WO1986004542A1 - Organes de retenue thermodeformables pour vehicules automobiles - Google Patents

Organes de retenue thermodeformables pour vehicules automobiles Download PDF

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Publication number
WO1986004542A1
WO1986004542A1 PCT/GB1986/000066 GB8600066W WO8604542A1 WO 1986004542 A1 WO1986004542 A1 WO 1986004542A1 GB 8600066 W GB8600066 W GB 8600066W WO 8604542 A1 WO8604542 A1 WO 8604542A1
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WO
WIPO (PCT)
Prior art keywords
article
polymer
recovery
temperature
stress
Prior art date
Application number
PCT/GB1986/000066
Other languages
English (en)
Inventor
Edward Matthew Ramsey
Ceinwen Delia Rowlands
Brian Edward Schott
Dennis Carl Siden
Original Assignee
Raychem Corporation
Raychem Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Raychem Corporation, Raychem Limited filed Critical Raychem Corporation
Publication of WO1986004542A1 publication Critical patent/WO1986004542A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
    • B29C61/003—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor characterised by the choice of material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
    • F16B4/00—Shrinkage connections, e.g. assembled with the parts at different temperature; Force fits; Non-releasable friction-grip fastenings
    • F16B4/006—Shrinkage connections, e.g. assembled with the parts being at different temperature
    • F16B4/008—Shrinkage connections, e.g. assembled with the parts being at different temperature using heat-recoverable, i.e. shrinkable, sleeves
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L33/00—Arrangements for connecting hoses to rigid members; Rigid hose connectors, i.e. single members engaging both hoses
    • F16L33/02—Hose-clips
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2071/00—Use of polyethers, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/727—Fastening elements
    • B29L2031/7278—Couplings, connectors, nipples

