EP0509574B1 - Fluides électrorhéologiques et méthode pour la préparation et l'application de ceux-ci - Google Patents
Fluides électrorhéologiques et méthode pour la préparation et l'application de ceux-ci Download PDFInfo
- Publication number
- EP0509574B1 EP0509574B1 EP92200905A EP92200905A EP0509574B1 EP 0509574 B1 EP0509574 B1 EP 0509574B1 EP 92200905 A EP92200905 A EP 92200905A EP 92200905 A EP92200905 A EP 92200905A EP 0509574 B1 EP0509574 B1 EP 0509574B1
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- European Patent Office
- Prior art keywords
- vermiculite
- electro
- composition
- quaternary ammonium
- treated
- Prior art date
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- C10M2229/053—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing sulfur
- C10M2229/0535—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing sulfur used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
- C10M2229/054—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing phosphorus
- C10M2229/0545—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing phosphorus used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/16—Dielectric; Insulating oil or insulators
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/17—Electric or magnetic purposes for electric contacts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/175—Pantographs, i.e. printing devices
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/18—Electric or magnetic purposes in connection with recordings on magnetic tape or disc
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/185—Magnetic fluids
Definitions
- the present invention relates to fluid compositions which demonstrate significant changes in their fluid properties in the presence of an electrical field.
- Electro-rheological response is a phenomenon in which the rheology of a fluid is modified by the imposition of an electrical field. Fluids which exhibit significant changes in their properties of flow in the presence of an electrical field have been known for several decades. The phenomena of electro-rheology was reported by W. M. Winslow, U.S. patent No. 2,417,850, in 1947. Winslow demonstrated that certain suspensions of solids in liquids show large, reversible electro-rheological effects. In the absence of electrical field, electro-rheological fluids generally exhibit Newtonian behavior. That is, the applied force per unit area, known as shear stress, is directly proportional to the shear rate, i.e., relative velocity per unit thickness.
- a complete understanding of the mechanisms through which electro-rheological fluids exhibit their particular behavior has eluded workers in the art. Many have speculated on the mechanisms giving rise to the behaviour characteristics of electro-rheological fluids.
- a first theory is that the applied electrical field restricts the freedom of particles to rotate, thus changing their bulk behavior.
- a second theory describes a change in properties to the formation of filament-like aggregates which form along the lines of the applied electrical field.
- This "induced fibrillation" results from small, lateral migrations of particles to regions of high field intensity between gaps of incomplete chains of particles, followed by mutual attraction of these particles.
- a third theory refers to an "electric double layer" in which the effect is explained by hypothesising that the application of electrical field causes a layer of materials adsorbed upon the discrete phase particles to move, relative to the particles, in the direction along the field toward the electrode having a charge opposite that of the mobile ions in the adsorbed layer.
- ER fluids in automotive applications, such as vibration damping, shock-absorbers, or torque transfer, stems from their ability to increase, by orders of magnitude, their apparent viscosity upon application of electrical field. This increase can be achieved with very fast (on the order of milliseconds) response times and with minimal power requirements.
- ER-fluids have been formulated and investigated since the early 1940's, basic limitations have prevented their utilization in practical devices.
- An object of this invention is to formulate a stable, substantially water-free, or non-aqueous ER-fluid with improved properties.
- one goal of this invention to remove the water without compromising the electro-rheological effect.
- This invention generally includes electro-rheological fluids comprising particles treated with polar salt such as an amine salt and a non-conducting or dielectric fluid.
- the particles are vermiculite and are chemically-defoliated and are plate-like.
- the preferred polar salts are quaternary ammonium salts.
- the fluid is non-aqueous.
- the liquid phase of the fluid is substantially free of quaterany ammonium salt not bound to the particles and substantially free of dispersing agents.
- Figure 1 is a graphic illustration of the effect on viscosity of an ester additive to an electro-rheological fluid.
