EP0482664A1 - Fluide éléctrovisqueux - Google Patents
Fluide éléctrovisqueux Download PDFInfo
- Publication number
- EP0482664A1 EP0482664A1 EP91118247A EP91118247A EP0482664A1 EP 0482664 A1 EP0482664 A1 EP 0482664A1 EP 91118247 A EP91118247 A EP 91118247A EP 91118247 A EP91118247 A EP 91118247A EP 0482664 A1 EP0482664 A1 EP 0482664A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- wet
- electroviscous
- fluid
- method silica
- silica
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000012530 fluid Substances 0.000 title claims abstract description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 8
- 125000002560 nitrile group Chemical group 0.000 claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 37
- 230000000694 effects Effects 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- -1 aliphatic nitriles Chemical class 0.000 description 12
- 239000000725 suspension Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 9
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- 125000003709 fluoroalkyl group Chemical group 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 150000007960 acetonitrile Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- AILKHAQXUAOOFU-UHFFFAOYSA-N hexanenitrile Chemical compound CCCCCC#N AILKHAQXUAOOFU-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000000063 preceeding effect Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Classifications
-
- 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
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/001—Electrorheological fluids; smart fluids
Definitions
- the present invention relates to an electroviscous fluid which comprises the dispersion of wet-method silica particles in an electrically insulating fluid.
- Fluids whose viscosity can be varied by the application of an external voltage have received attention in the last several years because they exhibit such functionalities as drive power transmission, impact absorption, valve-like behavior, and so forth.
- Such fluids whose viscosity is increased by means of an electric field are generally called "electroviscous fluids".
- electros fluids In order to be able to withstand the severe service in, for example, a clutch, engine mount, or shock absorber, a fluid is required which undergoes a substantial increase in yield value at low voltages.
- silica-based electroviscous fluids have limited application temperatures (approximately 10°C to 80 ° C), they abrade the surrounding machinery, and the particles form a sediment. Still, since silica is easily obtained on an industrial basis and is highly susceptible to improvement and manipulation, it has been considered potentially useful for certain areas of application, for example, machinery which would be used in the vicinity of room temperature and which would undergo little abrading motion.
- Silica-based electroviscous fluids are disclosed in United States Patent Number 3,047,507 and in Japanese Patent Application Laid Open [Kokai or Unexamined] Number 61-44998 [44,998/86], but in each case these exhibit an impractically weak Winslow effect.
- Japanese Patent Application Laid Open Number 01-284595 discloses an electroviscous fluid in the form of a dispersion in an electrically insulating fluid of wet-method silica whose surface adsorbed water has been replaced by polyvalent alcohol. Based on the formation of an electrical double layer by the polyvalent alcohol, this electroviscous fluid exhibits an electroviscous behavior more or less equal to that of the dispersion of the unmodified silica, but also retains its characteristics at higher temperatures (90 ° C). However, even in this case, the intensity of the Winslow effect is still basically equal to that of the prior wet-method silica-based systems. Moreover, because the dielectric constant of the polyvalent alcohol declines with increasing temperature, the Winslow effect still declines at higher temperatures.
- the present invention introduces a silica dispersion- type electroviscous fluid which develops a Winslow effect sufficient to satisfy industrial applications.
- the present inventor carried out extensive investigations with a view to solving the aforementioned problems, and discovered as a result that the aforementioned problems are substantially reduced by using the disperse phase of silica which is advantageously prepared by replacing the water adsorbed on the surface of the wet-method silica with a particular type of compound.
- the present invention was developed based on this discovery.
- the present invention relates to an electroviscous fluid which comprises a dispersion of 0.1 to 50 weight% wet-method silica whose surface adsorbed water has been replaced by a nitrile group-containing organic compound in an electrically insulating fluid.
- wet-method silica particles employed by the present invention are prepared by the production of silica by the addition of acid under wet conditions to a water glass starting material.
- These wet-method silica particles are an ideal disperse phase for electroviscous fluids because their surfaces possess a layer of adsorbed water, which is ideal for the development of the Winslow effect, and because they have optimal particle sizes.
- the type of wet-method silica employed by tile present invention is not specifically restricted.
