CA2469335A1 - Stable dispersions of nanoparticles in aqueous media - Google Patents
Stable dispersions of nanoparticles in aqueous media Download PDFInfo
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- CA2469335A1 CA2469335A1 CA002469335A CA2469335A CA2469335A1 CA 2469335 A1 CA2469335 A1 CA 2469335A1 CA 002469335 A CA002469335 A CA 002469335A CA 2469335 A CA2469335 A CA 2469335A CA 2469335 A1 CA2469335 A1 CA 2469335A1
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- 239000006185 dispersion Substances 0.000 title claims abstract description 96
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 50
- 239000012736 aqueous medium Substances 0.000 title claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 58
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- -1 cyclic phosphates Chemical class 0.000 claims abstract description 8
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 6
- 235000021317 phosphate Nutrition 0.000 claims abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 17
- 150000004706 metal oxides Chemical class 0.000 claims description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 9
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- 125000002091 cationic group Chemical group 0.000 claims description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 238000004873 anchoring Methods 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 230000003993 interaction Effects 0.000 claims 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims 4
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims 2
- 125000004122 cyclic group Chemical group 0.000 claims 2
- 125000000524 functional group Chemical group 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 2
- 239000010452 phosphate Substances 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 25
- 229920001519 homopolymer Polymers 0.000 description 23
- 239000002245 particle Substances 0.000 description 21
- 230000007774 longterm Effects 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 13
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 12
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000013049 sediment Substances 0.000 description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- 229920006318 anionic polymer Polymers 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 238000012388 gravitational sedimentation Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- GOOHAUXETOMSMM-VKHMYHEASA-N S-propylene oxide Chemical compound C[C@H]1CO1 GOOHAUXETOMSMM-VKHMYHEASA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 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
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002707 nanocrystalline material Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000002525 ultrasonication Methods 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- B01J13/0034—Additives, e.g. in view of promoting stabilisation or peptisation
-
- 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
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/145—After-treatment of oxides or hydroxides, e.g. pulverising, drying, decreasing the acidity
-
- 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
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- 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
- C01F7/021—After-treatment of oxides or hydroxides
- C01F7/026—Making or stabilising dispersions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/007—Metal oxide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/14—Derivatives of phosphoric acid
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
Abstract
A process to prepare a stable dispersion of nanoparticles in aqueous media. A dispersant and aqueous are combined to form a mixture. The dispersant is selected from the group comprising copolymers and cyclic phosphates. Nanoparticles are added to the mixture to form the dispersion.
Description
STABLE DISPERSIONS OF NANOPARTICLES IN AQUEOUS
MEDIA
FIELD OF THE INVENTION
The present invention relates to dispersions of nanoparticles in aqueous media, and more specifically to stable aqueous dispersions of nanocrystalline metals and metal oxides.
BACKGROUND OF THE INVENTION
Stable aqueous-based dispersions of nanoparticles, such as substantially spherical nanocrystalline metals and/or metal oxides would be useful for many applications. Such dispersions could serve as a component of transparent coatings, which could be used on surfaces to yield unique properties such as abrasion resistance, radiation absorption or reflection, electrical conductivity, and catalytic function. Other applications of dispersions include, but are not limited to, functioning as abrasive or polishing fluids, thermal transfer fluids, catalytic additives, ingredients to cosmetic and personal care formulations, and electro-rheological fluids.
Generally products utilizing the dispersions described above have different pH
values than the natural pH of metal and/or metal oxides in water. This often leads to dispersion instability because, as the dispersion pH is adjusted for application use, the isoelectric point of the dispersed phase is encountered and flocculation of the nanoparticles is initiated. Thus, it would be desirable to form stable aqueous-based dispersions at pH values required by the application, especially pH values above or near the isoelectric point of the metal and/or metal oxide. Therefore, a need exists for a method of preparation of stable dispersions of nanoparticles, such as substantially spherical nanocrystalline metals and/or metal oxides, and aqueous media at a variety of pH values.
SUMMARY OF THE INVENTION
In one example, the present invention relates to a method of preparing or forming stable dispersions of nanoparticles and aqueous media. The method comprises combining a dispersant with aqueous media to form a mixture. The dispersant in one example is selected from the group comprising water soluble copolymers and cyclic phosphates. Nanoparticles, such as substantially spherical nanocrystalline metal and/or metal oxide particles are added to the mixture.
DETAILED DESCRIPTION OF THE INVENTION
Following are definitions of terms that are used throughout the description:
Isoelectric point - the pH of zero net charge on a nanoparticle in dispersion.
The isoelectric point is determined by measuring the zeta-potential of a nanoparticle dispersion and a buffer to maintain dispersion pH. The pH where the zeta-potential is zero is the isoelectric point.
Long-term stable dispersion - the dispersed nanoparticles do not aggregate (no increase in particle size) and gravitational sedimentation is minimized on the time frame of 6 months and longer.
Short-term stable dispersion - the dispersed nanoparticles are initially well dispersed but begin to aggregate, displaying an increased particle size and concomitant sedimentation, on the time frame of days to weeks.
Water-soluble dispersants are used in a method of dispersing nanoparticles, such as substantially spherical metal and/or metal oxide nanoparticles. In one example, the nanoparticles comprise the nanocrystalline materials described in U.S.
Patent Number 5,874,684, entitled "Nanocrystalline Materials", which was granted to Parker et al. on February 23, 1999, and which is hereby incorporated by reference.
The aqueous-based dispersions, of the present invention, are made by dissolving dispersant in water and adding the nanoparticles while high shear mixing (e.g., ultrasonication, rotor-stator mixing, homogenizer mixing, etc.) Substantially spherical nanocrystalline metals and/or metal oxides are dispersed above their isoelectric points using a variety of water soluble dispersants, including but not limited to, pigment dispersants, surfactants, wetting agents, coupling agents (hereinafter referred to collectively in this document as "dispersants"). The dispersants range from small molecules to oligomeric materials to polymers to coupling agents and featured a variety of different surface anchoring groups (acidic, basic, or neutral), and had different ionic character (cationic, anionic, or neutral).
Screenings were conducted utilizing the dispersants to disperse substantially spherical nanocrystalline metals and metal oxides. Experiments were constructed to cover a number of different particle concentrations as well as a number of different dispersant levels with respect to the particle. Samples were prepared by ultrasonication and the quality of dispersion was measured by the following criteria:
1. Qualitative appearance of the dispersion 2. Particle size determination 3. Dispersion stability with respect to gravimetric sedimentation over time Surfactants, such as those given in the examples which follow, were employed to obtain stable dispersions of substantially spherical nanocrystalline metal and metal oxide particles. The pH was adjusted above the isoelectric point of the particles with hydroxide bases. Surprisingly, only water-soluble copolymers and, for some nanoparticles, cyclic phosphates, were found to yield stable aqueous-based dispersions of substantially spherical nanocrystalline metals and/or metal oxides above the isoelectric point of the particles. The resulting aqueous-based dispersions of substantially spherical nanocrystalline particles are stable, have a pH
greater that the isoelectric point of the particles in an aqueous-based medium, and could be incorporated into application formulations without inducing flocculation of the particles.
