GB2321470A - Sealing material - Google Patents

Abstract

Sealing material comprises from 45-90% by weight exfoliated graphite, from 5 to 20% by weight thermosetting resin, and from 5 to 50% by weight fibrous filler which is heat resistant at 250‹C. The fibrous filler has fibres at least 90% of which have a fibre length of less than 200Ám, and an aspect ratio of less than 10:1. The fibrous filler may be wollastonite and the resin may be phenolic.

Description

SEALING MATERIAL The invention relates to a sealing material comprising exfoliated graphite, thermosetting resin, and a fibrous filler.

Sealing materials comprising exfoliated graphite have been used as cylinder head gaskets and other types of seals in internal combustion engines, such as automobile engines for some time, since they have good heat resistance and stress relaxation properties. Graphite sheets have been found to have poor resistance to oil, and this has restricted their use. Means have been sought to improve the oil resistance of graphite sheets. Japanese patent application number 63-72780 relates to a graphite sheet which has expanded graphite particles, heat-resistant fibres, and an organic high-polymer binder as principal components. The graphite sheets produced are said to have improved oil resistance and antifreeze resistance. Heatresistant inorganic fibres such as rockwool, ceramic fibres, silicate fibres and surface-treated silicate fibres or heat-resistant organic fibres such as aromatic polyamide fibres and phenolic resin fibres can be used as the heatresistant fibres. The length of the heat-resistant fibres is said to be about 1-50mm, and the thickness from 10 300m.

In use, when a sealing material comprising exfoliated graphite is under pressure, extrusion of the material may occur jeopardizing the seal. This occurs considerably more easily when the graphite is oil-soaked than in an oil-free environment. Since such extrusion is an undesirable characteristic, it is desirable that extrusion of sealing material is avoided at pressures ordinarily experienced by them in oily environments. The pressure at which extrusion occurs (the extrusion collapse point) should be above such pressures.

According to the present invention, there is provided sealing material comprising from 45-90% by weight exfoliated graphite, from 5 to 20% by weight thermosetting resin, and from 5 to 50% by weight fibrous filler which is heat resistant at 2500C, the fibrous filler having fibres at least 90% of which have a fibre length of less than 200cm, and an aspect ratio of less than 10:1.

It has surprisingly been found that sealing materials comprising fibrous fillers with the short fibre lengths and aspect ratios of the present invention have considerably higher extrusion collapse points than sealing elements of graphite foil comprising exfoliated graphite alone, than graphite foil with phenolic resin, or than graphite foil comprising phenolic resin and fibrous fillers having fibre lengths of similar size to those described in JP 63 72780.

In some embodiments, the sealing material is in the form of a sheet or layer, for example, of a planar gasket such as an automotive head gasket.

In other embodiments the sealing material is in the form of a moulded shape, such as a shaft sealing ring.

A sealing material according to the invention may comprise from 5 to 20% by weight of the thermosetting resin, and from 5 to 30% by weight of the fibrous filler.

Conveniently, the thermosetting resin is a phenolic resin.

When a filler is used in which at least 90% of the fibres of the fibrous filler have a fibre length of less than 20cm, a further increase in the extrusion collapse point is found, and so it is preferred to use fibres of this length. Use of a fibrous filler at least 90% of the fibres of which have a fibre length of less than lOSm is more preferable.

Advantageously, the aspect ratio of the fibrous filler is less than 6:1.

The exfoliated graphite is mixed with the fibrous filler (and, optionally, the powdered thermosetting resin) in the dry state, eg by gentle tumbling or in the airborne state. A layer of the mixture is then compacted, usually by passage between rollers, to form a coherent foil or sheet. Alternatively, the mixture may be compacted to other shapes eg sealing rings. Such other shapes may also be made by re-moulding foil.

When the resin is added as a free-flowing powder, it may subsequently be made to flow, prior to cross-linking, by heating the consolidated foil (optionally under pressure). Further heating, normally to a higher temperature, then cross-linking the resin.

Alternatively, the powdered resin can be made to distribute itself more effectively through the foil by soaking in solvent and then drying.

A preferred method of introducing resin is to initially compress the exfoliated graphite to a relatively low density (eg 0.5kg m) so that some porosity is maintained. Liquid resin (solution or suspension in water, etc) is then allowed to soak in. After drying, the low density foil is compressed further to achieve the required final density.

The graphite sheet preferably has a final density of from 0.7 to 1.5 kg m3. Final densities of less than 0.7 are too weak and compressible. Densities of over 1.5 tend to be too hard and incompressible, giving a poor seal.

A particularly preferred fibrous filler is wollastonite the fibre length of which falls within the ranges of the present invention.

In addition to increasing the stress at which extrusion begins, shorter fibres and lower aspect ratios make it easier to mix the fibrous filler with the exfoliated graphite. This gives a more homogeneous product, which may contribute to improved performance.

A particular application of the sealing element of the present invention is used in a multi-layer steel gasket in the form of a thin coating on the gasket to fill fissures.

Typically, such a sealing element will be in the range from 50 to lOOpm thick, preferably approximately 75m thick.

In another application of the sealing element, a graphite layer or sheet from 0.5 to 2mm thick may be provided which acts to provide resilience in a gasket.

