WO2001048060A1 - A process for preparing composites of nano-particles and polymers - Google Patents
A process for preparing composites of nano-particles and polymers Download PDFInfo
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- WO2001048060A1 WO2001048060A1 PCT/IL2000/000806 IL0000806W WO0148060A1 WO 2001048060 A1 WO2001048060 A1 WO 2001048060A1 IL 0000806 W IL0000806 W IL 0000806W WO 0148060 A1 WO0148060 A1 WO 0148060A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
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- the present invention relates to a process for preparing nano-particles from a liquid suspension thereof. More particularly, the present invention relates to a process for producing composites of nano-particles and polymers and solid compacts formed therefrom.
- nano-particles Solid particles of dimensions below 100nm (one hundred nanometers) are commonly referred to as “nano-particles” and more loosely as “nano-materials” which term may cover products made of or containing nano-particles.
- Nano-fillers are much more efficient in imparting a specific property to products containing them than are particles of identical compositions but of larger size.
- nanostructured composites have a desired material property which differs by at least 20% from the same material property in micron-scale composites.
- the desired material property is selected from the group consisting of refractive index, transparency to light, reflection characteristics, resistivity, permittivity, permeability, coercivity, B-H product, magnetic hysteresis, breakdown voltage, skin depth, curie temperature, dissipation factor, work function, band gap, electromagnetic shielding effectiveness, radiation hardness, chemical reactivity, thermal conductivity, temperature coefficient of an electrical property, voltage coefficient of an electrical property, thermal shock resistance, biocompatibility and wear rate.
- nano-particles may comprise one or more elements selected from the s, p, d and f groups of the periodic table, or they may comprise a compound of one or more such elements with one or more suitable anions such as aluminum, antimony, boron, bromine, carbon, chlorine, fluorine, germanium, hydrogen, indium, iodine, nickel, nitrogen, oxygen, phosphorus, selenium, silicon, sulfur, or tellurium.
- suitable anions such as aluminum, antimony, boron, bromine, carbon, chlorine, fluorine, germanium, hydrogen, indium, iodine, nickel, nitrogen, oxygen, phosphorus, selenium, silicon, sulfur, or tellurium.
- Liquid suspensions of solid particles in general and aqueous suspensions in particular provide for non-contaminating disintegration of single crystallites and of aggregates by mechanical and other energies specifically directed to this end e g WO 9404459 which illustrates the formation of nano aluminum oxide by cavitation Suspensions of nano-particles of a desired average size and narrow size distribution thus obtained are still subject to re-aggregation over time and during drying
- a particular compact of this kind may be a final product, a component of a final product or an intermediate in the making of such a product or product component
- the usual method of making such compacts is by mixing a dry powder of nano-particles with a polymer in dry or liquid form for further processing
- dry nano-powder by present art have in general a history of separating and drying from suspensions of nano-particles in liquids obtained directly in wet processes or through comminution in liquid media
- the present invention provides a process for recovering nano-particles from a liquid suspension thereof, comprising mixing a liquid suspension of nano-particles with a polymer-solvent solution, said polymer-solvent solution being characterized in that said solvent is completely miscible with said liquid in which said nano-particles are suspended and said polymer is insoluble in said liquid, whereby a solid phase consisting of an intimate mixture of nano-particles and polymer separate from said liquid
- WO 98/56854 there is described a preferred method for producing a polymeric matrix with a nanoscale filler in which the filler is first suspended in deminerahzed water and the suspension's pH is measured The pH is then adjusted and stabilized with a small addition of acid (e g , acetic acid or dilute nitric acid) or base (e g , ammonium hydroxide or dilute sodium hydroxide) The pH adjustment produces a charged state on the surface of the filler Once a desired pH has been achieved, a coating material (for example, a polymer or other appropriate precursor) with opposite charge is introduced into the solvent This step results in coupling of the coating material around the nanoscale filler and formation of a coating layer around the nanoscale filler Once the layer has formed, the filler is removed from the solvent by drying, filtration, cent ⁇ fugation, or any other method appropriate for solid-liquid separation
- the composites are produced by mixing the nanostructured powder a polymer using a mortar and pestle or a hydraulic press
- NP nano-particles and polymer
