VEHICULAR LIQUID CONDUITS

FIELD OF THE INVENTION Vehicular liquid conduits comprising organic polymers which are metal plated.

TECHNICAL BACKGROUND

Vehicles such as automobiles, trucks, motorcycles, scooters, recreational and all terrain vehicles, farm equipment such as tractors, and construction equipment such as bulldozers and graders are of course important items in modern society, and they are made of a myriad of parts. Also important are stationary internal combustion engines such as those used to power generators. Many of these parts must have certain minimum physical properties such as stiffness and/or strength. Traditionally these types of parts have been made from metals such as steel, aluminum, zinc, and other metals, but in recent decades organic polymers have been increasingly used for such parts for a variety of reasons. Such polymeric parts are often lighter, and/or easier (cheaper) to fabricate especially in complicated shapes, and/or have better corrosion resistance. However such polymeric parts have not replaced metals in some application because they are not stiff and/or strong enough, or have other property deficiencies compared to metal.

Thus vehicle manufacturers have been searching for ways to incorporate more polymeric materials into their vehicles for a variety of reasons, for example to save weight, lower costs, or provide more design freedom.

Thus improved polymeric liquid conduits (LCs) have been sought by vehicle manufacturers. It has now been found

that metal plated organic polymeric LCs have the properties desired.

Metal plated polymeric parts have been used in vehicles, especially for ornamental purposes. Chrome or nickel plating of visible parts, including polymeric parts, has long been done. In this use the polymer is coated with a thin layer of metal to produce a pleasing visual effect. The amount of metal used is generally the minimum required to produce the desired visual effect and be durable.

US Patent 4,406,558 describes a gudgeon pin for an internal combustion engine which is metal plated polymer. US Patent 6,595,341 describes an aluminum plated plastic part for a clutch. Neither of these patents mentions LCs.

SUMMARY OF THE INVENTION

This invention concerns a vehicular liquid conduit, comprising an organic polymer composition which is coated, at least in part, by a metal. This invention concerns a vehicle comprising a liquid conduit, which comprises an organic polymer composition which is coated at least in part by a metal.

DETAILS OF THE INVENTION

Herein certain terms are used and some of them are defined below:

By an "organic polymer composition" is meant a composition which comprises one or more organic polymers. Preferably one or more of the organic polymers is the continuous phase. By an "organic polymer" (OP) is meant a polymeric material which has carbon-carbon bonds in the polymeric chains and/or has groups in the polymeric chains which have carbon bound to hydrogen and/or halogen. Preferably the organic polymer is synthetic, i.e., made by man. The

organic polymer may be for example a thermoplastic polymer (TPP) , or a thermoset polymer (TSP) .

By a "TPP" is meant a polymer which is not crosslinked and which has a melting point and/or glass transition point above 30 ⁰ C, preferably above about 100 ⁰ C, and more preferably above about 150 ⁰ C. The highest melting point and/or glass transition temperature is also below the point where significant thermal degradation of the TPP occurs. Melting points and glass transition points are measured using ASTM Method ASTM D3418-82. The glass transition temperature is taken at the transition midpoint, while the melting point is measured on the second heat and taken as the peak of the melting endotherm. By a "TSP" is meant a polymeric material which is crosslinked, i.e., is insoluble in solvents and does not melt. It also refers to this type of polymeric material before it is crosslinked, but in the final LC, it is crosslinked. Preferably the crosslinked TSP composition has a Heat Deflection Temperature of about 50 ⁰ C, more preferably about 100 ⁰ C, very preferably about 150 ⁰ C or more at a load of 0.455 MPa (66 psi) when measured using ASTM Method D648-07.

By a polymeric "composition" is meant that the organic polymer is present together with any other addi- tives usually used with such a type of polymer (see below) .

By "coated with a metal" is meant part or all of one or more surfaces of the LC is coated with a metal. The metal does not necessarily directly contact a surface of the organic polymer composition. For example an adhesive may be applied to the surface of the organic polymer and the metal coated onto that. Any method of coating the metal may be used (see below) .