A description of several exemplary experiments now follows for illustrative purposes.
Example l: Aqueous-Based Dispersions of Substantially Spherical Nanocrystalline Aluminum Oxide Dispersants evaluated in aqueous-based dispersions of aluminum oxide are listed in Table 1. Commercial dispersant names, maximum weight percent oxide in a fluid dispersion, weight percent dispersant with respect to aluminum oxide, mean particle size in dispersion on a volume-weight basis in dispersions as made, dispersion stability after the dispersion pH was increased above the isoelectric point of aluminum oxide dispersion using hydroxide bases (stable dispersion = S, long term - LT, short term - ST, flocculated dispersion = F), and dispersant type are tabulated. The dispersions that were initially stable were monitored over time and were further characterized. The general dispersion effectiveness falls into two groups depending on the length of time the dispersion remains stable. Long-term stable dispersions are stable for at least 6 months and do not exhibit aggregation and particle size growth.
MEDIA
FIELD OF THE INVENTION
The present invention relates to dispersions of nanoparticles in aqueous media, and more specifically to stable aqueous dispersions of nanocrystalline metals and metal oxides.
BACKGROUND OF THE INVENTION
Stable aqueous-based dispersions of nanoparticles, such as substantially spherical nanocrystalline metals and/or metal oxides would be useful for many applications. Such dispersions could serve as a component of transparent coatings, which could be used on surfaces to yield unique properties such as abrasion resistance, radiation absorption or reflection, electrical conductivity, and catalytic function. Other applications of dispersions include, but are not limited to, functioning as abrasive or polishing fluids, thermal transfer fluids, catalytic additives, ingredients to cosmetic and personal care formulations, and electro-rheological fluids.
Generally products utilizing the dispersions described above have different pH
values than the natural pH of metal and/or metal oxides in water. This often leads to dispersion instability because, as the dispersion pH is adjusted for application use, the isoelectric point of the dispersed phase is encountered and flocculation of the nanoparticles is initiated. Thus, it would be desirable to form stable aqueous-based dispersions at pH values required by the application, especially pH values above or near the isoelectric point of the metal and/or metal oxide. Therefore, a need exists for a method of preparation of stable dispersions of nanoparticles, such as substantially spherical nanocrystalline metals and/or metal oxides, and aqueous media at a variety of pH values.
SUMMARY OF THE INVENTION
In one example, the present invention relates to a method of preparing or forming stable dispersions of nanoparticles and aqueous media. The method comprises combining a dispersant with aqueous media to form a mixture. The dispersant in one example is selected from the group comprising water soluble copolymers and cyclic phosphates. Nanoparticles, such as substantially spherical nanocrystalline metal and/or metal oxide particles are added to the mixture.
DETAILED DESCRIPTION OF THE INVENTION
Following are definitions of terms that are used throughout the description:
Isoelectric point - the pH of zero net charge on a nanoparticle in dispersion.
The isoelectric point is determined by measuring the zeta-potential of a nanoparticle dispersion and a buffer to maintain dispersion pH. The pH where the zeta-potential is zero is the isoelectric point.
Long-term stable dispersion - the dispersed nanoparticles do not aggregate (no increase in particle size) and gravitational sedimentation is minimized on the time frame of 6 months and longer.
Short-term stable dispersion - the dispersed nanoparticles are initially well dispersed but begin to aggregate, displaying an increased particle size and concomitant sedimentation, on the time frame of days to weeks.
Water-soluble dispersants are used in a method of dispersing nanoparticles, such as substantially spherical metal and/or metal oxide nanoparticles. In one example, the nanoparticles comprise the nanocrystalline materials described in U.S.
Patent Number 5,874,684, entitled "Nanocrystalline Materials", which was granted to Parker et al. on February 23, 1999, and which is hereby incorporated by reference.
The aqueous-based dispersions, of the present invention, are made by dissolving dispersant in water and adding the nanoparticles while high shear mixing (e.g., ultrasonication, rotor-stator mixing, homogenizer mixing, etc.) Substantially spherical nanocrystalline metals and/or metal oxides are dispersed above their isoelectric points using a variety of water soluble dispersants, including but not limited to, pigment dispersants, surfactants, wetting agents, coupling agents (hereinafter referred to collectively in this document as "dispersants"). The dispersants range from small molecules to oligomeric materials to polymers to coupling agents and featured a variety of different surface anchoring groups (acidic, basic, or neutral), and had different ionic character (cationic, anionic, or neutral).
Screenings were conducted utilizing the dispersants to disperse substantially spherical nanocrystalline metals and metal oxides. Experiments were constructed to cover a number of different particle concentrations as well as a number of different dispersant levels with respect to the particle. Samples were prepared by ultrasonication and the quality of dispersion was measured by the following criteria:
1. Qualitative appearance of the dispersion 2. Particle size determination 3. Dispersion stability with respect to gravimetric sedimentation over time Surfactants, such as those given in the examples which follow, were employed to obtain stable dispersions of substantially spherical nanocrystalline metal and metal oxide particles. The pH was adjusted above the isoelectric point of the particles with hydroxide bases. Surprisingly, only water-soluble copolymers and, for some nanoparticles, cyclic phosphates, were found to yield stable aqueous-based dispersions of substantially spherical nanocrystalline metals and/or metal oxides above the isoelectric point of the particles. The resulting aqueous-based dispersions of substantially spherical nanocrystalline particles are stable, have a pH
greater that the isoelectric point of the particles in an aqueous-based medium, and could be incorporated into application formulations without inducing flocculation of the particles.
A description of several exemplary experiments now follows for illustrative purposes.
Example l: Aqueous-Based Dispersions of Substantially Spherical Nanocrystalline Aluminum Oxide Dispersants evaluated in aqueous-based dispersions of aluminum oxide are listed in Table 1. Commercial dispersant names, maximum weight percent oxide in a fluid dispersion, weight percent dispersant with respect to aluminum oxide, mean particle size in dispersion on a volume-weight basis in dispersions as made, dispersion stability after the dispersion pH was increased above the isoelectric point of aluminum oxide dispersion using hydroxide bases (stable dispersion = S, long term - LT, short term - ST, flocculated dispersion = F), and dispersant type are tabulated. The dispersions that were initially stable were monitored over time and were further characterized. The general dispersion effectiveness falls into two groups depending on the length of time the dispersion remains stable. Long-term stable dispersions are stable for at least 6 months and do not exhibit aggregation and particle size growth.