Definitions

  • This invention relates to automotive retaining members capable of replacing known metal "Jubilee” hose clips and the like with considerable advantages in terms of weight and installation costs.
  • the "Jubilee”-type retaining members have hitherto been regarded as virtually unparalleled in their ability to withstand the stresses of automotive service, especially in the high temperatures of the engine enclosures of vehicles.
  • the invention provides an automotive retaining member comprising a dimensionally heat recoverable semi-crystalline material having a glass transition temperature, Tg, above about 25°C, said member having a recovery stress of above about 1100 ⁇ (E-1) 0.5 pounds per square inch, wherein E is the unresolved recovery ratio.
  • the invention thus provides, contrary to expectation, polymeric retaining members, preferably in the form of rings, and preferably comprising polyester or polyamide material, which have surprisingly high resistance to the conditions encountered in automotive service, even in the relatively higher temprature environments in and around the engine enclosure of a vehicle.
  • the retaining members of this invention may thus replace metal clips (or clamps) for holding resi liently deformable articles, especially hoses or other hollow tubular articles, in contact with substantially non-resilient substrates, part of which, for example, may be gripped by an aperture of the hose or other resilient article. Fibers of the polymeric material may be used instead of continuous polymer to form the retaining member, if desired.
  • a dimensionally heat recoverable article is an article the dimensional configuration of which may be made substantially to change when subjected to heat treatment. Usually these articles recover towards an original shape from which they have previously been deformed but the term "heat-recoverable”, as used herein, also includes an article which, on heating, adopts a new configuration, even if it has not been previously deformed.
  • such articles comprise a heat-shrinkable sleeve made from a polymeric material exhibiting the property of elastic or plastic memory as described, for example, in U.S. Patents 2,027,962; 3,086,242 and 3,597,372.
  • the original dimensionally heat-stable form may be a transient form in a continuous process in which, for example, an extruded tube is expanded, whilst hot, to a dimensionally heat-unstable form but, in other applications, a preformed dimensionally heat-stable article is deformed to a dimensionally heat-unstable form in a separate stage.
  • such articles are prepared from po lymers that are capable of being cross-linked, for example, polyethylene, polybutene-1, poly 4-methyl pentene and fluorinated polyolefins for example, ethylene-trifluorochloroethylene copolymers, ethylenetetrafluoroethylene copolymers, and vinylidene fluoride polymers, especially polyvinylidene fluoride, and blends thereof, for example, the fluorinated olefin blends as described and claimed in British Patent No. 1,120,131, and the like.
  • the polymer material may be cross-linked at any stage in the production of the article that will enhance the desired dimensional recoverability.
  • One manner of producing a heat-recoverable article comprises shaping the polymeric material into the desired heat-stable form, subsequently cross-linking the polymeric material, heating the article to a temperature above the crystalline melting point or, for amorphous materials the softening point, as the case may be, of the polymer, deforming the article and cooling the article whilst in the deformed state so that the deformed state of the article is heat-unstable, whereafter application of heat will cause the article to assume its original heat-stable shape.
  • Heat recoverable articles from cross-linkable crystalline polymers can be prepared by deforming the uncrosslinked polymer below the crystalline melting point and without cross-linking, cooling the deformed article. Subsequent heating of the article to the deformation temperature causes the article to recover toward the undeformed configuration but it does so with a relatively low recovery stress. As a result such recoverable articles are generally unsuitable for use as mechanical devices, such as couplings, where a high recovery stress is required. Further, the use of such devices requires not only a high recovery stress but that the high stress be maintained after the device has been recovered against the substrate and subsequently cooled to ambient temperature. Heat recoverable devices disclosed in the art do not meet this requirement.
  • dimensionally heat-recoverable retaining members of semi-crystalline polymers having a glass transition temperature above about 25oC, preferably above 120°C exhibit exceptionally high recovery stress under certain conditions, which recovery stress is subsequently retained and in some instances increased, and the members can withstand conditions encountered in automotive use, as aforementioned.
  • Another aspect of this invention comprises a method of producing the dimensionally heat-recoverable automotive retaining members comprising
  • FIG. 1 is a graph of the peak values of unresolved recovery stress divided by the expansion stress vs. the difference between the recovery and expansion temperatures for 4 materials useful for preparing articles of the invention and for one material (lowest curve) incapable of providing articles of the present invention;