- the water adsorbed on the surface of this wet-method silica is replaced by a nitrile-containing organic compound. Therefore the surface of wet-method silica is normally covered with a layer of adsorbed water. While the particular weight proportion for this adsorbed water in the total silica weight will vary with the particular type of wet-method silica, in general it will fall within the range of 5% to 10%. Since this layer of adsorbed water is merely hydrogen bonded to a layer of structural water which resides immediately inward, it can be almost completely eliminated by heating to around 100°C. However, as discussed hereinabove, this adsorbed water layer plays a significant role in the development of the Winslow effect.
- the adsorbed water layer causes a Winslow effect due to the high dielectric constant of the water (approximately 80 at room temperature). However, its ease of elimination by heating extinguishes the Winslow effect.
- this adsorbed water layer on the surface of wet-method silica is replaced with a nitrile-group containing organic compound.
- nitrile group-containing organic compound as specified herein is exemplified by aliphatic nitriles such as acetonitrile, propionitrile, n-capronitrile, succinonitrile, etc., and by aromatic nitriles such as benzonitrile, alpha-tolunitrile, and so forth.
- aliphatic nitriles such as acetonitrile, propionitrile, n-capronitrile, succinonitrile, etc.
- aromatic nitriles such as benzonitrile, alpha-tolunitrile, and so forth.
- Various methods can be devised for the replacement procedure, but the following method has proven to be simple and straightforward. First, the wet-method silica is placed under a nitrogen current at 150°C in order to remove the surface adsorbed water.
- the nitrile compound is then added in a quantity corresponding to the weight loss due to the desorbed water with mixing to physical homogeneity in, for example, a mixer.
- the surface of the wet-method silica will be covered by a layer of the nitrile compound. Due to the high dielectric constant of the treated water, a Winslow effect can be developed which is at least equivalent to that for the adsorbed water. Moreover, because in this case the dielectric constant is only slightly temperature dependent, the decline in the Winslow effect at higher temperatures is suppressed.
- the electroviscous fluid according to the present invention comprises the dispersion of wet-method silica particles as specified hereinbefore in an electrically insulating fluid.
- the electrically insulating fluid itself is not particularly limited as long as it is a liquid at room temperature and is electrically insulating.
- Such electrically insulating fluids are exemplified by mineral oils, dibutyl sebacate, chlorinated paraffins, fluorine oils, and silicone oils. Among the preceding, silicone oils are preferred for their strong electrical insulation, low temperature-dependent viscosity variation, and so forth.
- the silicone oils are concretely exemplified by the fluid diorganopolysiloxanes with the following chemical structure: wherein each R denotes a monovalent hydrocarbon group as exemplified by alkyl groups such as methyl, ethyl, and propyl, and aryl groups such as phenyl and naphthyl. It is preferred that at least 30% of the R groups are methyl groups. Moreover, while the degree of polymerization n is not particularly limited, it preferable that n does not exceed 1,000 in order to achieve a practical viscosity range. Values not exceeding 100 are even more preferred. Silicone oils with this structure are available in the form of a large number of commercial products, for example, SH200 from Toray Dow Corning Silicone Company, Limited.
- fluoroalkyl- containing diorganopolysiloxanes are particularly preferred because they enhance the Winslow effect and inhibit the particle sedimentation caused by specific gravity differences.
- R is defined as above, R 2 is a fluoroalkyl group having 10 or fewer carbons, and m and p are integers with values not exceeding 1,000.
- the structure of the aforementioned C ⁇ 10 fluoroalkyl group is not particularly specified, but the 3,3,3-trifluoropropyl group is preferred from the standpoint of ease of synthesis.
- each molecule In order to obtain a substantial enhancement of the Winslow effect, it will be preferable for each molecule to contain at least 30 mole% fluoroalkyl group.
- the degree of polymerization m is again not particularly limited, it preferably does not exceed 1,000 in order to achieve a practical viscosity range. Values not exceeding 100 are even more preferred.
- the mechanism by which the fluoroalkyl group enhances the Winslow effect is not clear.
- fluoroalkyl-containing diorganopolysiloxanes are commercially available, for example, as FS1265 from Toray Dow Corning Silicone Company, Limited.