- Figure 2 is a graphic illustration of the effect on viscosity of treating a solid phase of an electro-rheological fluid with an amine salt.
- Figure 3 is a graphic illustration of the effect on viscosity of changing the frequency of an applied field and the temperature of an electro-rheological fluid.
- Figure 4 is a graphic illustration of the effect of varying the temperature of an electro-rheological fluid and varying the frequency of an applied field to maintain constant viscosity.
- Figure 5 is a graphic illustration of the effect on viscosity of adsorbing propylene carbonate on a solid phase of an electro-rheological fluid.
- Figure 6 is a graphic illustration of the effect on viscosity of absorbing propylene carbonate on the solid phase and of an ester additive to an electro-rheological fluid.
- Vermiculite is a gold-coloured mineral having the formula 3MgO(FeAl)2O3,3SiO2. Chemically-defoliated vermiculite, in a plate-like Al-Mg sheet silicate form, is commercially available from W. R. Grace, Inc., U.S.A., under the trade name MICROLITE 903 tm .
- the term "plate-like Al-Mg sheet silicate form” means that the particles are made up of multiple-layered planes ("sheets") consisting of extensive Si-O linkages (silicate). The planes are ionically-bonded to one another via cations such as Al3+ and Mg2+.
- the particles of vermiculite are partially-conductive particles.
- the vermiculite is hydrophilic which makes it a) difficult to disperse in typical base electro-rheological fluid phases such as silicon oils and hydrocarbons and b) is not likely to stay dispersed. If the vermiculite does not stay dispersed, it settles and forms a cake material. This is undesirable because considerable mechanical energy must be expended to continually re-disperse the solid in order for the material to function as an electro-rheological fluid.
- the present invention provides a method of treating this vermiculite to achieve advantageous results.
- chemically-de-laminated vermiculite plates are surface-treated with an organic amine salt.
- An ionic bond is formed between the vermiculite and the amine salt.
- the amine salt serves two purposes. Firstly, the amine salt allows the vermiculite, after proper drying, to form a very stable dispersion with silicon oil or other non-aqueous liquids such as hydrocarbon liquid phase materials. Secondly, the amine salt allows the individual plate-like vermiculite particles to be polarized in an electrical field without the presence of water. The polarization of the particles is a necessary requirement for a system to demonstrate an ER behaviour. The geometry of the plate-like vermiculite particles produces a greater polarization in an electric field than other shapes.
- the plate-like vermiculite has an average face diameter range from 1 to 30 micrometres, and a particle thickness of 6 to 10 nanometres (60 to 100 Angstroms).
- the vermiculite may be present in an amount range from 5 to 50, and preferably 10 to to 30 percent by weight of the composition.
- the chemically-defoliated vermiculite is surface-treated by exchanging lithium on the surface of an amine cation.
- the amine cation may be primary, secondary, or tertiary, and preferably is a quaternary ammonium salt.
- Suitable treating materials are amine salts including at least one selected from the group consisting of alkyl ammonium halides, preferably with an alkyl group having 2 to 18 carbons, and most preferably 12 carbons or dodecylamine salt.
- Suitable amine salts, and particularly quaternary ammonium salts, contemplated include those listed in Bosso et al, U.S. Patent No. 3,839,252.
- a quaternary ammonium salt is a type of organic nitrogen compound in which the molecular structure includes a central nitrogen atom joined to four groups (the cation) and an anion, the structure as indicated as: wherein R1, R2, R3 and R4 are alkyl or aromatic groups or hydrogen, and wherein at least one of the R-groups has from 2 to 18 carbons and the other R-groups have from 2 to 18 carbon atoms.
- Particularly suitable quaternary ammonium salts include at least one selected from the group consisting of octadecyldimethylbenzyl ammonium chloride, hexamethonium chloride, and lauryl pyridinium chloride.
- the vermiculite is placed in a solution of amine salts comprising the amine salt and de-ionized water as a solvent.