  • FIG. 2 is a graph of the unresolved recovery stress after 1 minute at the recovery temperature divided by the expansion stress vs. the difference between the recovery and expansion temperatures for 4 materials useful for preparing articles of the invention and for one material (lowest curve) incapable of providing articles of the present invention
  • FIG. 3 is a graph of the unresolved recovery stress vs. the unresolved recovery ratio for 4 materials useful for preparing articles of the present invention and for 2 materials (lowest 2 curves) incapable of providing articles of the present invention.
  • FIG. 4 is a graph of the unresolved recovery stress vs. percentage recovery for 4 materials useful for preparing articles of the present invention and for 1 material (PE) incapable of providing articles of the present invention.
  • the heat-recoverable articles of this invention are prepared using a semi-crystalline polymer having a glass transition temperature, Tg, above about 25°C.
  • Tg glass transition temperature
  • the polymer used to make the article has a Tg above about 100 °C , more preferably above 120 °C , and most preferably above about 150°C.
  • the polymer used should be a polymer having crystalline melting temperature of above about 150°C, preferably above about 180°C and most preferably above about 290oC.
  • Such polymers include for example, polyamides, such as polycaprolactam, nylon 6, and poly(ll-iminoundecanoyl), nylon 11, crystalline polyesters, such as crystalline polyethylene terephthalate, polybutylene terephthalate and the like, other crystalline or crystallizable aromatic polymers, such as polyphenylene sulfide and polyaryl ethers, in particular polyaryl ether ketones. Blends of these polymers with each other and/or with other polymers can also be utilized. Semi-crystalline polyaryl ether ketones are particular ly preferred polymers for the preparation of heat recoverable articles of this invention. Such polymers typically have a glass transition temperature in the range of between about 140°C to about 250°C and a crystalline melting temperature between about 270°C and 450°C.
  • Polyaryl ether ketones comprise repeat units of the formula:
  • E and E 1 are aromatic radicals at least one of which is a polynuclear aromatic moiety having two aromatic nuclei joined by a ketone group, the other of E and E 1 is an aromatic moiety containing at least one aromatic ring.
  • the polymer can contain other polynuclear moieties joined by other functional groups such as sulfone, sulfide, alkylene, etc.
  • Poly(aryl ether ketones) suitable for use in this invention have the repeat units of the formula:
  • Ar and Ar' are aromatic moieties at least one of which contains a diaryl ether linkage forming part of the polymer backbone and wherein both Ar and Ar' are covalently linked to the carbonyl groups through aromatic carbon atoms.
  • Ar and Ar' are independently selected from substituted and unsubstituted phenylene and substituted and unsubstituted polynuclear aromatic moieties.
  • polynuclear aromatic moieties is used to mean aromatic moieties containing at least two aromatic rings. The rings can be fused, joined by a direct bond or by a linking group.
  • linking groups include for example, carbonyl, ether sulfone, sulfide, amide, imide, azo, alkylene, perfluoroalkylene and the like.
  • Ar and Ar' contains a diaryl ether linkage.
  • the phenylene and polynuclear aromatic moieties can contain substituents on the aromatic rings. These substituents should not inhibit or otherwise interfere with the polymerization reaction to any significant extent.
  • substitutents include, for example, phenyl, halogen, nitro, cyano, alkyl, 2-alkynyl and the like.
  • Poly(aryl ether ketones) having the following repeat units are preferred:
  • Poly(aryl ether ketones) can be prepared by known methods of synthesis.
  • Preferred poly(aryl ether ketones) can be prepared by Friedel-Crafts polymerization of a monomer system comprising:
  • each Ar" is independently selected from substituted or unsubstituted phenylene, and substituted or unsubstituted polynuclear aromatic moieties free of ketone carbonyl or ether oxygen groups, in the presence of a reaction medium comprising:
  • a Lewis acid in an amount of one equivalent per equivalent of carbonyl groups present, plus one equivalent per equivalent of Lewis base, plus an amount effective to act as a catalyst for the polymerization;
  • the aromatic diacid dihalide employed is preferably a dichloride or dibromide.
  • Illustrative diacid dihalides which can be used include, for example
  • Illustrated polynuclear aromatic comonomers which can be used with such diacid dihalides are:
  • Monomer systems II and III comprise an acid halide.
  • acid halide is used herein to refer to a monoacid monohalide.
  • monomer system II the acid halide is of the formula:
  • the acid halide is of the formula
  • monomers can be employed.
  • one or more diacid dihalides can be used with one or more polynuclear aromatic comonomers as long as the correct stoichiometry is maintained.
  • one or more acid halides can be included.
  • monomers which contain other linkages such as those specified above, can be employed as long as one or more of the comonomers used contains at least one ether oxygen linkage.
  • Such comonomers include for example: which can be used as the sole comonomer with an ether containing diacid dihalide or with phosgene or any diacid dihalide when used in addition to a polynuclear aromatic comonomer as defined in I(ii)(a), I(ii)(b), I(ii)(c) or I(ii)(d). Similarly,
  • the monomer system can also contain up to about 30 mole % of a comonomer such as a su lfony l chloride which polymerizes under Friedel-Crafts conditions to provide ketone/sulfone copolymers.
