WO1992008917A1 - Improved gaskets - Google Patents

Improved gaskets Download PDF

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Publication number
WO1992008917A1
WO1992008917A1 PCT/GB1991/001997 GB9101997W WO9208917A1 WO 1992008917 A1 WO1992008917 A1 WO 1992008917A1 GB 9101997 W GB9101997 W GB 9101997W WO 9208917 A1 WO9208917 A1 WO 9208917A1
Authority
WO
WIPO (PCT)
Prior art keywords
gasket
filler
kaolin
gasket according
thermoplastic elastomer
Prior art date
Application number
PCT/GB1991/001997
Other languages
French (fr)
Inventor
Philip Ferdani
Original Assignee
T&N Technology 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 T&N Technology Limited filed Critical T&N Technology Limited
Publication of WO1992008917A1 publication Critical patent/WO1992008917A1/en

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Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16JPISTONS; CYLINDERS; SEALINGS
    • F16J15/00Sealings
    • F16J15/02Sealings between relatively-stationary surfaces
    • F16J15/06Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
    • F16J15/10Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing
    • F16J15/12Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing with metal reinforcement or covering
    • F16J15/121Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing with metal reinforcement or covering with metal reinforcement
    • F16J15/122Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing with metal reinforcement or covering with metal reinforcement generally parallel to the surfaces
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/10Materials in mouldable or extrudable form for sealing or packing joints or covers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02Inorganic compounds
    • C09K2200/0204Elements
    • C09K2200/0208Carbon
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02Inorganic compounds
    • C09K2200/0243Silica-rich compounds, e.g. silicates, cement, glass
    • C09K2200/0252Clays
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02Inorganic compounds
    • C09K2200/0243Silica-rich compounds, e.g. silicates, cement, glass
    • C09K2200/0252Clays
    • C09K2200/026Kaolin
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02Inorganic compounds
    • C09K2200/0243Silica-rich compounds, e.g. silicates, cement, glass
    • C09K2200/0265Mica
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0645Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
    • C09K2200/0655Polyesters