- Any NP is easily recovered by the application of a conventional solids/liquid separation process that suits best each case such as decantation, filtration cent ⁇ fugation followed by drying to remove residual liquid phase
- a washing operation may be introduced prior to drying in which the residual liquid is displaced by pure water or another pure solvent prior to drying
- the ratio of polymer to nano-particles can be chosen within a wide range to constitute 10% to 90% of the NP The actual choice is guided by the properties desired for efficiency and economy in the conversion of a particular NP to solid compacts and the intended further transformation of such compacts, if any
- Solid compacts consisting of nano-particles evenly dispersed in a polymeric matrix are formed from NP materials by conventional technologies of shaping polymers such as pressing, extrusion and casting Solvents or plasticisers may be added to NP prior to shaping as temporary or permanent composition modifiers of the solid compact produced Electrical or magnetic fields may be applied during or after shaping particular solid compacts, heat may be used to induce sintering of the nano-particles - as described extensively in prior art
- Barium titanate was prepared according to the best procedure established by Wei-ling Luan & al Cited above
- the preparation of the Barium Titanate PMM NP was repeated with the difference that the reactant solutions were fed continuously to a first agitated reactor consisting of a 50mls beaker with the overflow entering a second agitated 30mls reactor where it was continuously mixed with the PMM solution In this manner residence times were greatly shortened In fact the NP obtained provided solid compacts that sintered virtually to theoretical density in less than one hour
- the invention thus provides for improving on any current process in which nano-particles due to be incorporated in a solid compact are present in a liquid suspension in an obligatory stage of their preparation
- Example 2
- a NP of barium titanate and PMM was prepared by the same method as above with the difference that 54grs of PMM were dissolved in the acetone instead of the 3 4grs used in the previous example This NP could be extruded into cylindrical elements that had a density of 3 76gr/ml (compared to the computed maximum possible density of 3 762) and exhibited outstanding piezoelectric properties without undergoing any sintering whatsoever
- nano-particles of a copper alloy dispersed in a non-aromatic liquid such as hexane were precipitated by mixing with a solution of poly-methylstyrene in toluene to obtain a NP of nanocopper
- a non-aromatic liquid such as hexane
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Abstract
The invention provides a process for recovering nano-particles from a liquid suspension thereof, comprising mixing a liquid suspension of nano-particles with a polymer-solvent solution, said polymer-solvent solution being characterized in that said solvent is completely miscible with said liquid in which said nano-particles are suspended and said polymer is insoluble in said liquid, whereby a solid phase consisting of an intimate mixture of nano-particles and polymer separate from said liquid.
Description
A PROCESS FOR PREPARING COMPOSITES OF NANO- PARTICLES AND POLYMERS .
The present invention relates to a process for preparing nano-particles from a liquid suspension thereof. More particularly, the present invention relates to a process for producing composites of nano-particles and polymers and solid compacts formed therefrom.
Solid particles of dimensions below 100nm (one hundred nanometers) are commonly referred to as "nano-particles" and more loosely as "nano-materials" which term may cover products made of or containing nano-particles.
Properties that make nano-particles useful in numerous actual and potential applications have been widely described. PCT WO/56854 by YADAV et al deals with uses of nano-particles as fillers in solid polymer compositions. Said publication illustrates through numerous examples that "nano-fillers" are much more efficient in imparting a specific property to products containing them than are particles of identical compositions but of larger size.
The range of effects, proven or expected to be inducible by nano-particles, is remarkably wide.
Thus said publication, the relevant teachings of which are incorporated herein by reference, teaches that nanostructured composites have a desired material property which differs by at least 20% from the same material property in micron-scale composites. According to said publication the desired material property is selected from the group consisting of refractive index, transparency to light, reflection characteristics, resistivity, permittivity, permeability, coercivity, B-H product, magnetic hysteresis, breakdown voltage, skin depth, curie temperature, dissipation factor, work function, band gap, electromagnetic shielding effectiveness, radiation hardness, chemical reactivity, thermal conductivity, temperature coefficient of an electrical property, voltage coefficient of an electrical property, thermal shock resistance, biocompatibility and wear rate.