- the equivalent of amine in solution to vermiculite may range from 5 to 1, preferably 2 to 1 and most preferably 1 to 1.
- the time period for which the vermiculite is treated may range, depending on temperature, from 3 to 24 hours, preferably 3 to 12 hours and most preferably 6 to 12 hours at room temperature. Higher temperatures require less time to treat the particles.
- the attached hydrocarbon chain on the treated material will render it substantially hydrophobic, thereby increasing its inherent dispersity as well as its stability towards coagulation.
- the dried, treated vermiculite is substantially free of water.
- substantially free of water means less than 1% by weight water adhering to the vermiculite.
- the amount of water adhering to the vermiculite is less than that required (approximately 6-10% by weight) for the water to be an "activator" of ER-response.
- This drying is preferably carried out under vacuum to a constant pressure ranging from 13.3322 to 66.661 Pa (100 to 500 mTorr), preferably 13.3322 to 33.3305 (100 to 250 mTorr) and most preferably at least 19.9983 Pa (150 mTorr).
- the resultant treated, dried materials are then dispersed in a base fluid composition by ball-milling for 22 hours.
- the ball-milling substantially reduces the average face diameter to at least the range of from 5 to 25 micrometres, preferably 1-5 micrometres, more preferably 1 micrometre to 3 micrometres, and most preferably less than 1 micrometre which also promotes suspension stability and dispersibility.
- the ball-milling base fluid may comprise any suitable fluid known in the art, and is preferably 75% silicon oils/25% butyl benzoate.
- Other suitable ball-milling fluids include mineral oils or a material that is to be used as the liquid phase of the ER-fluid.
- Suitable liquid-phase materials are disclosed in Block et al, "Electro-Rheology", IEEE Symposium, London, 1985, which is hereby incorporated by reference.
- a suitable silicone oil is commercially available from Dow Corning Corporation, U.S.A., under the trade name Dow Corning 200 Fluid (20cS) tm .
- a defoliated vermiculate suspension is prepared by adding 7 to 15 grams of chemically-defoliated vermiculite to 1 to 100 ml of de-ionized water.
- a suitable chemically-defoliated vermiculite is MICROLITE 903 tm .
- the aqueous defoliated vermiculite suspension is added drop-wise to an aqueous solution of excess amine hydrochloride solution, mechanically agitated for six hours, and then filtered.
- the amine hydrochloride solution may be 6.2% by weight of octylamine hydrochloride or 3.0% of dodecylamine hydrochloride in an aqueous solution.
- the solid is re-dispersed and filtered twice with ethanol to remove any excess amine hydrochloride.
- the solid is then dried in a vacuum at 100 degrees C. until at least a 19.9983 Pa (150 millitorr) vacuum is reached.
- the amine-treated vermiculite is ball-milled with a base fluid (e.g., 75% silicon oil/25% butyl benzoate) for 24 hours.
- a base fluid e.g., 75% silicon oil/25% butyl benzoate
- esters include at least one selected from the group comprising benzoates, preferably alkyl, or alkyl adipates.
- the alkyl group may range from C1 to C18 and preferably the ester is n-butyl benzoate.
- Preferred adipates include di-isononyl adipate and dioctyl adipate.
- the amount of additional liquid may comprise from 5 to 75%, preferably 5 to 50%, and most preferably 5-25% by volume of the electro-rheological fluid.
- the additional fluid adds to the inherent stability and dispersibility of the treated solid phase as well as acting to lower quite substantially the base fluid viscosity and hence, the zero-field viscosity of the suspension.
- the primary basis for the utility of electro-rheological effect is the change in shear stress (i.e., increase in apparent viscosity) with applied electric field.
- an electro-rheological fluid composition comprising 10% vermiculite treated with dodecylamine, 75% silicon oils/25% butyl benzoate prepared in a manner described above has a viscosity at a shear rate of 400/seconds (which will be standard conditions for the purposes of illustration) of 28mPa sec (cP).