Definitions

  • This invention relates to gaskets at least partly comprised of non-metallic material.
  • Non-metallic gasket materials include fibre reinforced thermosett-ing mate-rials, typically fibrous compositions which employ rubber as a binder. More recently, it has been proposed to use thermoplastic elastomers as gasket materials, but although these materials have excellent properties, resistance to progressive permanent deformation under load (herein referred to as "creep") is not one of them. Creep resistance is an important characteristic for a gasket material .
  • a gasket is injection moulded from a fibre-free thermoplastic elastomer material including a filler in the form of plate-like particles the amount of said filler being ug to 30% by weight of the material.
  • Particularly preferred fillers include kaolin, graphite, mica and talc, although other minerals such as vermiculite may also be useful. Kaolin has proved especially useful in amounts of up to 30 percent by weight. Wherein kaolin is used, it is preferably calcined and surface modified by treatment with an aminosilane.
  • the use of plate-like fillers does not significantly detract from the elastomer flow properties, contrary to experience gained with fibre reinforced elastomers, so that the compositions can be injection moulded without a special mould design.
  • a kaolin content of 20 percent by weight has proved very satisfactory for injection moulding in circumstances where the same thermoplastic elastomer material was rendered virtually unmouldable by the addition of only 10 percent by weight of glass fibres.
  • the thermoplastic elastomer is preferably a polyester, polyester block copolymers being preferred.
  • a copolymer of polybutylene (polytetramethylene) terepthalate (PBT) with a polyester ether or a polyester glycol may be used, the "hard” segments of the PBT being complemented by the "soft" segments of the other component.
  • PBT itself is not an elastomer; the desired blend of hard and soft segments may be achieved by copolymerisation and/or by blending with a polyester elastomer which is itself a block copolymer of PBT.
  • a PBT content of at least about 70% by weight is preferred. It should be noted that blends of homopolymers are not generally desirable due to their tendency to undergo phase separation on injection moulding.
  • SUBSTITUTESHEET much more significant than tensile strength for a gasket.
  • the performance under injection moulding conditions is vastly superior to that of an equivalent fibre reinforced material for a given gasket configuration and moulding tool.
  • a further advantage of the invention resides in the discovery that the products tend to be very significantly less prone to warpage and distortion than fibre reinforced gaskets of the same material.
  • An automotive engine sump gasket was injection moulded from a thermoplastic elastomer constituted by a polyester block copolymer sold under the registered trade mark HYTREL.
  • the product was a flat gasket with good sealing properties, including heat resistance. However, it exhibited a tendency to creep, on prolonged exposure to normal clamping pressures in a test rig.
  • ASTM test F38 compares two grades of glass and kaolin filled HYTREL thermoplastic polyester elastomer when subjected to different tests, including the ASTM test designated F38.
  • the latter test determines the percentage of clamping load lost after 22 hours at 100°C, starting from an initial load of 60 kN. It will be appreciated that ASTM test F38 is in this instance really a measure of creep.
  • Gasket A was injection moulded from thermoplastic polyester block copolymer HYTREL grade 8238, with no filler.
  • Gasket B was injection moulded from HYTREL thermoplastic, polyester block copolymer grade 8238, as before, but this time containing 20% by weight of a finely divided calcined kaolin which had been treated with an aminosilane. Its leakage behaviour after 400 cycles was rated as good and the bolt load loss was 28%.
  • Gasket C was injection moulded from a pure polybutylene terepthalate (PBT) containing 10% by weight of the same kaolin as was used for gasket B.
  • PBT polybutylene terepthalate
  • the leakage performance at 400 cycles was again rated as good, but on inspection the gasket had cracked. Its bolt load loss was 36%.
  • the composition used for gasket B was also tested in several other engines, with similar results as regard leakage, no leakage being recorded in any case at 300 cycles and more. It is important to note with a gasket according to the present invention, satisfactory sealing was still achieved after 300-400 cycles, even in cases where a relatively high load loss was observed.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Injection moulded gaskets comprise a thermoplastic elastomer material containing a filler predominantly comprised of plate-like particles, the amount of filler being up to 30 % by weight of the material. The filler is preferably selected from the group comprising kaolin, graphite, mica and talc and the elastomer is preferably a polyester block copolymer predominantly comprised of polybutylene terephthalate.

