Stock material or miscellaneous articles – Hollow or container type article – Polymer or resin containing
Reexamination Certificate
1998-02-13
2001-01-30
Robinson, Ellis (Department: 1772)
Stock material or miscellaneous articles
Hollow or container type article
Polymer or resin containing
C428S474700, C428S477400, C428S517000, C428S525000, C138S137000, C138S141000
Reexamination Certificate
active
06180197
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to tubing for use in a motor vehicle. More particularly, the present invention relates to a multi-layer tube which can be employed for transporting hydrocarbon-containing fluids such as automotive fuel. Even more particularly, this invention relates to multi-layer tubing construction having enhanced characteristics of hydrocarbon non-permeability, integral layer lamination and performance durability. Such tubes would be employed in a fuel line or a vapor recovery line of a motor vehicle.
BACKGROUND OF THE INVENTION
Single layer fuel lines and vapor return lines of synthetic materials such as polyamides have been proposed and employed in the past. Fuel lines employing such materials generally have lengths of at least several meters. In order to fulfill their function, the material employed in the fuel line must be inert to the medium flowing through them and resistant to high and low temperatures and to mechanical loads. Once installed, it is important that the line not materially change during the length of operation either by shrinkage or elongation or as a result of the stresses to which the line may be subject during use.
Single layer tubes are not always capable of meeting the necessary requirements. Transport of materials containing aliphatic or aromatic chemicals can create undesirable disadvantages such as hydrocarbon permeation, dimensional changes or insufficient mechanical load bearing capacity.
It has become increasingly important that fuel lines be essentially impervious to hydrocarbon emissions due to hydrocarbon permeation through the tube itself. The permissible hydrocarbon emissions due to permeation through fuel lines is severely limited by federal and state regulations. Regulations in states such as California fix the total passive hydrocarbon emission for a vehicle at 2 g/m
2
per 24 hour period as calculated by evaporative emission testing methods outlined in Title 13 of the California Code of Regulations, Section 1976 as amended Sep. 26, 1991. To achieve the desired total vehicle emission levels, a hydrocarbon permeation level for fuel lines equal to or below 0.5 g/m
2
per 24 hour period is desirable. It is also necessary that the fuel line employed be impervious to interaction with corrosive materials present in the fuel such as oxidative agents and surfactants as well as additives such as methanol and ethanol.
In the past, various types of tubing have been proposed to address these concerns. Co-extruded multi-layer tubing has met with various levels of success. Such multi-layer tubing generally employs a relatively thick outer layer composed of a material resistant to the exterior environment. The innermost layer (or layers) is thinner and is composed of a material which is chosen for its ability to block diffusion of materials, such as aliphatic hydrocarbons, alcohols and other materials present in fuel blends, to the outer layer.
Alcohol and aromatic components in the fuel conveyed through the tube tend to diffuse through the tubing wall at rates different from any diffusion of aliphatic fuel components. It was feared that the resulting change in the composition of the liquid in the tubing would alter solubility thresholds of the tubing material to a degree sufficient to be able to crystalize monomers and oligomers of materials such as nylon 12 and nylon 11 into the liquid. It was feared that crystallized nylon precipitate would block fuel filters, fuel injectors and the like and would collect to limit the travel of the fuel pump or carburetor float as well as build up on critical control surfaces of the fuel pump.
In order to avoid this phenomenon, patents such as U.S. Pat. No. 5,076,329 to Brunhoffer disclosed a five-layer fuel line in which the inner fluid-contacting surface was composed of nylon 6. In U.S. Pat. No. 5,038,833 to Brunhoffer, a three layer fuel line was proposed in which a tube is formed having a co-extruded outer wall of nylon 11 or nylon 12, an intermediate alcohol barrier wall formed of ethylene vinyl alcohol copolymer and an inner water blocking wall formed of a polyamide such as nylon 11 or nylon 12. In DE 40 06 870, a fuel line was proposed in which an intermediate solvent barrier layer is formed of unmodified nylon 6.6 either separately or in combination with polyamide elastomers. The innermost layer is also composed of polyamides such as modified or unmodified nylon 6 while the outer layer is composed of either nylon 6 or nylon 12. UK 2 204 376A discloses a tube which has a thick outer layer composed of a polyamide such as nylon 6 or nylon 6.6 and/or nylon 11 or nylon 12 coextruded with an alcohol-resistant polyolefin, and a copolymer of propylene and maleic acid.
In certain situations, it has been found that multi-layer tube having an innermost layer composed of nylon 11 or nylon 12 can be employed without adverse effects. In U.S. Pat. No. 5,313,987, a multi-layer pipe is disclosed which has an outer polyamide layer and an intermediate layer formed from a mixture of a thermoplastic polyester such as polybutylene terepthalate and a compound having at least two isocyanate groups. The innermost layer may, optionally, be composed of a polyamide.
In all instances, it is necessary to provide proper uniform laminar adhesion between all layers of the multi-layer tubing while achieving appropriate permeation resistance. Thus, advances and innovations regarding bonding materials which can be successfully employed in permeation resistant multi-layer tubing would be highly desirable.
In many instances, it is also desirable to provide a tube which can address the phenomenon of the build up of electrostatic charge on the surfaces of the tubing body. Electrostatic charge is defined as electric charge on the surface of a body. In this instance, a fuel tube, which occurs when charges are created at a rate faster than they can be dissipated. A net charge imbalance results. The charge imbalance will continue to increase until a limiting event such as a spark discharge occurs. In multi-layer fuel tubing, the electric charge built up is derived from the passage of charged particles through tubing constructed from essentially nonconductive materials.
Spark discharges generally occur in one of three ways: (a) directly to ground (through air); (b) from one part of a component to another (through air); or (c) to ground through the walls of a component (by dielectric breakdown). If a spark discharge due to dielectric breakdown occurs, the energy released in the discharge event can melt, degrade or burn the polymeric material in the discharge path and produce a pinhole rupture. Once dielectric breakdown occurs, the insulative properties of the material are weakened and subsequent breakdowns will generally occur at lower electrical field strength. Any subsequent discharge or current flow will tend to occur along the more conductive path already created thereby enlarging the hole or rupture. If this occurs in multi-layer fuel tubing, the risk of tubing rupture is increased with associated increases in the danger of fire and/or explosion of flammable contents in the tubing.
Various patents discussed the problems of lamination strength, permeation resistance, and electrostatic discharge prevention. Among these are U.S. Pat. No. 5,383,087 to Noone et al which discloses a multi-layer polymeric tube having at least four layers in which an inner layer and an innermost electrostatic discharge layer preferably composed of a fluoroplastic are bonded to an outer layer composed of a thermoplastic material such as thermoplastic elastomers and polyamides. The bonding layer is preferably composed of thermoplastic made up of a polyvinyl fluoride compound and a polyamide.
U.S. Pat. No. 5,524,673 also to Noone et al, discloses various multi-layer tubing constructions having at least three layers in which an outer layer is composed of a thermoplastic material selected from the group consisting of thermoplastic elastomers, polyamides, and mixtures thereof. The inner fuel-contacting layers disclosed in this reference in
Bensko David
Nie Tao
Pontbriand Duane
Figueroa John J.
ITT Manufacturing Enterprises Inc.
Robinson Ellis
Seitter Robert P.
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