Comparative Example 1 Graphite foil having a thickness of approximately 2004m was formed by conventional means from expanded graphite. The graphite foil was consolidated by passing through calenders to achieve a foil thickness of 75m and a final density of 1.4 kg m.

Comparative Example 2 Graphite foil having a final thickness of approximately 200m as formed in the first stage of comparative example 1 but with an intermediate density of 0.5 kg m3 was impregnated with approximately 10% phenolic resin by first passing the foil throuah a bath containing

a resole phenolic resin, BordehLSC1008 resin in methyl isobutylketone solvent, and then by drying in an oven. The resin-impregnated graphite foil was then further consolidated as in comparative example 1.

Comparative Example 3 Graphite foil comprising approximately 10% by weight of mica was formed as in comparative examples 1 and 2 except that 10% of mica was added to the graphite prior to the expansion stage in the furnace. The foil was then impregnated and consolidated as in comparative example 2.

Comparative Examples 4 and 5 Comparative example 3 was repeated except that the graphite foil comprised (in Comparative Example 4) 10% of Nygloss wollastonite having a median fibre length of 0.25mm or (in Comparative Example 5) Franklin Fibre (calcium sulphate ex Franklin Institute with a length of about lmm) instead of Mica. When it was attempted to make a graphite foil of 75m thickness, the fibres coagulated and a foil was unable to be formed. The product was weak and inhomogeous and would not form a satisfactory seal.

There now follow examples 1 to 6 which are illustrative of the present invention.

Example 1 Comparative example 3 was repeated except that the graphite foil comprised 10% of wollastonite instead of mica.

The wollastonite incorporated was WollastocoatL 10 (from Nyco minerals), having an aspect ratio of 3:1, a median fibre length of 3Um, 96% of the fibres having a length below lOpm.

Example 2 Example 1 was repeated except that the wollastonite

was NyadL400 (from Nyco minerals) having an aspect ratio of 5:1 and a median fibre length of approximately 25cm.

Example 3 Example 1 was repeated except that the wollastonite was Vansil EW10 (from Vanderbilt, UK distributor, Microfine Minerals), having an aspect ratio of between 5:1 and 10:1, a median fibre length of approximately 32us, 97% of the fibres having a length below 63cm, and 40% below 20cm.

Example 4 Example 1 was repeated except that the woolastonite fibres formed 22% by weight and the final density was 1.1.

Example 5 Example 1 was repeated except that the woolastonite fibres formed 24% by weight and the phenolic resin formed 18% by weight. The final density was 1.4.

Example 6 Example 1 was repeated except that the woolastonite fibres formed 24% by weight and the phenolic resin formed 9% by weight. The final density was 1.4.

Tests were carried out on the products of the foils produced in the examples and the comparative examples as follows.

Each foil sample was soaked in a standard oil (ASTM oil 3) at 1500C for 5 hours. The foils were then subjected to pressure, to find their extrusion collapse points, that is the pressure at which extrusion occurs after the foils have been soaked in oil.

The results were as follows: Extrusion collapse point (MPa) Comparative Example 1 85 Comparative Example 2 87 Comparative Example 3 87 Comparative Examples 4 and 5 could not be determined Example 1 122 Example 2 99 Example 3 98 Example 4 164 Example 5 186 Example 6 155 This shows that the inclusion of the wollastonite of short fibre length as in examples 1 to 6 significantly raises the extrusion collapse point in this test.

Claims (12)

1 Sealing material comprising from 45-90% by weight exfoliated graphite, from 5 to 20% by weight thermosetting resin, and from 5 to 50% by weight fibrous filler which is heat resistant at 2500C, the fibrous filler having fibres at least 90% of which have a fibre length of less than 200mum, and an aspect ratio of less than 10:1.

2 Sealing material according to claim 1, wherein the material comprises from 5 to 20% by weight of the thermosetting resin, and from 5 to 30% by weight of the fibrous filler.

3 A sealing material as claimed in either one of claims

1 and 2, wherein the thermosetting resin is a phenolic resin.

4 A sealing material as claimed in any one of claims 1 to 3, wherein at least 90% of the fibres of the fibrous filler have a fibre length of less than 20cm.

5 A sealing material as claimed in claim 4, wherein at least 90% of the fibres of the fibrous filler have a fibre length of less than lOssm.

6 A sealing material as claimed in any one of the preceding claims, wherein the aspect ratio of the fibres of the fibrous filler is less than 6:1.

7 A sealing material as claimed in any one of the preceding claims, wherein the fibrous filler is wollastonite.

8 A sealing material as claimed in any one of the preceding claims, wherein the sealing material is in the form of a sheet or layer.

9 A sealing material as claimed in any one of the preceding claims, wherein the sheet or layer has a thickness of from 50ssm to 100m.

10 A sealing material as claimed in any one of claims 1 to 7, wherein the sealing material is in the form of a moulded shape.

11 A sealing material as claimed in any one of the preceding claims, wherein the sealing material has a density of from 0.7 to 1.5kgm3.

12 A sealing material substantially as hereinbefore described, with reference to example 1, 2, 3, 4, 5 or 6.