As is known and as also described in said publication, nano-particles may comprise one or more elements selected from the s, p, d and f groups of the periodic table, or they may comprise a compound of one or more such elements with one or
more suitable anions such as aluminum, antimony, boron, bromine, carbon, chlorine, fluorine, germanium, hydrogen, indium, iodine, nickel, nitrogen, oxygen, phosphorus, selenium, silicon, sulfur, or tellurium.
The control of each of these properties depends on a variety of factors specific to each case. The elucidation of these factors is the subject of ongoing studies that intensified some twenty years ago when nano particles were broadly recognized as having unique properties that are practically absent at larger sizes. Size is by far the strongest determinant with respect to the effects and the intensity of their expression of every nano material. Without exception the characteristic sought in any particular nano-material rises steeply below a defined size.
Consequently to the foregoing great efforts are being invested in devising processes that provide for controllably smaller particles in the nano range.
However, even when a desirably small size is initially obtained there are as a rule great difficulties in maintaining this size in further processing to desired products such as solid compacts. The coalescence of nano-particles to form aggregates is a source of difficulties of great practical importance, as described, e.g., in the review "RECENT DEVELOPMENTS IN THE MANUFACTURE OF BARIUM TITANATE POWDERS" BY A.D.HILTON and R.Frost, Key Engineering Materials Vols. 66&67 (1992) pp.145-184. The tendency to aggregate is understandable in terms of fundamental physics: the smaller the nano-particles the larger their surface and, proportionately, the surface free energy that drives particle coalescence.
Numerous procedures for making nano-particles of a great variety of compositions are available in patents and in other publications. They fall into two classes generally referred to as "wet" and "dry" methods. The former involve a liquid phase (aqueous or non-aqueous), the latter involving solid and vapor phases only.
As a rule, in wet preparations (e.g. Wei-ling Luan & al, NanoStructured Materials, Vol.10, No.7, pp 1119-1125, 1999) a suspension of very small nano-particles is initially formed. Such suspensions are subject to coalescence and aggregation. As a result it is difficult to maintain the nano-particles in suspension in the size range in which they are formed. Further aggregation may take place during recovery of the nano-material in powder form by drying.
Solid-state reactions result as a rule in particles in the micron (micrometer) range or higher Thus Hilton et al ibid state that BaTιO3 obtained by heating a mixture of fine powders of BaO and of TιO2 needs to be suspended in water and milled to reduce particle sizes to the nano range They find a need for comminution of aggregates associated with most of the wet methods of preparing nano barium titanate reviewed by them
US 5,851 ,507 and US 5,194,128 describe dry methods that involve high temperature required for vaporizing or ablating metals, oxides, nitrides etc The very rapid cooling required to prevent aggregation naturally invites the use of water for capturing particles in an early stage of their formation Thus dry methods frequently result in suspensions of nano-particles
Liquid suspensions of solid particles in general and aqueous suspensions in particular provide for non-contaminating disintegration of single crystallites and of aggregates by mechanical and other energies specifically directed to this end e g WO 9404459 which illustrates the formation of nano aluminum oxide by cavitation Suspensions of nano-particles of a desired average size and narrow size distribution thus obtained are still subject to re-aggregation over time and during drying
Numerous applications of nano-mateπals require the formation of solid compacts consisting of nano-particles and a polymer A particular compact of this kind may be a final product, a component of a final product or an intermediate in the making of such a product or product component The usual method of making such compacts is by mixing a dry powder of nano-particles with a polymer in dry or liquid form for further processing Thus, dry nano-powder by present art have in general a history of separating and drying from suspensions of nano-particles in liquids obtained directly in wet processes or through comminution in liquid media
It is the purpose of the present invention to improve in a major way on the separation of nano-particles from the suspending liquid, the subsequent drying and concurrently prevent, or at least contain, the aggregation taking place in present procedures for the sequence from nano-particles formation to the manufacture of compacts that contain them This improvement is obtained by mixing the freshly formed liquid suspension of nano-particles (obtained directly by reaction in a liquid phase or by
a comminuting treatment of a suspension of solid particles originally formed by a dry method) with a solution of a polymer which is characterized in that the solvent that holds the polymer in solution is completely miscible with the liquid in which the nano-particles are suspended and that the polymer is insoluble in the liquid in which the nano-particles are suspended, whereby a solid phase consisting of an intimate mixture of nano-particles and polymer separates