However, short-term stable dispersions exhibit aggregation and particle size growth on the time frame of days to weeks.
Only water-soluble copolymers that have polymer segments that are attractive to the nanocrystalline particle and different polymer segments that render them water-soluble yield long-term stable dispersions. This is a surprising result -homopolymers of acrylic acid as a class only render the dispersions stable for short times.
Table 1.
Dispersants for Aqueous-Based Aluminum Oxide Dispersions Dispersant Max Disp InitialDispersionDispersant Type Oxidewt% PS, Stability wt% nm <d>vol Long Term Stable Polyacryl 65 10 135 S - Acrylamidomethylpropane C50-45AN LT sulfonic acid l acrylic acid copolymer, neutral to pH = 8 Tego 752W 65 10 135 S-LT Malefic acid/vinyl polyether copolymer, pH=
Disperbyk-19050 10 135 S - Non-Ionic copolymer with LT carboxy anchor groups, pH= 7 Zephrym PD331550 10 135 S - Propylene oxidelacrylic LT acid copolymer, pH =
Short Term Stable Hydropalat 20 10 150 S - Acrylic acid homopolymer, 44 ST pH = 7.8 Polacryl 20 10 150 S - Acrylic acid homopolymer, A60-40S ST pH = 8.0 Polacryl 20 10 150 S - Acrylic acid homopolymer, B55-SOAN ST pH = 6.5 Polacryl 40 10 150 S - Acrylic acid homopolymer, A60-35S ST pH = 8.0 Hydropalat 10 20 150 S - Acrylic acid homopolymer, 100 ST pH = 6.5 HMP 20 2 150 S - Sodium hexametaphosphate, ST ring structure Unstable Solsperse 0 5 > F Nonionic polymer PVP IC-15 0 10 > F Polyvinylpropylidone, 500 MW = 9700 Ganex P-904 0 5 > F 90% PVP/10% Poly-C4, HLB
LC 500 = 18-20 Solsperse 0 10 > F Cationic polymer Solsperse 0 20 > F Anionic polymer neutralized 40000 500 with DEA
Solsperse 0 20 > F Anionic polymer, pH =
PVP/VA S-6300 10 > F Polyvinylpropylidone/Vinyl 500 acetate IHydropalat 0 I I F Nonionic and Ionic Surfactants 3216 20 >
Example 2: Aqueous-Based Dispersions of Substantially Spherical Nanocrystalline Cerium Oxide Dispersants evaluated in aqueous-based dispersions of cerium oxide are listed in Table 2. Commercial dispersant names, weight percent oxide in dispersion, weight percent dispersant with respect to cerium oxide, mean particle size in dispersion on a volume-weight basis in dispersions as made, dispersion stability after the dispersion pH
was increased above the isoelectric point of cerium oxide dispersion using hydroxide bases (stable dispersion = S, long term - LT, short term - ST, flocculated dispersion =
F), and dispersant type are tabulated. The dispersions that were initially stable were evaluated over time and were further characterized. As with alumina, the general dispersion effectiveness for ceria falls into two groups depending on the length of time the dispersion remains stable - long-term and short-term stable dispersions.
Only water-soluble copolymers that have polymer segments that are attractive to the nanocrystalline particle and polymer segments that render them water-soluble yield long-term stable dispersions. This is a surprising result - homopolymers of acrylic acid as a class only render the dispersions stable for short times. In the case of unstable dispersions the observed flocculation is irreversible.
Table 2.
Dispersants for Aqueous-Based Cerium Oxide Dispersions Dispersant OxideDispInitialDispersionDispersant Type wt% wt% PS, Stability nm <d>vol Long-Term Stable Polyacryl 20 10 120 S - Acrylamidomethylpropane C50-45AN LT sulfonic acid l acrylic acid copolymer, neutral to pH = 8 Tego 752W 20 10 120 S - Malefic acid/vinyl polyether LT copolymer, pH = 6 Disperbyk-19020 10 120 S - Non-Ionic copolymer with LT carboxy anchor groups, pH= 7 Zephrym PD331520 10 120 S - Propylene oxide/acrylic LT acid copolymer, pH =
Short-Term Stable Polacryl 20 10 150 S - Acrylic acid homopolymer, A60-35S ST pH = 8.0 Polacryl 20 10 150 S - Acrylic acid homopolymer, A60-40S ST pH = 8.0 Polacryl 20 10 150 S - Acrylic acid homopolymer, B55-SOAN ST pH = 6.5 Polacryl 20 10 150 S - Acrylic acid homopolymer Hydroplat 20 10 150 S - Hydrophobically modified 100 ST acrylic acid homopolymer Unstable PVP K-15 0 20 > F Polyvinylpropylidone, 500 MW = 9700 Solsperse 0 10 > F Nonionic polymer PVP/VA S-6300 10 > F Polyvinylpropylidone/Vinyl 500 acetate Ganex P-904 0 S > F 90% PVP/10% Poly-C4, HLB
LC 500 = 18-20 HMP 0 2 > F Sodium hexametaphosphate, 500 ring structure Solsperse 0 20 > F Anionic polymer neutralized 40000 500 with DEA
ISolsperse I I > F (Anionic polymer, pH =
I
Example 3: Aqueous-Based Dispersions of Substantially Spherical Nanocrystalline Zinc Oxide Dispersants evaluated in aqueous-based dispersions of zinc oxide are listed in Table 3. Commercial dispersant names, maximum weight percent oxide in fluid dispersion, weight percent dispersant with respect to zinc oxide, mean particle size in dispersion on a volume-weight basis in dispersions as made, dispersion stability after the dispersion pH was increased above the isoelectric point of zinc oxide using hydroxide bases (stable dispersion = S, long term - LT, short term - ST, flocculated dispersion = F), and dispersant type are tabulated. The dispersions that were initially stable were evaluated over time and were further characterized. As with alumina and ceria, the general dispersion effectiveness for ceria falls into two groups depending on the length of time the dispersion remains stable - long-term and short-term stable dispersions.
Only water-soluble copolymers that have polymer segments that are attractive to the nanocrystalline particle and polymer segments that render them water-soluble yield long-term stable dispersions. This is a surprising result - homopolymers of acrylic acid as a class only render the dispersions stable for short times.
Table 3.