- cP 28mPa sec
- the fluid At a field strength of 3.45kV/mm (AC, 60Hz), the fluid has an apparent viscosity of 1198mPa sec which is 43 times the zero-field value. This increase in apparent viscosity is greatly magnified as the shear rate decreases.
- Figure 2 is a plot of the viscosity ratio as a function of shear rate (3.45kV/mm to zero-field).
- the above-described electro-rheological composition (illustrated by Figure 1) is compared to the same composition but in which the vermiculite particles are not treated with an amine to form the dispersed phase.
- the composition containing the vermiculite particles not treated with an amine is basically unstable to the extent that, upon repeated application of an electric field, large particle aggregates form and precipitate out of the suspension.
- the fluid With time, the fluid will separate into two phases and must be subjected to ball-milling to re-disperse the solid. This is not the case with the treated vermiculite composition. After sitting for as long as six months, the solid is readily re-dispersed by shaking the composition.
- a method of changing the frequency of an alternating current electric field applied to an electro-rheological fluid and temperature of the fluid can be used to adjust the apparent viscosity of the fluid.
- apparent viscosity is the ratio of shear stress to shear rate.
- the other curves show significant increases/or decreases of viscosity with temperature depending on the frequency and temperature range.
- the invention is best illustrated by considering the vertical line at a temperature of 50 degrees C.
- the frequency at constant applied potential, from 50Hz to 5000Hz and preferably 60Hz to 1000Hz, any desired viscosity in the range shown can be achieved without changing the applied potential.
- This method may be adopted to the operation of a device such as a shock-absorber, or an engine mount, which requires that the viscosity be varied continuously from the field-off value to some maximum value at a given temperature.
- the frequency may be varied at any given operation temperature to produce a desired viscosity.
- Analog systems or "look-up tables" may be utilized in this regard.
- a method of changing the frequency of an alternating current electric field applied to an electro-rheological fluid can be used to maintain a constant viscosity therein over varying temperatures.
- This embodiment can be best illustrated by Figure 4 in which it can be seen that to achieve a constant viscosity of 0.3 Pas (300cP) (measured at shear rate of 400/sec) the frequency can be adjusted from 60 Hz to 1000 Hz to compensate for variation in temperatures ranging from 10 degrees C. to approximately 85 degrees C.
- the data illustrated in Figure 4 is for an electro-rheological fluid prepared as described for the embodiment illustrated by Figure 3.
- a method of activating (i.e., turning-on or producing a desired electro-rheological effect) or de-activating (i.e., turning-off or eliminating an electro-rheological effect) an electro-rheological response of a fluid under the influence of a substantially constant alternating current electric field comprises varying the frequency of the field to achieve the desired result.
- the method may be accomplished without substantially varying the temperature of the field.
- a method of producing a predetermined change in the viscosity of an electro-rheological fluid includes the steps of applying, for a predetermined period, a substantially constant alternating current electric field to the electro-rheological fluid and changing the frequency of the electric field from a first level, corresponding to a first viscosity, to a second level, corresponding to a second viscosity at a given shear rate.
- the difference between the first and second viscosities would be equivalent or equal to the predetermined change in viscosity desired.
- the strength of said alternating current electric field ranges from 1 to 5 kV/mm
- said first level of frequency is greater than 10Hz
- said second level of frequency is less than 10 kHz.
- Improvements in performance of the electro-rheological fluid can be achieved by absorption of an activator, preferably propylene carbonate, directly onto the surface of a solid phase.
- the solid phase of electro-rheological fluid is prepared in the manner described above with the additional step of adsorbing an activator directly onto the surface of the solid.
- Propylene carbonate which is insoluble in silicon oils, such as polydimethylsiloxane, is adsorbed onto the solid in specific amounts by weight. For example, pre-weighed amounts of a solid such as vermiculite of 10 to 50 percent by weight is immersed in ethanol solution containing 1 to 25 percent by weight of propylene carbonate. After thorough mixing, ethanol is removed from the solid by heating at about 100 degrees C. under vacuum for 24 hours.