Thus, the present invention provides a process for recovering nano-particles from a liquid suspension thereof, comprising mixing a liquid suspension of nano-particles with a polymer-solvent solution, said polymer-solvent solution being characterized in that said solvent is completely miscible with said liquid in which said nano-particles are suspended and said polymer is insoluble in said liquid, whereby a solid phase consisting of an intimate mixture of nano-particles and polymer separate from said liquid
In WO 98/56854 there is described a preferred method for producing a polymeric matrix with a nanoscale filler in which the filler is first suspended in deminerahzed water and the suspension's pH is measured The pH is then adjusted and stabilized with a small addition of acid (e g , acetic acid or dilute nitric acid) or base (e g , ammonium hydroxide or dilute sodium hydroxide) The pH adjustment produces a charged state on the surface of the filler Once a desired pH has been achieved, a coating material (for example, a polymer or other appropriate precursor) with opposite charge is introduced into the solvent This step results in coupling of the coating material around the nanoscale filler and formation of a coating layer around the nanoscale filler Once the layer has formed, the filler is removed from the solvent by drying, filtration, centπfugation, or any other method appropriate for solid-liquid separation
As described in the examples of said publication, the composites are produced by mixing the nanostructured powder a polymer using a mortar and pestle or a hydraulic press
Thus, it will be realized that the process described in said patent is much more complicated than that of the present invention and is dependent on pH adjustment and is charge dependent, whereas susoension in deminerahzed water will generally require
prior separation and the washing out of any reagent present which might have originated in the preparation of the nano-particles whereby irreversible growth by coalescence and aggregation is most likely to take place Furthermore, said process is not based on the simple expedient of polymer precipitation, wherein said polymer carries the nano-particles with it during precipitation and thus inherently forms a composite of nano-particles and polymer in situ
This intimate mixture of nano-particles and polymer will be referred to further below as NP Any NP is easily recovered by the application of a conventional solids/liquid separation process that suits best each case such as decantation, filtration centπfugation followed by drying to remove residual liquid phase A washing operation may be introduced prior to drying in which the residual liquid is displaced by pure water or another pure solvent prior to drying
The ratio of polymer to nano-particles can be chosen within a wide range to constitute 10% to 90% of the NP The actual choice is guided by the properties desired for efficiency and economy in the conversion of a particular NP to solid compacts and the intended further transformation of such compacts, if any
Solid compacts consisting of nano-particles evenly dispersed in a polymeric matrix are formed from NP materials by conventional technologies of shaping polymers such as pressing, extrusion and casting Solvents or plasticisers may be added to NP prior to shaping as temporary or permanent composition modifiers of the solid compact produced Electrical or magnetic fields may be applied during or after shaping particular solid compacts, heat may be used to induce sintering of the nano-particles - as described extensively in prior art
While the invention will now be described in connection with certain preferred embodiments in the following examples so that aspects thereof may be more fully understood and appreciated, it is not intended to limit the invention to these particular embodiments On the contrary, it is intended to cover all alternatives, modifications and equivalents as may be included within the scope of the invention as defined by the appended claims Thus, the following examples which include preferred embodiments will serve to illustrate the practice of this invention, it being understood that the particulars shown are by way of example and for purposes of illustrative discussion of
preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of formulation procedures as well as of the principles and conceptual aspects of the invention Example 1
Barium titanate was prepared according to the best procedure established by Wei-ling Luan & al Cited above
50grs of tetrabutyl titanate were dissolved in 200grs glacial acetic acid Distilled water was added with agitation until the initial cloudiness disappeared 29grs barium carbonate was added and the reaction allowed to reach completion as evidenced by termination of gas evolution The clear solution containing Ti and Ba in equivalent amounts was poured slowly into an intensely agitated solution of 50grs caustic soda in 500mls distilled water The precipitate that formed was filtered, thoroughly washed and freeze dried and then calcined for 1 hour at 800°C Scanning electron microscopy (SEM) indicated a size range of 30 to 40nm in good accord with the Wei's results The cold-pressing and sintering described by Wei was not repeated as further confirmation of Wei's procedure was not seen as necessary for acceptance of the results of sintering experiments that he describes
