account (i) a particle nucleation rate, (ii) a metal oxide deposition rate on existing metal oxide particles, and (iii) growth of metal oxide particles in the reaction vessel, the metal oxide mass addition rate being greater than 10.0 grams of reactive metal oxide per 1000 square meters (m) of total particle surface area per hour (g/1000 m2-hr) during at least a portion of the reaction period.
20. The method of Claim 18, wherein the colloidal metal oxide particles have an average final particle diameter of about 20 to about 100 nm.
21. Colloidal metal oxide particles formed by the method of claim 1.
22. A method of making colloidal metal oxide particles comprising: adding reactive metal oxide to a reaction vessel at a metal oxide mass addition rate according to a mathematical model provides that an optimum metal oxide mass addition rate, q, is represented by the formula:
q = (3m o G r/D po3) ( D po + G r t)2 wherein:
(a) m o represents a mass of metal oxide particles in the reaction vessel as measured in grams (g);
(b) G r represents a metal oxide particle growth rate of the metal oxide particles in the reaction vessel as determined by an increase in particle diameter and as measured in nanometers per hour (nm/hr);
(c) D po represents an average metal oxide particle diameter as measured in nanometers (nm); and (d) t represents time in hours (hr).
q = (3m o G r/D po3) ( D po + G r t)2 wherein:
(a) m o represents a mass of metal oxide particles in the reaction vessel as measured in grams (g);
(b) G r represents a metal oxide particle growth rate of the metal oxide particles in the reaction vessel as determined by an increase in particle diameter and as measured in nanometers per hour (nm/hr);
(c) D po represents an average metal oxide particle diameter as measured in nanometers (nm); and (d) t represents time in hours (hr).
23. A method of making colloidal silica particles, said method comprising the step of:
(a) adding reactive silica to a reaction vessel at a silica mass addition rate that is based on a mathematical model that takes into account (i) a particle nucleation rate, (ii) a silica deposition rate onto existing silica particles, and (iii) growth of silica particles in the reaction vessel, the silica mass addition rate increasing as a function of reaction time and being greater than 10.0 grams of reactive silica per 1000 square meters (m) of total particle surface area per hour (g/1000 m2-hr) during at least a portion of a reaction period.
(a) adding reactive silica to a reaction vessel at a silica mass addition rate that is based on a mathematical model that takes into account (i) a particle nucleation rate, (ii) a silica deposition rate onto existing silica particles, and (iii) growth of silica particles in the reaction vessel, the silica mass addition rate increasing as a function of reaction time and being greater than 10.0 grams of reactive silica per 1000 square meters (m) of total particle surface area per hour (g/1000 m2-hr) during at least a portion of a reaction period.
24. The method of Claim 23, wherein the mathematical model provides that an optimum silica mass addition rate, q, is represented by the formula:
q = (3m o G r/D po3)( D po + G r t)2 wherein:
(a) m o represents a mass of silica particles in the reaction vessel as measured in grams (g);
(b) G r represents a silica particle growth rate of the silica particles in the reaction vessel as determined by an increase in particle diameter and as measured in nanometers per hour (nm/hr);
(c) D po represents an average silica particle diameter as measured in nanometers (nm); and (d) t represents time in hours (hr).
q = (3m o G r/D po3)( D po + G r t)2 wherein:
(a) m o represents a mass of silica particles in the reaction vessel as measured in grams (g);
(b) G r represents a silica particle growth rate of the silica particles in the reaction vessel as determined by an increase in particle diameter and as measured in nanometers per hour (nm/hr);
(c) D po represents an average silica particle diameter as measured in nanometers (nm); and (d) t represents time in hours (hr).
25. The method of Claim 24, wherein G r ranges from about 10 to about 50 nm/hr, and q ranges from about 10.6 to about 52.8 g/1000 m2-hr during at least a portion of the reaction period.
26. The method of Claim 24, wherein G r ranges from about 20 to about 40 nm/hr, and q ranges from about 21.1 to about 42.3 g/1000 m2-hr during at least a portion of the reaction period.
27. The method of Claim 23, wherein the step of adding reactive silica comprises one or more stepwise increases in the silica mass addition rate during the reaction period.
28. The method of Claim 23, further comprising the step of:
(a) introducing seed silica particles into the reaction vessel prior to the step of adding reactive silica.
(a) introducing seed silica particles into the reaction vessel prior to the step of adding reactive silica.
29. The method of Claim 28, wherein the seed silica particles have an initial average particle size ranging from about 5 nm to about 15 nm.
30. The method of Claim 23, further comprising the step of:
(a) forming nucleated silica particles in the reaction vessel as a result of the step of adding reactive silica to the reaction vessel.
(a) forming nucleated silica particles in the reaction vessel as a result of the step of adding reactive silica to the reaction vessel.
31. The method of Claim 30, further comprising the step of:
(a) initially adding an aqueous solution to the reaction vessel prior to the step of adding reactive silica, the aqueous solution being substantially free of silica.