- the electroviscous fluid according to the present invention comprises the dispersion of wet-method silica particles as described hereinbefore in an electrically insulating fluid as described hereinbefore.
- the quantity dispersed should fall within the range of 0.1 to 50 wt% and preferably is in the range of 10 to 40 wt%. A satisfactory thickening effect is not obtained at less than 0.1 wt%. At values exceeding 50 wt%, the viscosity of the system is so substantially increased as to be impractical.
- the electroviscous fluid according to the present invention as described hereinabove is useful as the working oil or functional oil in particular types of machinery, for example, machinery which will be employed in the vicinity of room temperature and where there will be little abrading motion.
- cs centistokes and the viscosity is the value at 25 °C.
- D shear rate
- the torque applied to the rotor was measured with a torque sensor, and this was converted into the shear stress (S) and the D-versus-S curve was drawn on an X-Y recorder.
- the rotor was electrically grounded and D-versus-S curves were also recorded while applying a direct-current voltage to the cup.
- the intersection of the extrapolation of the linear segment with the S-axis was designated as the yield value at the particular field strength.
- the thermal and shear stress stability and the sedimentability of the wet-method silica particles were also examined.
- the electroviscosity test was also set up in such a manner that the cell temperature could be varied.
- Electroviscous fluid in the form of the suspension prepared in Example 1 was heated for 1 week at 90 ° C in an open system under air, then removed and cooled. After this heat treatment, the electroviscous behavior of the resulting electroviscous fluid was measured at a cell temperature of 25 ° C, and these results are reported in Table I.
- Example 1 An electroviscous fluid was prepared as in Example 1, but in this case using n-caprylonitrile in place of the acetonitrile used in Example 1. The electroviscous behavior of this electroviscous fluid was measured at a cell temperature of 25 ° C, and these results are reported in Table I below.
- Example 1 An electroviscous fluid in the form of a suspension was prepared as in Example 1, but in this case using the wet- method silica prior to its acetonitrile treatment in place of the acetonitrile-treated wet-method silica employed in Example 1. Its electroviscous behavior was measured, and these results are reported in Table I below.
- Electroviscous fluid as prepared in Comparison Example 1 was heated for 1 week at 90 ° C in an open system under air, then removed and cooled.
- the electroviscous behavior of the obtained electroviscous fluid was measured at a cell temperature of 25 ° C, and these results are reported in Table I below.
- the electroviscous fluid according to the present invention which comprises a dispersion, in an electrically insulating fluid, of 0.1 to 50 weight% wet-method silica whose surface adsorbed water has been replaced by a nitrile group-containing organic compound, is characterized by a substantial increase in yield value at low voltages and excellent shear stability.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Combined Devices Of Dampers And Springs (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29225590A JPH04164997A (ja) | 1990-10-26 | 1990-10-26 | 電気粘性液体 |
| JP292255/90 | 1990-10-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0482664A1 true EP0482664A1 (fr) | 1992-04-29 |
Family
ID=17779438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91118247A Withdrawn EP0482664A1 (fr) | 1990-10-26 | 1991-10-25 | Fluide éléctrovisqueux |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0482664A1 (fr) |
| JP (1) | JPH04164997A (fr) |
| CA (1) | CA2054216A1 (fr) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0374525A1 (fr) * | 1988-12-17 | 1990-06-27 | Bridgestone Corporation | Fluide électrovisqueux |
-
1990
- 1990-10-26 JP JP29225590A patent/JPH04164997A/ja active Pending
-
1991
- 1991-10-25 CA CA 2054216 patent/CA2054216A1/fr not_active Abandoned
- 1991-10-25 EP EP91118247A patent/EP0482664A1/fr not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0374525A1 (fr) * | 1988-12-17 | 1990-06-27 | Bridgestone Corporation | Fluide électrovisqueux |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2054216A1 (fr) | 1992-04-27 |
| JPH04164997A (ja) | 1992-06-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE DE FR GB |
|
| 17P | Request for examination filed |
Effective date: 19920630 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
| 18W | Application withdrawn |
Withdrawal date: 19921023 |