To compare with the present invention the same BaTi in acetic acid and NaOH in water were prepared Additionally a solution of 3 4grs of polymethylmethacrylate (PMM) in 100mls acetone was prepared Immediately after the end of mixing the two former solutions (in about 4mιn) just as in Wei's procedure, repeated and confirmed above, the polymer solution was added slowly (in about 2mιn) while continuing a vigorous agitation On stopping the agitation, a visibly flocculated precipitate settled rapidly It was mixed repeatedly with distilled water and decanted to eliminate all solutes and dried at 40°C to 38grs of a colorless NP of barium titanate and PMM
A small sample of this NP was heated in an open porcelain dish for one hour at 800°C The organic matter was completely burned-off SEM of the residual powder showed a size range of 12-30nm Evidently the nano-particles obtained in the NP were
much smaller than in the reference preparation with the wide size distribution being ascπbable to some aggregation during calcination
A 3grs of the NP were heated in a metal mold (consisting of a cylindrical cavity of 30mm diameter in a metal block) at 150°C under manually exercised pressure A dense cylindrical solid compact was obtained When calcined to sintering for two hours at 1 100°C - it condensed to 98% of theoretical, better than Wei.s best result of about 95%
The preparation of the Barium Titanate PMM NP was repeated with the difference that the reactant solutions were fed continuously to a first agitated reactor consisting of a 50mls beaker with the overflow entering a second agitated 30mls reactor where it was continuously mixed with the PMM solution In this manner residence times were greatly shortened In fact the NP obtained provided solid compacts that sintered virtually to theoretical density in less than one hour
The invention thus provides for improving on any current process in which nano-particles due to be incorporated in a solid compact are present in a liquid suspension in an obligatory stage of their preparation Example 2
A NP of barium titanate and PMM was prepared by the same method as above with the difference that 54grs of PMM were dissolved in the acetone instead of the 3 4grs used in the previous example This NP could be extruded into cylindrical elements that had a density of 3 76gr/ml (compared to the computed maximum possible density of 3 762) and exhibited outstanding piezoelectric properties without undergoing any sintering whatsoever
The choice of polymers available in the exercise of this option is very extensive It includes primarily common commercial thermoplastic materials such as cellulose esters and ethers (c-acetate, c-acetate/butyrate, ethyl-c ), synthetic polyesters and polyethers such as the PMM mentioned in the example, Polyvinyl Butyral ("Butacite") Natural polymers such as xanthane gum (XG) can also used to advantage as illustrated further below
The solvents that can be used in the exercise of the invention cover a very wide range Water plays of course a special role since it is the medium in which a majority of nano-mateπals are prepared Solvents of useful polymers that are fully (or to marked extent water miscible) are numerous Acetone, Ci to C4 alkanols, methylacetate, formamide, alkanolamides are fully water miscible and the range can be extended by blending two or more solvents The relevant information is available in reference books and need not be repeated here
The foregoing should not be read as excluding non-aqueous systems Thus nano-particles of a copper alloy dispersed in a non-aromatic liquid such as hexane were precipitated by mixing with a solution of poly-methylstyrene in toluene to obtain a NP of nanocopper Thus the present invention provides for extending the boundaries of nano-mateπals technology
Compatibility considerations can be applied in a variety of ways to adapt to special situations Thus for example the preparation of an alumina/XG NP with the alumina obtained by precipitation in dilute aqueous solution and the XG being inherently soluble only in water - posed seemingly a difficult problem It was simply solved according to the present invention by the procedure as described in Example 3 hereinafter Example 3
100mls of a suspension of alumina nano-particles (obtained by known art) containing approximately 7grs Al203 was mixed with 60mls t-Butanol The 160mls of extended suspension thus obtained were mixed with 100mls of a 2 7% aqueous solution of XG The mixing was done continuously by metering the solutions intoa small mixing chamber A flocculated precipitate was formed that settled out of the collected mixture In this case the tertButanol provided a modification of the suspending aqueous liquid sufficient to make it incompatible with XG
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative examples and that the present invention may be embodied in other specific forms without departing from the essential attributes thereof, and it is therefore desired that the present embodiments and examples be considered in all respects as illustrative and not restrictive, reference being made to the appended
claims, rather than to the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims
1. A process for recovering nano-particles from a liquid suspension thereof, comprising mixing a liquid suspension of nano-particles with a polymer-solvent solution, said poiymer-solvent solution being characterized in that said solvent is completely miscible with said liquid in which said nano-particles are suspended and said polymer is insoluble in said liquid, whereby a solid phase consisting of an intimate mixture of nano-particles and polymer separate from said liquid.