(a) initially adding an aqueous solution to the reaction vessel prior to the step of adding reactive silica, the aqueous solution being substantially free of silica.
32. The method of Claim 23, wherein the reactive silica comprises a reaction product of a cationic ion exchange resin and an alkali metal silicate.
33. The method of Claim 23, further comprising one or more of the following steps:
(a) quenching a reaction between one or more silicates and one or more ion exchange resins with a sufficient amount of water.
(a) quenching a reaction between one or more silicates and one or more ion exchange resins with a sufficient amount of water.
34. The method of Claim 23, wherein the reactive period represents at least a 50% reduction in reaction time when compared to a method of forming silica particles in which the silica mass addition rate is constant and below 10.0 g/1000 m2-hr.
35. A method of making colloidal silica particles, said method comprising the step::
of:
(a) adding one or more reactants to a reaction vessel containing water and being substantially free of any seed silica particles, said one or more reactants being capable of forming nucleated silica particles;
(b) forming nucleated silica particles within the reaction vessel; and (c) growing the nucleated silica particles within the reaction vessel so as to form colloidal silica particles, said growing step comprising increasing a feed rate of said one or more reactants over a reaction period.
of:
(a) adding one or more reactants to a reaction vessel containing water and being substantially free of any seed silica particles, said one or more reactants being capable of forming nucleated silica particles;
(b) forming nucleated silica particles within the reaction vessel; and (c) growing the nucleated silica particles within the reaction vessel so as to form colloidal silica particles, said growing step comprising increasing a feed rate of said one or more reactants over a reaction period.
36. The method of Claim 35, wherein the feed rate of said one or more reactants is a function of reaction time and is greater than 10.0 grams of reactive silica per 1000 square meters (m2) of total particle surface area per hour (g/1000 m2-hr) during at least a portion of the reaction period.
37. The method of Claim 35, wherein the step of adding one or more reactants comprises one or more stepwise increases in the feed rate of the one or more reactants during the reaction period, the one or more stepwise increases being based on a mathematical model that provides an optimum silica mass addition rate, q, represented by the formula:
q = (3m o G r/D po3) ( D po + G r t)2 wherein:
(a) m o represents a mass of silica particles in the reaction vessel as measured in grams (g);
(b) G r represents a silica particle growth rate of the silica particles in the reaction vessel as determined by an increase in particle diameter and as measured in nanometers per hour (nm/hr);
(c) D po represents an average silica particle diameter as measured in nanometers (nm); and (d) t represents time in hours (hr).
q = (3m o G r/D po3) ( D po + G r t)2 wherein:
(a) m o represents a mass of silica particles in the reaction vessel as measured in grams (g);
(b) G r represents a silica particle growth rate of the silica particles in the reaction vessel as determined by an increase in particle diameter and as measured in nanometers per hour (nm/hr);
(c) D po represents an average silica particle diameter as measured in nanometers (nm); and (d) t represents time in hours (hr).
38. The method of Claim 35, wherein the one or more reactants comprise a cationic ion exchange resin and a silicate.
39. A method of making colloidal silica particles, said method comprising the step of:
(a) adding reactive silica to a reaction vessel at a silica mass addition rate over a reaction period so as to form colloidal silica particles having an average final particle diameter ranges from about 20 nm to about 200 nm, the silica mass addition rate increasing at least once during the reaction period.
(a) adding reactive silica to a reaction vessel at a silica mass addition rate over a reaction period so as to form colloidal silica particles having an average final particle diameter ranges from about 20 nm to about 200 nm, the silica mass addition rate increasing at least once during the reaction period.
40. The method of Claim 39, wherein the silica mass addition rate is based on a mathematical model that takes into account (i) a particle nucleation rate, (ii) a silica deposition rate on existing silica particles, and (iii) growth of silica particles in the reaction vessel, the silica mass addition rate being greater than 10.0 grams of reactive silica per 1000 square meters (m) of total particle surface area per hour (g/1000 m2-hr) during at least a portion of the reaction period.
41. The method of Claim 39, wherein the colloidal silica particles have an average final particle diameter of about 20 to about 100 nm.
