EP0372366A1 - Elektroviskose Flüssigkeit - Google Patents

Elektroviskose Flüssigkeit Download PDF

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Publication number
EP0372366A1
EP0372366A1 EP89122000A EP89122000A EP0372366A1 EP 0372366 A1 EP0372366 A1 EP 0372366A1 EP 89122000 A EP89122000 A EP 89122000A EP 89122000 A EP89122000 A EP 89122000A EP 0372366 A1 EP0372366 A1 EP 0372366A1
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EP
European Patent Office
Prior art keywords
weight
electroviscous fluid
electroviscous
fluid according
fluid
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.)
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Application number
EP89122000A
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English (en)
French (fr)
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EP0372366B1 (de
Inventor
Yoshiki Fukuyama
Yuichi Ishino
Toshiyuki Osaki
Takayuki Maruyama
Tasuku Saito
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bridgestone Corp
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Bridgestone Corp
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Publication of EP0372366A1 publication Critical patent/EP0372366A1/de
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    • 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
    • C10M2229/051—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing halogen
    • C10M2229/0515—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing halogen 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
    • C10M2229/052—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing nitrogen
    • C10M2229/0525—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing nitrogen 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
    • C10M2229/053—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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • 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

Definitions

  • the present invention relates to an electroviscous fluid which increases its viscosity when an electric potential difference is applied thereto.
  • the electroviscous fluid is a suspension composed of a finely divided hydrophilic solid dispersed in an electrically nonconductive oil.
  • the viscosity of the fluid increases swiftly and reversibly under influence of an electric field applied thereto and the fluid turns to a state of plastic or solid when the influence of the electric field is sufficiently strong.
  • the electric field to be applied for changing the viscosity of the fluid can be not only that of a direct current but also that of an alternating current, and the electric power requirement is very small to make it possible to give a wide range of viscosity variation from liquid state to almost solid state with a small consumption of electric power.
  • the electroviscous fluid has been studied with an expectation that it can be a system component to control such apparatus or parts as a crutch, a hydraulic valve, a shock absorber, a vibrator, a vibration-isolating rubber, an actuator, a robot arm, a damper, for example.
  • USP 3,047,507 proposed various kinds of materials as the dispersed phase of an electroviscous fluid, and silica gel was mentioned as a preferable material among them.
  • silica gel was mentioned as a preferable material among them.
  • an electrically nonconductive oil such as silicone oil was used.
  • the electroviscous fluid using silica gel as the dispersed phase showed small electroviscous effect which is unsatisfactory for practical usages.
  • Japanese Patent Provisional Publication Tokkaisho 53-93186 proposed lithium polyacrylate particles as the dispersed phase.
  • the electroviscous fluid using lithium polyacrylate particles as the dispersed phase has a disadvantage of large electric power consumption, because the lithium polyacrylate dispersed phase requires to contain a large amount of water to exhibit the electroviscous effect and the water induces an excessive electric conductivity.
  • Japanese Patent Provisional Publication Tokkaisho 62-95397 proposed electroviscous fluids using alumino-silicates having Al/Si atomic ratio of 0.15-0.80 at the surface and water content of 1-25% by weight as the dispersed phase, and mentioned electroviscous fluids using various kinds of crystalline zeolite as the dispersed phase in its examples.
  • crystalline zeolites are expressed with following general formula: M (x/n) [(AlO2) x (SiO2) y ] ⁇ wH2O, wherein, M is a hydrogen ion, a metallic cation or a mixture of metallic cations having an average electron value n; x and y are integers; w is a mole number of crystallization water.
  • Al content of a crystalline zeolite as a whole particle is larger than Al content at the surface of it.