  • a comonomer such as a su lfony l chloride which polymerizes under Friedel-Crafts conditions to provide ketone/sulfone copolymers.
  • semi-crystalline aromatic polymers or polymers which can be rendered semi-crystalline include polyphenylene sulfide, polyphenylene ethers, and the like. Blends of these polymers with each other and with other polymers can be used.
  • the polymer used in making the heat recoverable articles of this invention is semi-crystalline polymers or polymers capable of being rendered crystalline, that is are crystallizable.
  • the polymer should have a crystallinity of above about 5%.
  • the degree of crystallinity varies depending on the particular polymer. It is generally desirable that the crystallinity of the polymer used is at a maximum. However, high recovery stresses can be obtained using semi-crystalline polymers with lower crystallinity.
  • the polymer can be treated, for example by annealing, solvent swelling or the like to increase the crystallinity.
  • the dimensionally heat-recoverable articles of this invention are produced by deforming the polymeric material at a temperature above the glass transition temperature of the polymer but below the melting temperature of the polymer.
  • the glass transition temperature is meant the temperature which is the approximate midpoint of the temperature range over which a reversible change in the amorphous region of the polymer from (or to) a viscous or rubbery condition to (or from) a hard and relatively brittle one (see ASTM D883).
  • the crystalline melting temperature of the polymer is the temperature at which the last trace of crystallinity disappears as the temperature of the polymer is raised.
  • Tg and the crystalline melting temperature as Tm.
  • the dimensionally heat-recoverable article is preferably in the form of a ring (not necessarily round) of the polymeric material.
  • Such articles can be produced by conventional techniques such as injection molding, extruding, rotation molding and the like.
  • the article is then rendered dimensionally heat-recoverable by heating the article to a temperature T 1 between Tg and Tm of the polymer then deforming the article, for example, expanding it by passing it over a tapered mandrel or the like resulting in a heat shrinkable article, or compressing it by swaging or the like resulting in a heat expandable article.
  • T 1 between Tg and Tm of the polymer
  • the temperature at which the deformation step takes place is preferably about 5°C above Tg of the polymer.
  • the article is cooled, for example, to a temperature, T 2 , below the glass transition temperature of the polymer. Generally the article is cooled to ambient temperature.
  • Another method of producing the article is to take a film of the polymer, the film being produced by extrusion, casting, or the like.
  • the film is then heated to a temperature between Tg and Tm of the polymer and stretched. While maintained in the stretched configuration the film is cooled, generally to a temperature below the Tg of the polymer.
  • the film can then converted to the dimensionallyrecoverable ring or tubular article, for example, by wrapping it over a mandrel or by otherwise forming it and securing the ends.
  • the article is then removed.
  • the film can be wrapped around the substrate to be covered. On application of heat to a temperature above Tg but below Tm the article recovers with high recovery stress.
  • Another method of producing a heat-shrinkable article of this invention is to produce a heat-shrinkable fiber of a semi-crystalline aromatic polymer.
  • the fiber can be prepared by conventional spinning techniques, slit film processes and the like.
  • the fiber is heated to a temperature between Tg and Tm of the polymer and stretched by conventional fiber stretching techniques.
  • the fiber is cooled, for example to a temperature below Tg of the polymer.
  • the fiber or film or tape as described above
  • the fiber is in itself a heat-recoverable article within the scope of this invention.
  • the fiber can be wound around a mandrel and the ends thereof secured.
  • the resulting article is removed from the mandrel.
  • the film can be wrapped around the substrate to be covered.
  • the article will shrink with a high recovery stress.
  • Orientation of the polymer molecules in the hoop direction of the retaining member is preferable to maximise hoop strength during expansion and gripping force on recovery.
  • members made by wrapping and securing suitably oriented fibres or films may be advantageous.
  • this ratio is the ratio of the length after expansion or during recovery to the original length before expansion.
  • this ratio is approximately the ratio of the corresponding diameters.
  • this ratio is given by
  • x is the ratio of the internal diameter of the heat-recoverable article to the diameter (r i ) of the original article before being rendered heat-recoverable and r o is the external diameter of the heat recoverable article.
  • the high recovery stress is exhibited by articles of this invention when the article is constrained from complete recovery, that is, is prevented from recovering to its original dimensions.
  • the high recovery stress is exhibited when the article is recovered less than 25%, based on the dimension of the deformed article.
  • the article is prevented by the substrate against which it is recovered from recovery of more than about 20% and particularly more than about 15%, based on the dimension of the deformed article.
  • the articles of this invention are typically used by recovering the article against a substrate.