By "metal" is meant any pure metal or alloy or combination of metals. More than one layer of metal may be present, and the layers may have the same or different compositions. Many different liquids are present in a typical motor vehicle, especially one having an internal combustion engine. Among these may be coolant (usually antifreeze and water) , oil, brake fluid, transmission fluid, power steering fluid, windshield washer solvent, fuel, etc. Usually they are conveyed through and/or present in hollow longitudinal items called by various names such as tubing, pipe, (brake) line, fuel rail, header, nozzle and port, etc. However in one preferred form, the LC is not a fuel rail. These LCs must withstand the environment they may be in, such as heat from the engine, as well as the effects of the liquids in them. In many cases, such as brake lines and fuel lines, their function is vital to the safe operation of the vehicle.

LCs coated with metals have improved stiffness and strength, reduced permeation to the liquid especially when fully coated, the organic polymer is further protected from degradation by the liquid in the LC when fully coated on the interior of the LC. Also because the metal's properties generally do not change much in the operating temperature range of the LC, when the metals fully coat the LC they provide an extra measure of protection against leaks due to abnormally high operating temperatures and/or abnormally high internal pressures. The LCs may perform a variety of functions, such as coolant pipes, windshield washer solvent tubes, brake lines, oil tubes, fuel rails, or fuel lines. It is preferred that the OP composition used in the LC has resistance to the liquid being carried in the LC even if the LC is metal coated on the interior. This provides an ex-

tra measure of protection for the LC even if the metal coating is somehow not continuous.

Useful TSPs include epoxy, phenolic, and melamine resins. Parts may be formed from the thermoset resin by conventional methods such as reaction injection molding or compression molding.

Useful TPPs include poly (oxymethylene) and its copolymers; polyesters such as poly (ethylene terephtha- late) , poly (1, 4-butylene terephthalate) , poly (1,4- cyclohexyldimethylene terephthalate), and poly (1,3- poropyleneterephthalate) ; polyamides such as nylon-6, 6, nylon-6, nylon-12, nylon-11, and aromatic-aliphatic co- polyamides; polyolefins such as polyethylene (i.e. all forms such as low density, linear low density, high den- sity, etc.), polypropylene, polystyrene, polystyrene/poly (phenylene oxide) blends, polycarbonates such as poly (bisphenol-A carbonate); fluoropolymers including perfluoropolymers and partially fluorinated polymers such as copolymers of tetrafluoroethylene and hexafluoropro- pylene, poly (vinyl fluoride), and the copolymers of ethylene and vinylidene fluoride or vinyl fluoride; poly- sulfides such as poly (p-phenylene sulfide); polyetherke- tones such as poly (ether-ketones) , poly (ether-ether- ketones) , and poly (ether-ketone-ketones) ; poly (etherimides) ; acrylonitrile-1, 3-butadinene-styrene copolymers; thermoplastic (meth) acrylic polymers such as poly (methyl methacrylate) ; and chlorinated polymers such as poly (vinyl chloride), polyimides, polyamideimides, vinyl chloride copolymer, and poly (vinylidene chloride) . "Thermotropic liquid crystalline polymer" (LCP) herein means a polymer that is anisotropic when tested using the TOT test or any reasonable variation thereof, as described in U.S. Patent 4,118,372, which is hereby incorporated by reference. Useful LCPs include polyesters,

poly (ester-amides) , and poly (ester-imides) . One preferred form of LCP is "all aromatic", that is all of the groups in the polymer main chain are aromatic (except for the linking groups such as ester groups) , but side groups which are not aromatic may be present. The TPPs may be formed into parts by the usual methods, such as injection molding, thermoforming, compression molding, extrusion, and the like.

The OP, whether a TSP, TPP or other polymer composi- tion may contain other ingredients normally found in such compositions such as fillers, reinforcing agents such as glass and carbon fibers, pigments, dyes, stabilizers, toughening agents, nucleating agents, antioxidants, flame retardants, process aids, and adhesion promoters. An- other class of materials may be substances that improve the adhesion to the resin of the metal to be coated onto the resin. Some of these may also fit into one or more of the classes named above.