  • Al content of the crystalline zeolite as a whole particle is larger than Al content at the surface of it.
  • the Al/Si atomic ratio of 0.15-0.80 (which is equivalent to Si/Al atomic ratio of 1.25-­6.67) at the surface is thought to correspond Si/Al atomic ratio of from about 1 to about 6.7 as a whole particle.
  • the crystalline zeolite of such composition is hydrophilic and contains much water in its crystal. Accordingly, an electroviscous fluid using such crystalline zeolite as the dispersed phase shows an excessive electric conductivity to have a disadvantage of much electric power consumption.
  • USP 4,744,914 proposed an electroviscous fluid using crystalline zeolite having the following general formula and containing substantially no adsorbed water as the dispersed phase; M (x/n) [(AlO2) x (SiO2) y ] ⁇ wH2O, wherein, M is a hydrogen ion, a metallic cation or a mixture of metallic cations having an average electron value n; x and y are integers; y/x of from about 1 to about 5; w is an indefinite number.
  • USP 4,744,914 proposed a treatment wherein the electric insulating oil and the crystalline zeolite particles were treated under a temperature higher than temperatures expected to be employed at the usage of the electroviscous fluid for enough time required to attain necessary degree of degassing and elimination of water.
  • the characteristics of the electroviscous fluid disclosed in USP 4,744,914 is that, by using crystalline zeolite particles containing substantially no adsorbed water as the dispersed phase, the electroviscous fluid shows a reversible increase of viscosity under a high electrical potential difference without discharging undesirable water even at temperatures higher than 100°C.
  • the surface of the zeolite becomes very active and tends to cause secondary coagulation.
  • Mechanism of the electroviscous effect is that the application of an electric potential difference to the electroviscous fluid induces formation of bridges among the particles dispersed therein due to polarization and elevation of viscosity of the fluid.
  • the object of the present invention is to provide an electroviscous fluid which requires no drying step at preparation and shows a quick responses at the application and cancellation of an electric potential difference and can exhibit a greater electroviscous effect with less electric power consumption.
  • the electroviscous fluid of the present invention comprises;
  • the crystalline zeolite having the above-mentioned general formula and Si/Al atomic ratio (y/x) of 10-200, preferably of 30-­120 is hydrophobic and contains 0.05-10% by weight of water, especially 1-5% by weight of water at the preferable atomic ratio without any treatment. It shows a large electroviscous effect with less electric conductivity without drying. Accordingly the problem of secondary coagulation can be avoided.
  • Si/Al atomic ratio (y/x) When the Si/Al atomic ratio (y/x) is smaller than 10, electric conductivity due to water becomes larger and the drying step is required. When the Si/Al atomic ratio (y/x) is larger than 200, the electroviscous effect becomes smaller due to insufficient water content.
  • ZSM-5 type zeolite As an example of the crystalline zeolite having the Si/Al atomic ratio (y/x) of 10-200, ZSM-5 type zeolite is well known.
  • the particle size and shape of the crystalline zeolite to be used in the present invention can be easily controlled by adopting an appropriate manufacturing method to improve the sedimenting property of the particles which is an important property in an electroviscous fluid.
  • the particle size of the crystalline zeolite suitable for the dispersed phase of the electroviscous fluid is in the range of 0.01-20 micrometer, preferably in the range of 0.3-5 micrometer.
  • the size is smaller than 0.01 micrometer, initial viscosity of the fluid under no application of electric field becomes extremely large and the change in viscosity due to the electroviscous effect is small.
  • the size is over 20 micrometer, the dispersed phase can not be held sufficiently stable in the liquid.
  • hydrocarbon oils As the electric insulating oil to constitute the liquid phase of an electroviscous fluid, hydrocarbon oils, ester oils, aromatic oils, halogenated hydrocarbon oils such as perfluoropolyether and polytrifluoromonochloroethylene, phosphazene oils and silicone oils are mentioned. They may be used alone or in a combination of more than two kinds. Among these oils, such silicone oils as polydimethylsiloxane, polymethylphenylsiloxane and polymethyltrifluropropylsiloxane are preferred, since they can be used in direct contact with materials such as rubber and various kinds of polymers.