2. A solid compact of nano-particles and polymer whenever formed according to the process of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU17288/01A AU1728801A (en) | 1999-12-27 | 2000-11-30 | A process for preparing composites of nano-particles and polymers |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IL133745 | 1999-12-27 | ||
| IL13374599A IL133745A0 (en) | 1999-12-27 | 1999-12-27 | A process for the recovery of nano-particles from liquid suspensions thereof |
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| Publication Number | Publication Date |
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| WO2001048060A1 true WO2001048060A1 (en) | 2001-07-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/IL2000/000806 WO2001048060A1 (en) | 1999-12-27 | 2000-11-30 | A process for preparing composites of nano-particles and polymers |
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| AU (1) | AU1728801A (en) |
| IL (1) | IL133745A0 (en) |
| WO (1) | WO2001048060A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8734898B2 (en) | 2012-09-21 | 2014-05-27 | E I Du Pont De Nemours And Company | Method for producing encapsulated nanoparticles |
| US11707649B2 (en) | 2020-12-08 | 2023-07-25 | Kevin Osborne | Portable golf ball scrubber assembly |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19639632A1 (en) * | 1996-09-26 | 1998-04-09 | Zenneck Ulrich Prof Dr | Ion-free nano-metal-polymer composites |
| WO1998056854A1 (en) * | 1997-06-09 | 1998-12-17 | Nanomaterials Research Corporation | Nanostructured fillers and carriers |
| DE19756790A1 (en) * | 1997-12-19 | 1999-07-01 | Fraunhofer Ges Forschung | Prepolymer with dispersed nanoscale solid particles isolated therein, process for its preparation and its use |
-
1999
- 1999-12-27 IL IL13374599A patent/IL133745A0/en unknown
-
2000
- 2000-11-30 WO PCT/IL2000/000806 patent/WO2001048060A1/en active Application Filing
- 2000-11-30 AU AU17288/01A patent/AU1728801A/en not_active Abandoned
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19639632A1 (en) * | 1996-09-26 | 1998-04-09 | Zenneck Ulrich Prof Dr | Ion-free nano-metal-polymer composites |
| WO1998056854A1 (en) * | 1997-06-09 | 1998-12-17 | Nanomaterials Research Corporation | Nanostructured fillers and carriers |
| DE19756790A1 (en) * | 1997-12-19 | 1999-07-01 | Fraunhofer Ges Forschung | Prepolymer with dispersed nanoscale solid particles isolated therein, process for its preparation and its use |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8734898B2 (en) | 2012-09-21 | 2014-05-27 | E I Du Pont De Nemours And Company | Method for producing encapsulated nanoparticles |
| US11707649B2 (en) | 2020-12-08 | 2023-07-25 | Kevin Osborne | Portable golf ball scrubber assembly |
Also Published As
| Publication number | Publication date |
|---|---|
| AU1728801A (en) | 2001-07-09 |
| IL133745A0 (en) | 2001-04-30 |
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