Dispersants for Aqueous-Based Zinc Oxide Dispersions Dispersant Max Disp,PS, DispersionDispersant Type Oxide,wt% nm Stability wt% <d>vol Long-Term Stable Polyacryl 40 5 310 S - Acrylamidomethylpropane C50-45AN LT sulfonic acid /
acrylic acid copolymer, neutral to pH = 8 Disperbyk 60 4 310 S - Non-Ionic copolymer with 190 LT carboxy anchor groups, pH= 7 Zephrym PD331540 3 310 S - Propylene oxide / acrylic LT acid copolymer, pH =
HMP 30 2 310 S - Sodium hexametaphosphate, LT ring structure Short-Term Stable Zephrym PD 28 10 250 S - Acrylic acid-based homopolymer Hydropalat 30 0.7 390 S - Acrylic acid homopolymer, 44 ST pH = 7.8 Hydropalat 30 20 430 S - Acrylic acid homopolymer, 100 ST pH = 6.5 Polacryl 40 5 390 S - Acrylic acid homopolymer, A60-35S ST pH = 8.0 Polacryl 40 5 370 S - Acrylic acid homopolymer, A60-40S ST pH = 8.0 Polacryl 40 5 300 S - Acrylic acid homopolymer, B55-SOAN ST pH = 6.5 Unstable Polacryl 0 10 > F Acrylic acid homopolymer, B55-SOA S00 pH = 3.5 PVP K-15 0 10 > F Polyvinylpropylidone, MW
500 = 9700 Hydropalat 0 20 > F Nonionic and Ionic Surfactants Solsperse 0 5 > F Basic, cationic single 20000 500 anchor, single polymer chain Solsperse 0 5 > F Nonionic polymer Solsperse 0 20 > F Anionic polymer neutralized 40000 500 with DEA
Solsperse 0 18 > F Anionic polymer Zephrym PD 0 10 > F Nonionic/Anionic Surfactant 3800 500 blend Zephrym PD 0 10 > F Alcohol ethoxylate Zephrym PD 0 10 > F Nonionic surfactant Zephrym PD 0 20 > F Polymeric dispersant Disperbyk 0 20 > F Polymeric dispersant Disperbyk 0 20 > F Polymeric dispersant PVP/VA S-6300 10 > F Polyvinylpropylidone/Vinyl 500 acetate Ganex P-904 0 10 > F 90% PVP/10% Poly-C4, HLB
LC 500 = 18-20 Copolymer 0 11 > F PVP/Dimethylaminoethylmethacrylate 958 500 copolymer PVP/VA W-6350 10 > F PVPlvinyl acetate copolymer IHydropalat I 20 > I F Polyethyleneglycol dioleate, 188A 0 500 Nonionic surfactant Hydropalat 0 20 > 500 F Oleoalkylenoxide block 535N copolymer Hydropalat 0 20 > 500 F Oleoalkylenoxide block 1080 copolymer Zonyl FSO1000 2 > 500 F Fluorinated surfactant Alkox E-30 0 10 > S00 F Polyethyleneoxide Alkox E-160 0 10 > S00 F Polyethyleneoxide Alkox R-150 0 20 > 500 F Polyethyleneoxide Alkox R-400 0 20 > 500 F Polyethyleneoxide I
Example 4: Aqueous-Based Dispersions of Other Substantially Spherical Nanocrystalline Particles - Copper Oxide, Silver, Antimony Tin Oxide, Indium Tin Oxide Long-term stable, aqueous-based dispersions of other substantially spherical nanocrystalline particles - copper oxide, silver, antimony tin oxide, indium tin oxide -are produced using water-soluble copolymer dispersant levels from 1 to 20-wt%
dispersant with respect to nanocrystalline particles, depending on the copolymer dispersant used. The copolymer dispersant stabilizes the volume-weighted mean particle size preventing aggregation (the formation of grape-like clusters).
Example 5: The Stability of Aqueous-Based Dispersions of Substantially Spherical Nanocrystalline Cerium Oxide The mean particle size, of substantially spherical ceria, in aqueous dispersion at pH 7.5 on a volume-weight basis (measured using dynamic light scattering), as functions of time and dispersant type, are given in Table 4. The mean particle size is stable for Zephrym PD 3315 and Polyacryl C50-45AN, water-soluble copolymers that have polymer segments that are attractive to the nanocrystalline particle and polymer segments that render them water-soluble. Where as the mean particle size grows over time for Polyacryl B55-SOAN and Hydropatat 44, homopolymers of acrylic acid.
This is a surprising result. - homopolymers of acrylic acid as a class are claimed to render the dispersions stable (see US Patent 5,876,490) Dispersant PS PS PS PS PS PS
0 days 1 day 3 days 21 54 days 12 mo days Hydropatat 289 nm 268 330 327 402 nm 378 44 nm nm nm nm Polacryl 155 nm 171 152 315 376 nm 415 B55-SOAN nm nm nm nm Zephrym PD 173 nm 212 141 163 200 nm 216 3315 nm nm nm nm Polyacryl 178 nm 155 146 172 180 nm 196 C50-45AN nm nm nm nm Example 6. Settling Stability of Aqueous Dispersions of Substantially Spherical Nanocrystalline Ceria at Elevated pH
The stability of aqueous dispersions of substantially spherical nanocrystalline ceria at elevated pH with respect to gravitational sedimentation was quantified as a function of dispersant type, dispersant concentration, and pH. A slow rate of gravitational sedimentation is desired in storage containers to minimize the amount of mixing required to homogenize the concentration. For aqueous ceria dispersions the problem is particularly challenging since the density of the ceria is approximately seven times the density of water and for 20-wt% ceria dispersions the dispersion viscosity is less than 10 cP.
Dispersions were prepared using C50-45AN and B55-SOAN. Each sample in Table 5 was placed into a 500 mL polypropylene graduated cylinder. The cylinder contained a column of ceria dispersion 27.5 cm high. The graduated cylinder was covered tightly with Parafilm and set aside for 30 days.
Table 5.
Dispersion Samples in Gravimetric Sedimentation Study Sample weight % Dispersantinitial d<vol>
(based on ceria nm SD nm 114A 8 % C50-45AN 94 (21) 114B 9 % C50-45AN 93 (21) 114C 10 % C50-45AN 94 (21) 114D 11 % C50-45AN 92 (20) 114E 12 % C50-45AN 94 (21) 114F 10 % B55-SOAN 94 (22) * Horiba LA-910; mean volume weighted PS and standard deviation After thirty days, 100 mL aliquots (5.5 cm of dispersion) of the ceria dispersion were carefully removed from the cylinder. These aliquots were taken from the top of the cylinder with a polypropylene syringe equipped with a virgin 6" stainless steel needle, located just beneath the surface of the liquid in a fashion such that the liquid below was not disturbed. Each 100 mL aliquot was stored in a separate 125 mL
polypropylene container and named "1" through "5" depending on where in the graduated cylinder it was taken. For example, 114A-1 was taken from the top of the graduated cylinder while 114A-5 was taken from the bottom of the graduated cylinder.