  • the desirable viscosity of the electric insulating oil is in the range of 0.65-500 centistokes (cSt), preferably in the range of 5-200 cSt, and more preferably in the range of 10-50 cSt at 25°C.
  • cSt centistokes
  • stability of the liquid phase becomes inferior due to an increased content of volatile components, and a too high viscosity of the oil brings about an heightened initial viscosity under no application of electric field to result in a decreased changing range of viscosity by the electroviscous effect.
  • an electric insulating oil having an appropriate low viscosity is employed as the liquid phase, the liquid phase can suspend a dispersed phase efficiently.
  • the content of the dispersed phase composed of the aforementioned crystalline zeolite particles is 1-60% by weight, preferably 20-50% by weight, and the content of the liquid phase composed of the aforementioned electrical insulating oils is 99-40% by weight, preferably 80-50% by weight.
  • the dispersed phase is less than 1% by weight, the electroviscous effect is too small, and when the content is over 60% by weight an extremely large initial viscosity under no application of electric field appears.
  • H-ZSM-5 type crystalline zeolite particles manufactured by Catalysts & Chemicals Industries Co.
  • a liquid phase component being 60 parts by weight of a silicone oil (Toshiba-Silicone Co.: TSF 451-20 ®) having 20 cSt viscosity at 25°C to prepare an electroviscous fluid in a suspension form.
  • H-ZSM-5 type crystalline zeolite particles manufactured by Catalysts & Chemicals Industries Co.
  • a liquid phase component being 60 parts by weight of a silicone oil (Toshiba-Silicone Co.: TSF 451-20 ®) having 20 cSt viscosity at 25°C to prepare an electroviscous fluid in a suspension form.
  • H-ZSM-5 type crystalline zeolite particles manufactured by Catalysts & Chemicals Industries Co.
  • a liquid phase component being 60 parts by weight of a silicone oil (Toshiba-Silicone Co.: TSF 451-20 ®) having 20 cSt viscosity at 25°C to prepare an electroviscous fluid in a suspension form.
  • a silica-gel (Nippon Silica Co.: NIPSIL VN-3 ®) was treated to make the water content to 6% by weight, and 13 parts by weight thereof were dispersed in a liquid phase component being 87 parts by weight of a silicone oil (Toshiba-Silicone Co.: TSF 451-20 ®) having 20 cSt viscosity at 25°C to prepare an electroviscous fluid in a suspension form.
  • a silicone oil Toshiba-Silicone Co.: TSF 451-20 ®
  • Na-Y type crystalline zeolite particles manufactured by Catalysts & Chemicals Industries Co.
  • a liquid phase component being 70 parts by weight of a silicone oil (Toshiba-Silicone Co.: TSF 451-20 ®) having 20 cSt viscosity at 25°C to prepare an electroviscous fluid in a suspension form.
  • T is the shearing force under application of electric potential difference of 2 KV/mm
  • T-To is the difference of T
  • To and the current density is the value under application of electric potential difference of 2KV/mm.
  • T-To indicates the magnitude of electroviscous effect of the fluid. That is, a fluid showing a larger T-To in Table 1 exhibits a larger electroviscous effect. And the value of the current density ( ⁇ A/cm2) concerns an electric power required to apply the electric potential difference (2KV/mm).
  • the electroviscous fluids of Examples 1-3 showed large electroviscous effects with little electric power consumptions.
  • the electroviscous fluids of Comparative Example 1 using silica gel as the dispersed phase showed an inferior electroviscous effect though the electric power consumption was small.
  • the electroviscous fluids of Comparative Example 2 and 3 using high water content crystalline zeolite as the dispersed phase showed enormous electric power consumption.
  • the electroviscous fluids of Example 4 which used the same crystalline zeolite particles as the dispersed phase after drying, showed a large electroviscous effect with less electric power consumption.
  • the electroviscous fluid of Comparative Example 4 showed unstable behavior at the application of the electric potential difference E (2 KV/mm) and delayed response at the cancellation of the electric potential difference. The reason of this phenomenon is supposed to be caused by secondary coagulation of zeolite particles.
  • the electroviscous fluid of Example 1 showed a rapid and sharp response at the application and cancellation of electric potential difference (2 KV/mm).
  • E in abscissa shows the period of the application of electric field 2 KV/mm at 25°C and ordinate shows the shearing force observed.
EP89122000A 1988-12-01 1989-11-29 Elektroviskose Flüssigkeit Expired - Lifetime EP0372366B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP63302227A JPH02150494A (ja) 1988-12-01 1988-12-01 電気粘性液体
JP302227/88 1988-12-01