Description

r
- 1 -
Improved gaskets
This invention relates to gaskets at least partly comprised of non-metallic material.
Known non-metallic gasket materials include fibre reinforced thermosett-ing mate-rials, typically fibrous compositions which employ rubber as a binder. More recently, it has been proposed to use thermoplastic elastomers as gasket materials, but although these materials have excellent properties, resistance to progressive permanent deformation under load (herein referred to as "creep") is not one of them. Creep resistance is an important characteristic for a gasket material .
Whilst the introduction of some fibrous material as a reinforcement does improve the resistance to creep, this improvement is only achieved at the expense of mouldabilit . The mouldability of fibre-free thermoplastic elastomer compositions is important, because it enables gasket manufacture by injection moulding, a process which makes optimum use of expensive materials by largely eliminating waste. But fibre reinforced materials have intrinsically higher melt viscosities which adversely affect their flow behaviour, for example in the passageways in moulding tools.
According to this invention, a gasket is injection moulded from a fibre-free thermoplastic elastomer material including a filler in the form of plate-like particles the amount of said filler being ug to 30% by weight of the material. Particularly preferred fillers include kaolin, graphite, mica and talc, although other minerals such as vermiculite may also be useful. Kaolin has proved especially useful in amounts of up to 30 percent by weight. Wherein kaolin is used, it is preferably calcined and surface modified by treatment with an aminosilane. The use of plate-like fillers does not significantly detract from the elastomer flow properties, contrary to experience gained with fibre reinforced elastomers, so that the compositions can be injection moulded without a special mould design. A kaolin content of 20 percent by weight has proved very satisfactory for injection moulding in circumstances where the same thermoplastic elastomer material was rendered virtually unmouldable by the addition of only 10 percent by weight of glass fibres.
The thermoplastic elastomer is preferably a polyester, polyester block copolymers being preferred. For example, a copolymer of polybutylene (polytetramethylene) terepthalate (PBT) with a polyester ether or a polyester glycol may be used, the "hard" segments of the PBT being complemented by the "soft" segments of the other component. It will be appreciated that PBT itself is not an elastomer; the desired blend of hard and soft segments may be achieved by copolymerisation and/or by blending with a polyester elastomer which is itself a block copolymer of PBT. However, for the present purposes a PBT content of at least about 70% by weight is preferred. It should be noted that blends of homopolymers are not generally desirable due to their tendency to undergo phase separation on injection moulding.
It has been found that whilst gaskets made according to the invention by injection moulding are in some ways inferior to fibre reinforced gaskets made from the same thermoplastic elastomer, they are at least equal when used as gaskets. Thus, although their tensile strength properties may well be inferior, their behaviour under compression is very similar to that of the fibre reinforced material. Behaviour under compressive loads is
SUBSTITUTESHEET much more significant than tensile strength for a gasket. However, the performance under injection moulding conditions is vastly superior to that of an equivalent fibre reinforced material for a given gasket configuration and moulding tool. A further advantage of the invention resides in the discovery that the products tend to be very significantly less prone to warpage and distortion than fibre reinforced gaskets of the same material.
In order that the invention be better understood, a preferred embodiment of it will now be described with the aid of the following Examples.
Comparative Example 1
An automotive engine sump gasket was injection moulded from a thermoplastic elastomer constituted by a polyester block copolymer sold under the registered trade mark HYTREL. The product was a flat gasket with good sealing properties, including heat resistance. However, it exhibited a tendency to creep, on prolonged exposure to normal clamping pressures in a test rig.
Comparative Example 2
An attempt was made to produce an identical gasket from the same elastomer material as that of comparative Example 1, but this time compounded to contain about 10 percent by weight . of short glass fibres. In order to satisfactorily injection mould this new composition, it was necessary to modify the tooling, to provide wider flow channels. Even so, it was not easy to produce a satisfactory moulding. The product had significantly better tensile strength than the unreinforced gasket and its resistance to creep was greatly improved. However, its processing by injection moulding was at best difficult and the finished product exhibited unacceptable warpage for use in practical gasket applications.
Example 3
Next an identical gasket was produced in accordance with the present invention by injection moulding -the same fibre-free elastomer material as was used in comparative Example 1 and to which had been added about 20 percent by weight of finely divided kaolin. The kaolin used was of a calcined and surface modified grade, the latter taking the form of an aminosilane surface treatment. Moulding performance was similar to that of unreinforced material', but the tensile strength was not as good as that of the glass fibre reinforced material. However, the behaviour under compression, including resistance to creep, was excellent, even after sustained exposure to clamping loads in a test rig. To further illustrate this, the following table compares two grades of glass and kaolin filled HYTREL thermoplastic polyester elastomer when subjected to different tests, including the ASTM test designated F38. The latter test determines the percentage of clamping load lost after 22 hours at 100°C, starting from an initial load of 60 kN. It will be appreciated that ASTM test F38 is in this instance really a measure of creep.
Tensile
Compres- Elong- F38
Tensile sive ation load
Modulus Modulus at loss
Grade Filler % wt (GPA) (GPA) break % %
8238 none - 0.5 0.97 400 52
8238 glass fibre 20% 1.41 2.24 6 27
8238 kaolin 20% 0.63 2.20 31 39
7246 none - 0.29 0.27 28 59
7246 glass fibre 20% 1.05 1.02 8 41
7246 kaolin 20% 0.46 0.83 33 40 1 -
It can be seen that whilst the tensile modulus of kaolin filled material was inferior to that of the glass fibre filled material, the compressive moduli were comparable. The F38 load loss test confirmed this. The behaviour under injection moulding was however very much better, clearly demonstrating the benefit of the invention. Elastomer containing as much as 20 percent by weight of glass fibres was in fact useless for moulding into the form of the test sump gasket mentioned earlier. The F38 test results reflect the fact that in real gaskets, some load loss is to be expected. However, the 52-59 percent determined for unreinforced elastomer was too great for commercial utility in the particular application under investigation.
The invention is further illustrated by the accompanying bar chart Figure 1 in which the effect on compressive modulus of various fillers is shown by comparison with that of an unreinforced thermoplastic elastomer sold under the trade mark HYTRE , grade 8238. It will be seen that kaolin was superior to other materials tested, although finely divided mica ("MICA 200") also performed well.
To further illustrate the behaviour of gaskets made in accordance with the invention, a series of tests were carried out on a range of engines from a given manufacturer. Each test took the form of running the engine with a sample sump gasket through a series of hot/cold cycles. The gasket was monitored for leakage and examined after testing to determine the loss of bolt loading developed.
Engine No 1 was tested with three different sump gaskets.
Gasket A was injection moulded from thermoplastic polyester block copolymer HYTREL grade 8238, with no filler.
Its leakage behavious after only 100 cycles was rated as good, but a bolt load loss of 47% was observed. A test on a different engine showed oil leakage at 400 cycles, with a load loss of 33%.
Gasket B was injection moulded from HYTREL thermoplastic, polyester block copolymer grade 8238, as before, but this time containing 20% by weight of a finely divided calcined kaolin which had been treated with an aminosilane. Its leakage behaviour after 400 cycles was rated as good and the bolt load loss was 28%.
Gasket C was injection moulded from a pure polybutylene terepthalate (PBT) containing 10% by weight of the same kaolin as was used for gasket B. The leakage performance at 400 cycles was again rated as good, but on inspection the gasket had cracked. Its bolt load loss was 36%. The composition used for gasket B was also tested in several other engines, with similar results as regard leakage, no leakage being recorded in any case at 300 cycles and more. It is important to note with a gasket according to the present invention, satisfactory sealing was still achieved after 300-400 cycles, even in cases where a relatively high load loss was observed.