Each 100 mL aliquot was characterized by the loss on drying and by Horiba particle size determination. The amount of sediment that would not pour out of the graduated cylinder after 20 seconds of inversion was also determined. These data are presented in Table 6.
Table 6. Sediment, solids, and PS for Table Dispersions Sample sediment (g) % solids (LOD)d<vol>, nm (SD, nm)*
114A-1 10.1 85 (16) 114A-2 15.2 95 (20) 114A-3 16.6 103 (22) 114A-4 17.0 105 (23) 114A-5 21.2 108 (25) 114A-sediment 10.04 - -114B-1 9.8 86 (16) 114B-2 15.2 96 (20) 114B-3 16.4 103 (23) 114B-4 16.7 105 (24) 114B-5 20.2 108 (25) 114B-sediment 9.06 -1140-1 10.9 86 (17) 114C-2 15.6 97 (20) 114C-3 16.3 104 (23) 114C-4 17.1 106 (24) 114C-5 21.4 109 (25) 1140-sediment 6.78 -114D-1 10.5 86 (16) 114D-2 15.8 96 (20) 114D-3 16.7 103 (22) 114D-4 16.9 106 (24) 114D-5 20.7 108 (25) 114D-sediment 6.94 -114E-1 11.5 86 (17) 114E-2 16.1 98 (21) 114E-3 17.0 105 (23) 114E-4 17.2 106 (24) 114E-5 21.2 111 (27) 114E-sediment 7.06 -114F-1 7.5 84 (16) 114F-2 9.3 87 (17) 114F-3 9.5 88(17) 114F-4 9.3 89 (18) 114F-5 21.6 120 (37) 114F-sediment 51.5 -* Horiba LA-910; mean volume weighted PS and standard deviation Data in Table 6 show the amount of sediment in C50-45AN samples decreases until 10% CSO-45AN is reached, after which there is little improvement to be gained by adding more dispersant. The sediment obtained with the dispersant B55-SOAN, a homopolymer of acrylic acid, at 10% by weight (51.5%) is by far greater than 45AN at any concentration examined.
Although various examples have been depicted and described in detail herein, it will be apparent to those skilled in the relevant art that various modifications, additions, substitutions and the like can be made without departing from the spirit of the invention and these are therefore considered to be within the scope of the invention defined.
Only water-soluble copolymers that have polymer segments that are attractive to the nanocrystalline particle and different polymer segments that render them water-soluble yield long-term stable dispersions. This is a surprising result -homopolymers of acrylic acid as a class only render the dispersions stable for short times.
Table 1.
Dispersants for Aqueous-Based Aluminum Oxide Dispersions Dispersant Max Disp InitialDispersionDispersant Type Oxidewt% PS, Stability wt% nm <d>vol Long Term Stable Polyacryl 65 10 135 S - Acrylamidomethylpropane C50-45AN LT sulfonic acid l acrylic acid copolymer, neutral to pH = 8 Tego 752W 65 10 135 S-LT Malefic acid/vinyl polyether copolymer, pH=
Disperbyk-19050 10 135 S - Non-Ionic copolymer with LT carboxy anchor groups, pH= 7 Zephrym PD331550 10 135 S - Propylene oxidelacrylic LT acid copolymer, pH =
Short Term Stable Hydropalat 20 10 150 S - Acrylic acid homopolymer, 44 ST pH = 7.8 Polacryl 20 10 150 S - Acrylic acid homopolymer, A60-40S ST pH = 8.0 Polacryl 20 10 150 S - Acrylic acid homopolymer, B55-SOAN ST pH = 6.5 Polacryl 40 10 150 S - Acrylic acid homopolymer, A60-35S ST pH = 8.0 Hydropalat 10 20 150 S - Acrylic acid homopolymer, 100 ST pH = 6.5 HMP 20 2 150 S - Sodium hexametaphosphate, ST ring structure Unstable Solsperse 0 5 > F Nonionic polymer PVP IC-15 0 10 > F Polyvinylpropylidone, 500 MW = 9700 Ganex P-904 0 5 > F 90% PVP/10% Poly-C4, HLB
LC 500 = 18-20 Solsperse 0 10 > F Cationic polymer Solsperse 0 20 > F Anionic polymer neutralized 40000 500 with DEA
Solsperse 0 20 > F Anionic polymer, pH =
PVP/VA S-6300 10 > F Polyvinylpropylidone/Vinyl 500 acetate IHydropalat 0 I I F Nonionic and Ionic Surfactants 3216 20 >
Example 2: Aqueous-Based Dispersions of Substantially Spherical Nanocrystalline Cerium Oxide Dispersants evaluated in aqueous-based dispersions of cerium oxide are listed in Table 2. Commercial dispersant names, weight percent oxide in dispersion, weight percent dispersant with respect to cerium oxide, mean particle size in dispersion on a volume-weight basis in dispersions as made, dispersion stability after the dispersion pH
was increased above the isoelectric point of cerium oxide dispersion using hydroxide bases (stable dispersion = S, long term - LT, short term - ST, flocculated dispersion =
F), and dispersant type are tabulated. The dispersions that were initially stable were evaluated over time and were further characterized. As with alumina, the general dispersion effectiveness for ceria falls into two groups depending on the length of time the dispersion remains stable - long-term and short-term stable dispersions.
Only water-soluble copolymers that have polymer segments that are attractive to the nanocrystalline particle and polymer segments that render them water-soluble yield long-term stable dispersions. This is a surprising result - homopolymers of acrylic acid as a class only render the dispersions stable for short times. In the case of unstable dispersions the observed flocculation is irreversible.
Table 2.