42. Colloidal silica particles formed by the method of claim 23.
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US924507P | 2007-12-27 | 2007-12-27 | |
US61/009,245 | 2007-12-27 | ||
PCT/US2008/013358 WO2009085091A2 (en) | 2007-12-27 | 2008-12-04 | Method for making colloidal metal oxide particles |
Publications (1)
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CA2710768A1 true CA2710768A1 (en) | 2009-07-09 |
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CA2710768A Abandoned CA2710768A1 (en) | 2007-12-27 | 2008-12-04 | Method for making colloidal metal oxide particles |
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EP (1) | EP2231323A2 (en) |
JP (1) | JP5637863B2 (en) |
KR (1) | KR101629035B1 (en) |
CN (1) | CN101959590B (en) |
AR (1) | AR069976A1 (en) |
AU (1) | AU2008344012A1 (en) |
BR (1) | BRPI0821516A2 (en) |
CA (1) | CA2710768A1 (en) |
CL (1) | CL2008003914A1 (en) |
MX (1) | MX2010007105A (en) |
RU (1) | RU2557238C2 (en) |
TW (1) | TWI466714B (en) |
WO (1) | WO2009085091A2 (en) |
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JP5602190B2 (en) * | 2012-06-08 | 2014-10-08 | 住友ゴム工業株式会社 | Method for simulating polymer materials |
CN110217799B (en) * | 2018-03-02 | 2020-12-18 | 中国石油化工股份有限公司 | Silica sol and preparation method thereof |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3538015A (en) * | 1967-12-07 | 1970-11-03 | Nalco Chemical Co | Large particle silica sols and method of production |
US3969266A (en) * | 1971-06-23 | 1976-07-13 | E. I. Du Pont De Nemours And Company | Microporous membrane process for making concentrated silica sols |
US3789009A (en) * | 1971-07-15 | 1974-01-29 | Du Pont | Process for the preparation of large particle silica sols |
SU1452789A1 (en) * | 1987-03-13 | 1989-01-23 | Армянский филиал Всесоюзного научно-исследовательского института химических реактивов и особо чистых химических веществ | Method of producing silica hydrosols |
US5352277A (en) * | 1988-12-12 | 1994-10-04 | E. I. Du Pont De Nemours & Company | Final polishing composition |
SU1712307A1 (en) * | 1989-11-01 | 1992-02-15 | Всесоюзный Научно-Исследовательский И Проектный Институт "Теплопроект" | Method of producing silicon sol |
US5100581A (en) * | 1990-02-22 | 1992-03-31 | Nissan Chemical Industries Ltd. | Method of preparing high-purity aqueous silica sol |
DE4216119C2 (en) * | 1992-05-15 | 1995-08-10 | Bayer Ag | Process for the preparation and concentration of silica sols |
US6906109B2 (en) * | 2000-09-01 | 2005-06-14 | Chemical Products Corp. | Method for controling uniformity of colloidal silica particle size |
FR2819245B1 (en) * | 2001-01-09 | 2004-11-26 | Clariant | NOVEL AQUEOUS SUSPENSIONS OF NEUTRAL PH ANIONIC COLLOIDAL SILICA AND PREPARATION METHOD THEREOF, AND APPLICATIONS THEREOF |
WO2004035473A1 (en) * | 2002-10-14 | 2004-04-29 | Akzo Nobel N.V. | Colloidal silica dispersion |
US20070034116A1 (en) * | 2005-08-10 | 2007-02-15 | Mac Donald Dennis L | Silica sols with controlled minimum particle size and preparation thereof |
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2008
- 2008-12-04 AU AU2008344012A patent/AU2008344012A1/en not_active Abandoned
- 2008-12-04 EP EP08866152A patent/EP2231323A2/en not_active Withdrawn
- 2008-12-04 WO PCT/US2008/013358 patent/WO2009085091A2/en active Application Filing
- 2008-12-04 RU RU2010131001/04A patent/RU2557238C2/en not_active IP Right Cessation
- 2008-12-04 MX MX2010007105A patent/MX2010007105A/en unknown
- 2008-12-04 KR KR1020107016727A patent/KR101629035B1/en not_active IP Right Cessation
- 2008-12-04 CA CA2710768A patent/CA2710768A1/en not_active Abandoned
- 2008-12-04 BR BRPI0821516A patent/BRPI0821516A2/en not_active IP Right Cessation
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- 2008-12-04 JP JP2010540633A patent/JP5637863B2/en not_active Expired - Fee Related
- 2008-12-23 AR ARP080105717A patent/AR069976A1/en unknown
- 2008-12-24 TW TW97150396A patent/TWI466714B/en not_active IP Right Cessation
- 2008-12-26 CL CL2008003914A patent/CL2008003914A1/en unknown
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AR069976A1 (en) | 2010-03-03 |
WO2009085091A3 (en) | 2009-11-12 |
BRPI0821516A2 (en) | 2017-06-06 |
EP2231323A2 (en) | 2010-09-29 |
KR101629035B1 (en) | 2016-06-09 |
JP5637863B2 (en) | 2014-12-10 |
RU2010131001A (en) | 2012-02-10 |
MX2010007105A (en) | 2010-08-26 |
CN101959590A (en) | 2011-01-26 |
KR20100105863A (en) | 2010-09-30 |
TW200938294A (en) | 2009-09-16 |
CL2008003914A1 (en) | 2010-10-01 |
JP2011508719A (en) | 2011-03-17 |
TWI466714B (en) | 2015-01-01 |
WO2009085091A2 (en) | 2009-07-09 |
AU2008344012A1 (en) | 2009-07-09 |
RU2557238C2 (en) | 2015-07-20 |
CN101959590B (en) | 2014-12-10 |
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