Claims

1. An injection moulded gasket comprising an essentially fibre-free thermoplastic elastomer material including a filler in the form of plate-like particles, the amount of said filler being up to 30 percent by weight.
2. A gasket according to claim 1 wherein said filler is selected from kaolin, graphite, mica and talc.
3. A gasket according to any preceding claim wherein the filler is finely divided kaolin present in an amount from 1O to 20 percent by weighty s
4. A gasket according to -claim 2 or claim 3 wherein the kaolin is calcined and surface modified with a aminosilane prior to incorporation into the fibre-free thermoplastic elastomer material.
5. A gasket according to any preceding claim wherein said thermoplastic elastomer comprises a thermoplastic polyester.
6. A gasket according to any preceding claim wherein the thermoplastic elastomer is a polyester block copolymer.
7. A gasket according to claim 6 wherein the polyester block copolymer comprises polybutylene terepthalate
? and a polyether ester.
8. A gasket according to claim 6 wherein the polyester block copolymer comprises polybutylene terepthalate and a polyether glycol.
9. A gasket according to claim 7 or claim 8 wherein the polybutylene terepthalate constitutes at least about 70% of the copolymer.
10. An injection moulded gasket comprising a thermoplastic elastomer including finely divided^ kaolin as a filler, substantially as described and illustrated with reference to Example 3.
PCT/GB1991/001997 1990-11-13 1991-11-13 Improved gaskets WO1992008917A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB909024678A GB9024678D0 (en) 1990-11-13 1990-11-13 Improved gaskets
GB9024678.6 1990-11-13

Publications (1)

Publication Number Publication Date
WO1992008917A1 true WO1992008917A1 (en) 1992-05-29