  • the article for example can be used to grip a hose around a pipe over which the end of the hose is fitted. It can also be used to grip a flexible, preferably corrugated, protective housing around moving parts such as steering gear to be protected from dust and/or to retain lubricants.
  • Poly(oxy-p-phenylenecarbonyl-p-phenylene) (Stilan), poly(oxy-p-phenyleneoxy-p-phenylenecarbonyl-p-phenylene) (PEEK), polyethylene terephthalate (PET), poly(lliminoundecanoyl) (nylon 11) and polyethylene (PE) were extruded as tape of about the same thickness (0.03 in.), width (1.5 in.) and melt draw ratio under the conditions described in Table 1. Tapes of the first four polymers, which have glass transition temperatures above 25 °C, were cut into 5 in. ⁇ 1/4 in.
  • polyethylene terephthalate amorphous tape extruded as described in example 1 was stretched at 100°C this being the maximum temperature that we found could be used without crystallization of the amorphous tape during the drawing.
  • the heat recoverable polyethylene terephthalate when tested as desribed in example 1 achieved a maximum recovery stress of 677 psi at 100 °C recovery temperature after having previously been expanded 555%.
  • a strip of crystalline Stilan was placed in the jaws of an Instron Tensile Tester and elongated at room temperature. We found that the strip necked non-uniformly and broke at a low elongation well before the strip had completely drawn.
  • Strips of crystalline tapes prepared and annealed as described in example 1 were expanded 100% at a temperature 50°C above the Tg of each polymer, cooled to room temperature and specimens cut from the expanded strips were heated to a temperature 50 °C above their Tg while clamped in the jaws of an Instron Tensile tester.
  • Table 3 shows the values of the recovery stress obtained after 1 minute of exposure to the hot oven.
  • Strips of crystalline tapes prepared and annealed as described in example 1 were expanded to various degrees at a temperature 100 °C above the Tg of each polymer and cooled to room temperature. Specimens cut from the expanded strips were then heated to the temperature of expansion while clamped in the jaws of an Instron Tensile tester.
  • Table 4 shows the peak recovery stresss generated within the first five minutes of exposure to the hot oven.
  • Figure 3 shows the peak recovery stress for these specimens plotted as a function of unresolved recovery. The lowest two curves in Figure 3 show the peak recovery stresses observed with materials incapable of use in the present invention (see Table 4, amorphous PET and PE).
  • Example 3 The expanded specimens of Example 3 were heated to Tg + 50 °C and allowed to shrink to varying degrees, the recovery stress being measured as a function of the degree of recovery. Table 5 shows the values obtained; the variation of shrinkage stress with percent recovery is plotted in figure 4.
  • the recoverable articles of the instant invention exhibit significant recovery stresss after shrinkages of as much as 16% based on the expanded dimensions.
  • Example 1 The expanded specimens of Example 1 were reheated to their expansion temperature while clamped in the jaws of an Instron Tensile tester then cooled to room temperature in the way described in Example 1, the percentage change in stress on cooling to room temperature being recorded.
  • Table 6 The results obtained are given in Table 6 and show that heat recoverable articles of the instant invention retain a substantial proportion of or even increase the force which they exert on any substrate they are recovered onto on cooling.
  • Tubular rings of engineering thermoplastics useful in this invention were injection molded using the conditions stated in Table 7, annealed as necessary to develop substantial crystallinity and preheated in an oven for ten minutes at Tg + 50 °C.
  • the preheated rings were removed from the oven and expanded over a mandrel (similarly preheated) as rapidly as possible and quenched in water, then removed from the mandrel.
  • the mandrel size was chosen so that each expanded ring had a diameter twice that of the unexpanded rings after removal from the mandrel.
  • the expanded rings were recovered over tinned copper braid placed on mandrels of varying size so that the braid extended beyond the end of each mandrel.
  • the braid used is typical of that used to electrically shield signal cables used in electronic equipment.
  • the temperature of recovery was the same as that used to expand each ring.
  • Each assembly was allowed to cool to room temperature.
  • the free end of the braid was clamped in one jaw of the Instron Tensile tester and the mandrel in the other. The jaws were separated at a rate of 0.2 in. per minute.
  • the peak force required to pull off the braid is given in table 8.
  • Table 8 also shows the force required to pull of a polyethylene (Marlex 6003) ring expanded at 85°C as taught by the prior art. Table 8 shows that considerably greater force was required to pull of the heat recoverable rings of the instant invention than that required to remove the rings made following a teaching of the prior art.
  • Annealed crystalline rings of Stilan were expanded onto a mandrel at room temperature. In every instance the rings expanded non-uniformly and broke at an elongation of about 30%.
  • Screw type 1 was a linear low density polyethylene screw.
  • Screw type 2 was a low density polyethylene screw.
  • Nylon 6 was in the form of injection-molded du ⁇ tells, ASTM D638 Type TV.
  • Table 7 TABLE 2 Recovery Stress Versus Recovery Temperature