- the specific amount of adsorbed propylene carbonate was determined by weighing the treated solid. In this fashion, solids were prepared in amounts of adsorbed propylene carbonate ranging from 1.4 to 16% by weight. Preferably the amount of adsorbed propylene carbonate for enhanced electro-rheological response ranges from 9% to 16%, and preferably 9 to 12% by weight.
- Electro-rheological fluids were prepared having a solid content of about 10% by weight.
- a first fluid was prepared containing amine-treated vermiculite having 6% by weight propylene carbonate adsorbed on the vermiculite and dispersed in silicone oil.
- the ER-response is represented by a first curve of Figure 6.
- a second material was prepared with amine-treated vermiculite in a liquid phase containing 65% by volume DOA and 35% by volume silicone oil.
- This ER-response of the second fluid is represented by a second curve of Figure 6.
- a third fluid was prepared having amine-treated vermiculite having 6% propylene carbonate adsorbed on the vermiculite and a liquid phase containing 65% by volume DOA and 35% by volume silicone oil.
- the ER-response of the third fluid is represented by a third curve of Figure 6.
- the three fluids were subjected to an electric field strength of 2.07 kV/mm.
- the ER-response of the fluids is plotted as shear stress ratio (that is, the ratio of excess shear stress under field to that same fluid at zero field) versus shear rate.
- the third fluid has a greater ER-response at 50/sec shear rate than the first and second fluids added together. Aspects of this procedure are claimed in our co-pending EP-A-0,509,572 corresponding to USSN 684,750.
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
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Claims (19)
- Composition contenant une phase solide en suspension dans une phase liquide, cette composition donnant lieu à une réponse électro-rhéologique en présence d'un champ électrique, caractérisée en ce que la composition est une composition anhydre dans laquelle la phase liquide comprend un fluide non conducteur ou diélectrique ; et la phase solide comprend des particules de vermiculite chimiquement exfoliées, présentes selon une quantité de 5 à 50 % en poids par rapport à la composition totale, ces particules de vermiculite ayant été traitées avec un sel d'ammonium quaternaire pour donner lieu à une efficacité d'échange de cations dans celles-ci variant de 58 % à 95 %, cette plage d'efficacités d'échange de cations étant efficace pour produire une réponse électro-rhéologique, dans la composition, à l'égard d'un champ électrique.
- Composition selon la revendication 1, dans laquelle les particules de vermiculite ont une forme de paillette.
- Composition selon la revendication 1, dans laquelle la vermiculite a un diamètre moyen de face variant de 1 à 3 µm.
- Composition selon la revendication 1, dans laquelle la vermiculite a un diamètre moyen de face inférieur à 1 µm.
- Composition selon la revendication 1, dans laquelle le sel d'ammonium quaternaire est préparé à partir d'un halogénure d'alkylammonium.
- Composition selon la revendication 1, dans laquelle le sel d'ammonium quaternaire comprend du chlorhydrate d'octylamine.
- Composition selon la revendication 1, dans laquelle le sel d'ammonium quaternaire comprend du chlorhydrate de dodécylamine.
- Composition selon la revendication 1, dans laquelle la phase liquide comprend au moins une matière choisie parmi le polydiméthylsiloxane et une huile minérale.
- Composition selon la revendication 1, dans laquelle la phase liquide comprend une huile de silicone.
- Procédé d'une préparation d'une composition selon la revendication 1, dans lequel les particules de vermiculite chimiquement exfoliées, sont traitées avec le sel d'ammonium quaternaire pour obtenir ladite plage d'efficacités d'échange de cations ; la vermiculite traitée étant séchée à une température et sous une pression suffisantes pour produire de la vermiculite traitée à peu près exempte d'eau, et on ajoute une quantité suffisante de vermiculite traitée à peu près exempte d'eau, dans le fluide non conducteur ou diélectrique, pour donner lieu à une réponse électro-rhéologique dans ladite composition, en présence d'un champ électrique appliqué.