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ID=10685312

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Application Number Title Priority Date Filing Date
PCT/GB1991/001997 WO1992008917A1 (en) 1990-11-13 1991-11-13 Improved gaskets

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EP (1) EP0513270A1 (en)
JP (1) JPH05503313A (en)
GB (2) GB9024678D0 (en)
WO (1) WO1992008917A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003033377A1 (en) 2001-10-12 2003-04-24 Shin-Etsu Polymer Co., Ltd. Gaskets for substrate containers and substrate containers equipped with the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE8510511U1 (en) * 1985-04-10 1986-08-07 Feodor Burgmann Dichtungswerke Gmbh & Co, 8190 Wolfratshausen poetry
EP0205914A1 (en) * 1985-05-28 1986-12-30 W.R. Grace & Co.-Conn. Sealing compound
EP0320287A2 (en) * 1987-12-11 1989-06-14 Eagle-Picher Industries, Inc. High temperature metal rubber gasket

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GB1177088A (en) * 1966-10-29 1970-01-07 Dunlop Co Ltd Improvements in and relating to Elastomeric Polyurethane Compositions
GB1136350A (en) * 1966-11-25 1968-12-11 Grace W R & Co Improvements relating to non-permeable polymer films
US3438932A (en) * 1966-12-09 1969-04-15 Us Air Force High strength,heat resistant fluoroelastomers
US4140669A (en) * 1977-12-30 1979-02-20 General Electric Company Warp-resistant reinforced thermoplastic compositions comprising polyester resins, talc and silica
GB2048285B (en) * 1979-04-26 1983-10-19 Gen Electric Polyester compositions
JPS5826381B2 (en) * 1979-04-28 1983-06-02 信越ポリマ−株式会社 Electromagnetic shield gasket and its manufacturing method
JPS60202144A (en) * 1984-03-27 1985-10-12 Sumitomo Chem Co Ltd Polypropylene resin composition
GB8429608D0 (en) * 1984-11-23 1985-01-03 Ici Plc Aromatic polymer composition
JPH072902B2 (en) * 1985-09-03 1995-01-18 住友バイエルウレタン株式会社 Reinforced resin molded product
DE3638703A1 (en) * 1986-11-13 1988-05-26 Merkel Martin Gmbh Co Kg FLUORINE PLASTIC GASKET MATERIAL
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Publication number Priority date Publication date Assignee Title
DE8510511U1 (en) * 1985-04-10 1986-08-07 Feodor Burgmann Dichtungswerke Gmbh & Co, 8190 Wolfratshausen poetry
EP0205914A1 (en) * 1985-05-28 1986-12-30 W.R. Grace & Co.-Conn. Sealing compound
EP0320287A2 (en) * 1987-12-11 1989-06-14 Eagle-Picher Industries, Inc. High temperature metal rubber gasket

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* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 11, no. 038 (C-401)4 February 1987 & JP,A,61 203 165 ( TORAY ) 9 September 1986 see abstract *
PATENT ABSTRACTS OF JAPAN vol. 9, no. 324 (C-320)19 December 1985 & JP,A,60 155 284 ( BRIGESTONE ) 15 August 1985 see abstract *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003033377A1 (en) 2001-10-12 2003-04-24 Shin-Etsu Polymer Co., Ltd. Gaskets for substrate containers and substrate containers equipped with the same
EP1435331A1 (en) * 2001-10-12 2004-07-07 Shin-Etsu Polymer Co., Ltd. Gaskets for substrate containers and substrate containers equipped with the same
EP1435331A4 (en) * 2001-10-12 2010-05-05 Shinetsu Polymer Co Gaskets for substrate containers and substrate containers equipped with the same

Also Published As

Publication number Publication date
GB9124116D0 (en) 1992-01-02
GB9024678D0 (en) 1991-01-02
EP0513270A1 (en) 1992-11-19
GB2250024A (en) 1992-05-27
JPH05503313A (en) 1993-06-03

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