Dispersants for Aqueous-Based Cerium Oxide Dispersions Dispersant OxideDispInitialDispersionDispersant Type wt% wt% PS, Stability nm <d>vol Long-Term Stable Polyacryl 20 10 120 S - Acrylamidomethylpropane C50-45AN LT sulfonic acid l acrylic acid copolymer, neutral to pH = 8 Tego 752W 20 10 120 S - Malefic acid/vinyl polyether LT copolymer, pH = 6 Disperbyk-19020 10 120 S - Non-Ionic copolymer with LT carboxy anchor groups, pH= 7 Zephrym PD331520 10 120 S - Propylene oxide/acrylic LT acid copolymer, pH =
Short-Term Stable Polacryl 20 10 150 S - Acrylic acid homopolymer, A60-35S ST pH = 8.0 Polacryl 20 10 150 S - Acrylic acid homopolymer, A60-40S ST pH = 8.0 Polacryl 20 10 150 S - Acrylic acid homopolymer, B55-SOAN ST pH = 6.5 Polacryl 20 10 150 S - Acrylic acid homopolymer Hydroplat 20 10 150 S - Hydrophobically modified 100 ST acrylic acid homopolymer Unstable PVP K-15 0 20 > F Polyvinylpropylidone, 500 MW = 9700 Solsperse 0 10 > F Nonionic polymer PVP/VA S-6300 10 > F Polyvinylpropylidone/Vinyl 500 acetate Ganex P-904 0 S > F 90% PVP/10% Poly-C4, HLB
LC 500 = 18-20 HMP 0 2 > F Sodium hexametaphosphate, 500 ring structure Solsperse 0 20 > F Anionic polymer neutralized 40000 500 with DEA
ISolsperse I I > F (Anionic polymer, pH =
I
Example 3: Aqueous-Based Dispersions of Substantially Spherical Nanocrystalline Zinc Oxide Dispersants evaluated in aqueous-based dispersions of zinc oxide are listed in Table 3. Commercial dispersant names, maximum weight percent oxide in fluid dispersion, weight percent dispersant with respect to zinc oxide, mean particle size in dispersion on a volume-weight basis in dispersions as made, dispersion stability after the dispersion pH was increased above the isoelectric point of zinc oxide using hydroxide bases (stable dispersion = S, long term - LT, short term - ST, flocculated dispersion = F), and dispersant type are tabulated. The dispersions that were initially stable were evaluated over time and were further characterized. As with alumina and ceria, the general dispersion effectiveness for ceria falls into two groups depending on the length of time the dispersion remains stable - long-term and short-term stable dispersions.
Only water-soluble copolymers that have polymer segments that are attractive to the nanocrystalline particle and polymer segments that render them water-soluble yield long-term stable dispersions. This is a surprising result - homopolymers of acrylic acid as a class only render the dispersions stable for short times.
Table 3.
Dispersants for Aqueous-Based Zinc Oxide Dispersions Dispersant Max Disp,PS, DispersionDispersant Type Oxide,wt% nm Stability wt% <d>vol Long-Term Stable Polyacryl 40 5 310 S - Acrylamidomethylpropane C50-45AN LT sulfonic acid /
acrylic acid copolymer, neutral to pH = 8 Disperbyk 60 4 310 S - Non-Ionic copolymer with 190 LT carboxy anchor groups, pH= 7 Zephrym PD331540 3 310 S - Propylene oxide / acrylic LT acid copolymer, pH =
HMP 30 2 310 S - Sodium hexametaphosphate, LT ring structure Short-Term Stable Zephrym PD 28 10 250 S - Acrylic acid-based homopolymer Hydropalat 30 0.7 390 S - Acrylic acid homopolymer, 44 ST pH = 7.8 Hydropalat 30 20 430 S - Acrylic acid homopolymer, 100 ST pH = 6.5 Polacryl 40 5 390 S - Acrylic acid homopolymer, A60-35S ST pH = 8.0 Polacryl 40 5 370 S - Acrylic acid homopolymer, A60-40S ST pH = 8.0 Polacryl 40 5 300 S - Acrylic acid homopolymer, B55-SOAN ST pH = 6.5 Unstable Polacryl 0 10 > F Acrylic acid homopolymer, B55-SOA S00 pH = 3.5 PVP K-15 0 10 > F Polyvinylpropylidone, MW
500 = 9700 Hydropalat 0 20 > F Nonionic and Ionic Surfactants Solsperse 0 5 > F Basic, cationic single 20000 500 anchor, single polymer chain Solsperse 0 5 > F Nonionic polymer Solsperse 0 20 > F Anionic polymer neutralized 40000 500 with DEA
Solsperse 0 18 > F Anionic polymer Zephrym PD 0 10 > F Nonionic/Anionic Surfactant 3800 500 blend Zephrym PD 0 10 > F Alcohol ethoxylate Zephrym PD 0 10 > F Nonionic surfactant Zephrym PD 0 20 > F Polymeric dispersant Disperbyk 0 20 > F Polymeric dispersant Disperbyk 0 20 > F Polymeric dispersant PVP/VA S-6300 10 > F Polyvinylpropylidone/Vinyl 500 acetate Ganex P-904 0 10 > F 90% PVP/10% Poly-C4, HLB
LC 500 = 18-20 Copolymer 0 11 > F PVP/Dimethylaminoethylmethacrylate 958 500 copolymer PVP/VA W-6350 10 > F PVPlvinyl acetate copolymer IHydropalat I 20 > I F Polyethyleneglycol dioleate, 188A 0 500 Nonionic surfactant Hydropalat 0 20 > 500 F Oleoalkylenoxide block 535N copolymer Hydropalat 0 20 > 500 F Oleoalkylenoxide block 1080 copolymer Zonyl FSO1000 2 > 500 F Fluorinated surfactant Alkox E-30 0 10 > S00 F Polyethyleneoxide Alkox E-160 0 10 > S00 F Polyethyleneoxide Alkox R-150 0 20 > 500 F Polyethyleneoxide Alkox R-400 0 20 > 500 F Polyethyleneoxide I
Example 4: Aqueous-Based Dispersions of Other Substantially Spherical Nanocrystalline Particles - Copper Oxide, Silver, Antimony Tin Oxide, Indium Tin Oxide Long-term stable, aqueous-based dispersions of other substantially spherical nanocrystalline particles - copper oxide, silver, antimony tin oxide, indium tin oxide -are produced using water-soluble copolymer dispersant levels from 1 to 20-wt%
dispersant with respect to nanocrystalline particles, depending on the copolymer dispersant used. The copolymer dispersant stabilizes the volume-weighted mean particle size preventing aggregation (the formation of grape-like clusters).
Example 5: The Stability of Aqueous-Based Dispersions of Substantially Spherical Nanocrystalline Cerium Oxide The mean particle size, of substantially spherical ceria, in aqueous dispersion at pH 7.5 on a volume-weight basis (measured using dynamic light scattering), as functions of time and dispersant type, are given in Table 4. The mean particle size is stable for Zephrym PD 3315 and Polyacryl C50-45AN, water-soluble copolymers that have polymer segments that are attractive to the nanocrystalline particle and polymer segments that render them water-soluble. Where as the mean particle size grows over time for Polyacryl B55-SOAN and Hydropatat 44, homopolymers of acrylic acid.