- Procédé selon la revendication 10, comprenant en outre l'étape de broyage à l'aide de boulets de la vermiculite à peu près exempte d'eau, traitée et séchée, selon une longueur de particule variant de 1 à 3 µm.
- Procédé selon la revendication 11, dans lequel l'opération de broyage à l'aide de boulets est effectuée de façon à produire des particules de vermiculite ayant une longueur inférieure à 1 µm.
- Procédé selon la revendication 11, dans lequel la phase liquide comprend une huile de silicone et on ajoute un fluide de broyage à l'aide de boulets, comprenant au moins une matière choisie parmi une huile de silicone, le benzoate de N-butyle et les mélanges de ceux-ci.
- Procédé selon la revendication 13, dans lequel le fluide de broyage à l'aide de boulets, comprend 75 % en poids d'huile de silicone et 25 % en poids de benzoate de n-butyle.
- Procédé selon la revendication 10, dans lequel de 7 à 15 g de particules de vermiculite sont en suspension dans 100 ml et la suspension est ajoutée goutte à goutte dans une solution aqueuse comprenant de 3,0 à 6,2 % en poids du sel d'ammonium quaternaire.
- Procédé selon la revendication 10, dans lequel le sel d'ammonium quaternaire est le chlorhydrate d'octylamine ou le chlorhydrate de dodécylamine.
- Particules de vermiculite chimiquement exfoliées, destinées à être employées pour former une composition selon la revendication 1, caractérisées en ce que les particules de vermiculite sont traitées avec un sel d'ammonium quaternaire.
- Particules de vermiculite chimiquement exfoliées selon la revendication 17, dans lesquelles les particules de vermiculite sont à peu près exemptes d'eau.
- Particules de vermiculite chimiquement exfoliées selon la revendication 17, dans lesquelles le sel d'ammonium quaternaire est le chlorhydrate d'octylamine ou le chlorhydrate de dodécylamine.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US68474891A | 1991-04-15 | 1991-04-15 | |
US684748 | 1991-04-15 |
Publications (2)
Publication Number | Publication Date |
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EP0509574A1 EP0509574A1 (fr) | 1992-10-21 |
EP0509574B1 true EP0509574B1 (fr) | 1994-05-18 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP92200905A Expired - Lifetime EP0509574B1 (fr) | 1991-04-15 | 1992-03-30 | Fluides électrorhéologiques et méthode pour la préparation et l'application de ceux-ci |
Country Status (2)
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EP (1) | EP0509574B1 (fr) |
DE (1) | DE69200137T2 (fr) |
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DE4337200C2 (de) * | 1993-10-30 | 2002-09-05 | Vorwerk Co Interholding | Bauteil |
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Publication number | Priority date | Publication date | Assignee | Title |
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US3367872A (en) * | 1967-02-15 | 1968-02-06 | Union Oil Co | Electroviscous fluid composition |
JP3061058B2 (ja) * | 1988-05-13 | 2000-07-10 | 三菱化学株式会社 | 電気粘性流体 |
EP0393831A1 (fr) * | 1989-03-20 | 1990-10-24 | Imperial Chemical Industries Plc | Fluides électrorhéologiques |
JPH03221595A (ja) * | 1989-11-07 | 1991-09-30 | Dow Chem Co:The | 電気流動性液体 |
-
1992
- 1992-03-30 DE DE69200137T patent/DE69200137T2/de not_active Expired - Lifetime
- 1992-03-30 EP EP92200905A patent/EP0509574B1/fr not_active Expired - Lifetime
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Publication number | Publication date |
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DE69200137T2 (de) | 1994-09-01 |
EP0509574A1 (fr) | 1992-10-21 |
DE69200137D1 (de) | 1994-06-23 |
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