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EP0372366A1 true EP0372366A1 (de) 1990-06-13
EP0372366B1 EP0372366B1 (de) 1992-09-02

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0424840A1 (de) * 1989-10-25 1991-05-02 Bridgestone Corporation Elektrorheologische Flüssigkeit
EP0374525B1 (de) * 1988-12-17 1993-11-18 Bridgestone Corporation Elektroviskose Flüssigkeit
EP0589637A1 (de) * 1992-09-21 1994-03-30 Dow Corning Corporation Organosiloxane enthaltende verbesserte elektrorheologische Flüssigkeitzubereitungen
GB2562309A (en) * 2017-05-12 2018-11-14 Univ Belfast Porous liquids

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3047507A (en) * 1960-04-04 1962-07-31 Wefco Inc Field responsive force transmitting compositions
EP0170939A1 (de) * 1984-07-26 1986-02-12 Bayer Ag Elektroviskose Flüssigkeiten
FR2612910A1 (fr) * 1987-03-31 1988-09-30 Mizusawa Industrial Chem Procede de preparation de particules siliceuses, analcime active et silice amorphe obtenues par ce procede, et charges et fluide electrovisqueux qui en contiennent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3047507A (en) * 1960-04-04 1962-07-31 Wefco Inc Field responsive force transmitting compositions
EP0170939A1 (de) * 1984-07-26 1986-02-12 Bayer Ag Elektroviskose Flüssigkeiten
FR2612910A1 (fr) * 1987-03-31 1988-09-30 Mizusawa Industrial Chem Procede de preparation de particules siliceuses, analcime active et silice amorphe obtenues par ce procede, et charges et fluide electrovisqueux qui en contiennent

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0374525B1 (de) * 1988-12-17 1993-11-18 Bridgestone Corporation Elektroviskose Flüssigkeit
EP0424840A1 (de) * 1989-10-25 1991-05-02 Bridgestone Corporation Elektrorheologische Flüssigkeit
US5130042A (en) * 1989-10-25 1992-07-14 Bridgestone Corporation Electrorheological fluids comprising carbonaceous particulates dispersed in electrical insulating oily medium having P═N bonds in the molecule
EP0589637A1 (de) * 1992-09-21 1994-03-30 Dow Corning Corporation Organosiloxane enthaltende verbesserte elektrorheologische Flüssigkeitzubereitungen
US5480573A (en) * 1992-09-21 1996-01-02 Dow Corning Corporation Electrorheological fluid compositions containing alkylmethylsiloxanes
GB2562309A (en) * 2017-05-12 2018-11-14 Univ Belfast Porous liquids
US11565212B2 (en) 2017-05-12 2023-01-31 The Queen's University Of Belfast Porous liquids
US11571656B2 (en) 2017-05-12 2023-02-07 The Queen's University Of Belfast Type 3 porous liquids
EP4134151A1 (de) * 2017-05-12 2023-02-15 The Queen's University of Belfast Poröse flüssigkeiten

Also Published As

Publication number Publication date
DE68902734T2 (de) 1993-01-14
DE68902734D1 (de) 1992-10-08
EP0372366B1 (de) 1992-09-02
JPH02150494A (ja) 1990-06-08

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