This is a surprising result. - homopolymers of acrylic acid as a class are claimed to render the dispersions stable (see US Patent 5,876,490) Dispersant PS PS PS PS PS PS
0 days 1 day 3 days 21 54 days 12 mo days Hydropatat 289 nm 268 330 327 402 nm 378 44 nm nm nm nm Polacryl 155 nm 171 152 315 376 nm 415 B55-SOAN nm nm nm nm Zephrym PD 173 nm 212 141 163 200 nm 216 3315 nm nm nm nm Polyacryl 178 nm 155 146 172 180 nm 196 C50-45AN nm nm nm nm Example 6. Settling Stability of Aqueous Dispersions of Substantially Spherical Nanocrystalline Ceria at Elevated pH
The stability of aqueous dispersions of substantially spherical nanocrystalline ceria at elevated pH with respect to gravitational sedimentation was quantified as a function of dispersant type, dispersant concentration, and pH. A slow rate of gravitational sedimentation is desired in storage containers to minimize the amount of mixing required to homogenize the concentration. For aqueous ceria dispersions the problem is particularly challenging since the density of the ceria is approximately seven times the density of water and for 20-wt% ceria dispersions the dispersion viscosity is less than 10 cP.
Dispersions were prepared using C50-45AN and B55-SOAN. Each sample in Table 5 was placed into a 500 mL polypropylene graduated cylinder. The cylinder contained a column of ceria dispersion 27.5 cm high. The graduated cylinder was covered tightly with Parafilm and set aside for 30 days.
Table 5.
Dispersion Samples in Gravimetric Sedimentation Study Sample weight % Dispersantinitial d<vol>
(based on ceria nm SD nm 114A 8 % C50-45AN 94 (21) 114B 9 % C50-45AN 93 (21) 114C 10 % C50-45AN 94 (21) 114D 11 % C50-45AN 92 (20) 114E 12 % C50-45AN 94 (21) 114F 10 % B55-SOAN 94 (22) * Horiba LA-910; mean volume weighted PS and standard deviation After thirty days, 100 mL aliquots (5.5 cm of dispersion) of the ceria dispersion were carefully removed from the cylinder. These aliquots were taken from the top of the cylinder with a polypropylene syringe equipped with a virgin 6" stainless steel needle, located just beneath the surface of the liquid in a fashion such that the liquid below was not disturbed. Each 100 mL aliquot was stored in a separate 125 mL
polypropylene container and named "1" through "5" depending on where in the graduated cylinder it was taken. For example, 114A-1 was taken from the top of the graduated cylinder while 114A-5 was taken from the bottom of the graduated cylinder.
Each 100 mL aliquot was characterized by the loss on drying and by Horiba particle size determination. The amount of sediment that would not pour out of the graduated cylinder after 20 seconds of inversion was also determined. These data are presented in Table 6.
Table 6. Sediment, solids, and PS for Table Dispersions Sample sediment (g) % solids (LOD)d<vol>, nm (SD, nm)*
114A-1 10.1 85 (16) 114A-2 15.2 95 (20) 114A-3 16.6 103 (22) 114A-4 17.0 105 (23) 114A-5 21.2 108 (25) 114A-sediment 10.04 - -114B-1 9.8 86 (16) 114B-2 15.2 96 (20) 114B-3 16.4 103 (23) 114B-4 16.7 105 (24) 114B-5 20.2 108 (25) 114B-sediment 9.06 -1140-1 10.9 86 (17) 114C-2 15.6 97 (20) 114C-3 16.3 104 (23) 114C-4 17.1 106 (24) 114C-5 21.4 109 (25) 1140-sediment 6.78 -114D-1 10.5 86 (16) 114D-2 15.8 96 (20) 114D-3 16.7 103 (22) 114D-4 16.9 106 (24) 114D-5 20.7 108 (25) 114D-sediment 6.94 -114E-1 11.5 86 (17) 114E-2 16.1 98 (21) 114E-3 17.0 105 (23) 114E-4 17.2 106 (24) 114E-5 21.2 111 (27) 114E-sediment 7.06 -114F-1 7.5 84 (16) 114F-2 9.3 87 (17) 114F-3 9.5 88(17) 114F-4 9.3 89 (18) 114F-5 21.6 120 (37) 114F-sediment 51.5 -* Horiba LA-910; mean volume weighted PS and standard deviation Data in Table 6 show the amount of sediment in C50-45AN samples decreases until 10% CSO-45AN is reached, after which there is little improvement to be gained by adding more dispersant. The sediment obtained with the dispersant B55-SOAN, a homopolymer of acrylic acid, at 10% by weight (51.5%) is by far greater than 45AN at any concentration examined.
Although various examples have been depicted and described in detail herein, it will be apparent to those skilled in the relevant art that various modifications, additions, substitutions and the like can be made without departing from the spirit of the invention and these are therefore considered to be within the scope of the invention defined.
Claims (29)
1. A process to prepare a stable dispersion of nanoparticles in aqueous media, the process comprising:
combining a dispersant with the aqueous media to form a mixture, wherein the dispersant is selected from the group comprising copolymers and cyclic phosphates: and adding nanoparticles to the mixture.
combining a dispersant with the aqueous media to form a mixture, wherein the dispersant is selected from the group comprising copolymers and cyclic phosphates: and adding nanoparticles to the mixture.
2. The process of claim 1, further comprising:
selecting one of metal oxides and mixed metal oxides as the nanoparticles to add to the mixture.
selecting one of metal oxides and mixed metal oxides as the nanoparticles to add to the mixture.
3. The process of claim 2, further comprising:
selecting metal oxides from a group comprising aluminum oxide, zinc oxide, iron oxide, cerium oxide, chromium oxide, antimony tin oxide, and indium tin oxide as the nanoparticles to add to the mixture.
selecting metal oxides from a group comprising aluminum oxide, zinc oxide, iron oxide, cerium oxide, chromium oxide, antimony tin oxide, and indium tin oxide as the nanoparticles to add to the mixture.
4. The process of claim 1, further comprising:
selecting one of substantially spherical nanocrystalline metal oxides and substantially spherical nanocrystalline mixed metal oxides as the nanoparticles to add to the mixture.
selecting one of substantially spherical nanocrystalline metal oxides and substantially spherical nanocrystalline mixed metal oxides as the nanoparticles to add to the mixture.
5. The process of claim 1, further comprising:
selecting the nanoparticles generally to have a size distribution and range in mean diameter from about 1 nm to about 900 nm.
selecting the nanoparticles generally to have a size distribution and range in mean diameter from about 1 nm to about 900 nm.
6. The process of claim 5, wherein the selecting step comprises:
selecting the nanoparticles generally to have a size distribution and range in mean diameter from about 2 nm to about 100 nm.
selecting the nanoparticles generally to have a size distribution and range in mean diameter from about 2 nm to about 100 nm.