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

Organes de retenue thermodéformables pour véhicules automobiles, préparés à partir de polymères semi-cristallins dont la température de transition de l'état vitreux, Tg, est située au-dessus de 25oC.De manière inattendue, ces organes présentent un effort de déformation élevé dans certaines conditions et peuvent supporter les sollicitations intervenant dans un véhicule automobile, ce qui permet de les utiliser, par exemple, comme conduites de retenue, etc., dans des enceintes de moteurs à haute température.
PCT/GB1986/000066 1985-02-07 1986-02-06 Organes de retenue thermodeformables pour vehicules automobiles WO1986004542A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US69910285A 1985-02-07 1985-02-07
US699,102 1985-02-07

Publications (1)

Publication Number Publication Date
WO1986004542A1 true WO1986004542A1 (fr) 1986-08-14

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PCT/GB1986/000066 WO1986004542A1 (fr) 1985-02-07 1986-02-06 Organes de retenue thermodeformables pour vehicules automobiles

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EP (1) EP0214173A1 (fr)
JP (1) JPS62501695A (fr)
WO (1) WO1986004542A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5145938A (en) * 1987-11-17 1992-09-08 Raychem Limited Preparation of poly(arylene ether ketones)
WO1993017272A1 (fr) * 1992-02-26 1993-09-02 The Gates Rubber Company Collier de serrage de tuyau et tubulure polymeres thermoretractable
US5531483A (en) * 1993-12-06 1996-07-02 The Gates Rubber Company Heat shrinkable hose clamp with heating indicator
WO1998015770A1 (fr) * 1996-10-10 1998-04-16 The Gates Corporation Dispositif de blocage auto-ajustable pour tube et tuyau en polymere au minimum bi-oriente
FR2925625A1 (fr) * 2007-12-21 2009-06-26 Cetim Cermat Ass Loi De 1901 Dispositif d'assemblage reversible

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2297342A1 (fr) * 1975-01-10 1976-08-06 Raychem Sa Nv Attaches douees de reprise thermique
EP0105775A1 (fr) * 1982-09-20 1984-04-18 Norsolor S.A. Produits finis à fonction mémoire
BE901683A (fr) * 1984-02-08 1985-05-29 Raychem Corp Produits manufactures polymeres thermoretractiles.
EP0152279A2 (fr) * 1984-02-08 1985-08-21 Raychem Limited Palier

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2297342A1 (fr) * 1975-01-10 1976-08-06 Raychem Sa Nv Attaches douees de reprise thermique
EP0105775A1 (fr) * 1982-09-20 1984-04-18 Norsolor S.A. Produits finis à fonction mémoire
BE901683A (fr) * 1984-02-08 1985-05-29 Raychem Corp Produits manufactures polymeres thermoretractiles.
EP0152279A2 (fr) * 1984-02-08 1985-08-21 Raychem Limited Palier

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5145938A (en) * 1987-11-17 1992-09-08 Raychem Limited Preparation of poly(arylene ether ketones)
WO1993017272A1 (fr) * 1992-02-26 1993-09-02 The Gates Rubber Company Collier de serrage de tuyau et tubulure polymeres thermoretractable
US5340167A (en) * 1992-02-26 1994-08-23 The Gates Rubber Company Heat shrinkable polymer hose and tubing clamp
US5531483A (en) * 1993-12-06 1996-07-02 The Gates Rubber Company Heat shrinkable hose clamp with heating indicator
WO1998015770A1 (fr) * 1996-10-10 1998-04-16 The Gates Corporation Dispositif de blocage auto-ajustable pour tube et tuyau en polymere au minimum bi-oriente
US6170885B1 (en) 1996-10-10 2001-01-09 The Gates Corporation Self-adjusting at-least-twice-oriented polymer hose and tubing clamp
CN1083961C (zh) * 1996-10-10 2002-05-01 盖茨公司 一种改进的软管夹、相关组件以及生产方法
FR2925625A1 (fr) * 2007-12-21 2009-06-26 Cetim Cermat Ass Loi De 1901 Dispositif d'assemblage reversible
WO2009081076A2 (fr) 2007-12-21 2009-07-02 Cetim-Cermat Dispositif d'assemblage reversible
WO2009081076A3 (fr) * 2007-12-21 2009-09-24 Cetim-Cermat Dispositif d'assemblage reversible

Also Published As

Publication number Publication date
EP0214173A1 (fr) 1987-03-18
JPS62501695A (ja) 1987-07-09

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