7. The process of claim 6, wherein the selecting step comprises:
selecting the nanoparticles generally to have a size distribution and range in mean diameter from about 5 nm to about 40 nm.
selecting the nanoparticles generally to have a size distribution and range in mean diameter from about 5 nm to about 40 nm.
8. The process of claim 1, further comprising:
selecting the dispersant to be a copolymer having one or more functional groups capable of anchoring to a surface of at least one of the nanoparticles.
selecting the dispersant to be a copolymer having one or more functional groups capable of anchoring to a surface of at least one of the nanoparticles.
9. The process of claim 8, wherein the dispersant anchors to the nanoparticle surface through at least one of acidic interactions, basic interactions, neutral interactions, and covalent interactions.
10. The process of claim 9, wherein interaction between the dispersant and the at least one of the nanoparticles is of one of cationic character, anionic character, and neutral character.
11. The process of claim 1, wherein the dispersant is soluble in the aqueous media.
12. The process of claim 1, wherein the dispersant is a cyclic phosphate.
13. The process of claim 1, wherein the step of combining comprises:
mixing the dispersant to the aqueous media.
mixing the dispersant to the aqueous media.
14. The process of claim 13 wherein the step of mixing is accomplished through one of high-shear mixing and ultrasonic mixing of the dispersant to the aqueous media.
15. The process of claim 1, wherein the step of adding comprises:
mixing the nanoparticles with the mixture.
mixing the nanoparticles with the mixture.
16. The process of claim 15, wherein the step of adding is accomplished through one of high-shear mixing and ultra-sonic mixing the nanoparticles with the mixture.
17. A composition of nanoparticles dispersed in aqueous media produced by the process of claim 1.
18. The composition of claim 17, further comprising:
selecting one of metal oxides and mixed metal oxides as the nanoparticles.
selecting one of metal oxides and mixed metal oxides as the nanoparticles.
19. The composition of claim 18, further comprising:
selecting metal oxides from a group comprising aluminum oxide, zinc oxide, iron oxide, cerium oxide, chromium oxide, antimony tin oxide, and indium tin oxide as the nanoparticles to add to the mixture.
selecting metal oxides from a group comprising aluminum oxide, zinc oxide, iron oxide, cerium oxide, chromium oxide, antimony tin oxide, and indium tin oxide as the nanoparticles to add to the mixture.
20. The composition of claim 17, further comprising:
selecting one of substantially spherical nanocrystalline metal oxides and substantially spherical nanocrystalline mixed metal oxides as the nanoparticles to add to the mixture.
selecting one of substantially spherical nanocrystalline metal oxides and substantially spherical nanocrystalline mixed metal oxides as the nanoparticles to add to the mixture.
21. The composition of claim 17, further comprising:
selecting the nanoparticles generally to have a size distribution and range in mean diameter from about 1 nm to about 900 nm.
selecting the nanoparticles generally to have a size distribution and range in mean diameter from about 1 nm to about 900 nm.
22. The composition of claim 21, wherein the selecting step comprises:
selecting the nanoparticles generally to have a size distribution and range in mean diameter from about 2 nm to about 100 nm.
selecting the nanoparticles generally to have a size distribution and range in mean diameter from about 2 nm to about 100 nm.
23. The composition of claim 22, wherein the selecting step comprises:
selecting the nanoparticles generally to have a size distribution and range in mean diameter from about 5 nm to about 40 nm.
selecting the nanoparticles generally to have a size distribution and range in mean diameter from about 5 nm to about 40 nm.
24. The composition of claim 17, further comprising:
selecting the dispersant to be a copolymer.
selecting the dispersant to be a copolymer.
25. The composition of claim 24, further comprising:
selecting the dispersant to have one or more functional groups capable of anchoring to a surface of at least one of the nanoparticles.
selecting the dispersant to have one or more functional groups capable of anchoring to a surface of at least one of the nanoparticles.
26. The composition of claim 25, wherein the copolymeric dispersant anchors to the nanoparticle surface through at least one of acidic interactions, basic interactions, neutral interactions, and covalent interactions.
27. The composition of claim 26, wherein interaction between the copolymeric dispersant and the at least one of the nanoparticles is of one of cationic character, anionic character, and neutral character.
28. The composition of claim 17, wherein the dispersant is soluble in the aqueous media.
29. The composition of claim 17, wherein the dispersant is cyclic phosphate-based.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| US35418402P | 2002-02-04 | 2002-02-04 | |
| US60/354,184 | 2002-02-04 | ||
| PCT/US2003/003188 WO2004000916A2 (en) | 2002-02-04 | 2003-02-04 | Stable dispersions of nanoparticles in aqueous media |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2469335A1 true CA2469335A1 (en) | 2003-12-31 |
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| CA002469335A Abandoned CA2469335A1 (en) | 2002-02-04 | 2003-02-04 | Stable dispersions of nanoparticles in aqueous media |
Country Status (6)
| Country | Link |
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| US (1) | US20040258608A1 (en) |
| EP (1) | EP1481020A2 (en) |
| JP (1) | JP2005519761A (en) |
| AU (1) | AU2003272186A1 (en) |
| CA (1) | CA2469335A1 (en) |
| WO (1) | WO2004000916A2 (en) |
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| US8557895B2 (en) | 2003-06-24 | 2013-10-15 | Ppg Industries Ohio, Inc. | Aqueous dispersions of polymer-enclosed particles, related coating compositions and coated substrates |
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- 2003-02-04 JP JP2004515609A patent/JP2005519761A/en active Pending
- 2003-02-04 US US10/357,941 patent/US20040258608A1/en not_active Abandoned
- 2003-02-04 CA CA002469335A patent/CA2469335A1/en not_active Abandoned
- 2003-02-04 AU AU2003272186A patent/AU2003272186A1/en not_active Abandoned
- 2003-02-04 EP EP03754358A patent/EP1481020A2/en not_active Withdrawn
- 2003-02-04 WO PCT/US2003/003188 patent/WO2004000916A2/en not_active Application Discontinuation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8557895B2 (en) | 2003-06-24 | 2013-10-15 | Ppg Industries Ohio, Inc. | Aqueous dispersions of polymer-enclosed particles, related coating compositions and coated substrates |
| US8987349B2 (en) | 2004-03-25 | 2015-03-24 | Ppg Industries Ohio, Inc. | Aqueous dispersions of polymer-enclosed particles, related coating compositions and coated substrates |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004000916A2 (en) | 2003-12-31 |
| EP1481020A2 (en) | 2004-12-01 |
| JP2005519761A (en) | 2005-07-07 |
| WO2004000916A3 (en) | 2004-07-22 |
| AU2003272186A1 (en) | 2004-01-06 |
| US20040258608A1 (en) | 2004-12-23 |
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