The OP (composition) should preferably not soften significantly at the expected maximum operating temperature of the LC. Since it is often present at least in part for enhanced structural purposes, it will better maintain its overall physical properties if no softening occurs. Thus preferably the OP has a melting point and/or glass transition temperature and/or a Heat Deflection Temperature at or above the highest use temperature of the OP.

The OP composition (without metal coating) should also preferably have a relatively high flexural modulus, preferably at least about 1 GPa, more preferably at least about 2 GPa, and very preferably at least about 10 GPa. Flexural modulus is measured by ASTM Method D790-03, Procedure A, preferably on molded parts, 3.2 mm thick (1/8 inch), and 12.7 mm (0.5 inch) wide, under a standard

laboratory atmosphere. Since these are structural parts, and are usually preferred to be stiff, a higher flexural modulus improves the overall stiffness of the metal coated LC. The OP composition may be coated with metal by any known methods for accomplishing that, such as vacuum deposition (including various methods of heating the metal to be deposited) , electroless plating, electroplating, chemical vapor deposition, metal sputtering, and electron beam deposition. Preferred methods are electroless plating and electroplating, and a combination of the two. Although the metal may adhere well to the OP composition without any special treatment, usually some method for improving adhesion will be used. This may range from simple abrasion of the OP composition surface to roughen it, addition of adhesion promotion agents, chemical etching, functionalization of the surface by exposure to plasma and/or radiation (for instance laser or UV radiation) or any combination of these. Which methods may be used will depend on the OP composition to be coated and the adhesion desired. Methods for improving the adhesion of coated metals to many OPs are well known in the art. More than one metal or metal alloy may be plated onto the organic resin, for example one metal or alloy may be plated directly onto the organic resin surface because of its good adhesion, and another metal or alloy may be plated on top of that because it has a higher strength and/or stiffness, and optionally an additional metal or alloy may be plated on top to provide corrosion protection.

Useful metals and alloys to form the metal coating include copper, nickel, cobalt, cobalt-nickel, iron- nickel, and chromium, and combinations of these in different layers. Preferred metals and alloys are copper,

nickel, cobalt, cobalt-nickel, and iron-nickel, and nickel is more preferred.

The surface of the organic resin of the structural part may be fully or partly coated with metal. In dif- ferent areas of the part the thickness and/or the number of metal layers, and/or the composition of the metal layers may vary.

When electroplating it is known that grain size of the metal deposited may be controlled by the electroplat- ing conditions, see for instance U.S. Patents 5,352,266 and 5,433,797 and U.S. Patent Publication 20060125282, all of which are hereby included by reference. In one preferred form at least one of the metal layers deposited has an average grain size in the range of about 5 nm to about 200 nm, more preferably about 10 nm to about 100 nm. In another preferred form of electroplated metal, the metal has an average grain size of at least 500 nm, preferably at least about 1000 nm, and/or a maximum average grain size of 5000 nm. For all these grain size preferences, it is preferred that that thickest metal layer, if there is more than one layer, be the specified grain size. The thickness of the metal layer (s) deposited on the organic resin is not critical, being determined mostly by the desire to minimize weight while pro- viding certain minimum physical properties such as modulus, strength and/or stiffness. These overall properties will depend to a certain extent not only on the thickness and type of metal or alloy used, but also on the design of the structural part and the properties of the organic resin composition.

In one preferred embodiment the flexural modulus of the metal coated LC is at least about twice, more preferably at least about thrice the flexural modulus of the uncoated OP composition. This is measured in the follow-

ing way. The procedure used is ISO Method 178, using molded test bars with dimensions 4.0 mm thick and 10.0 mm wide. The testing speed is 2.0 mm/min. The composition from which the LCs are made is molded into the test bars, and then some of the bars are completely coated (optionally except for the ends which do not affect the test results) with the same metal using the same procedure used to coat the LC. The thickness of the metal coating on the bars is the same as on the LC. If the thickness on the LC. varies, the test bars will be coated to the greatest metal thickness on the LC. The flexural moduli of the coated and uncoated bars are then measured, and these values are used to determine the ratio of flexural moduli (flexural modulus of coated/flexural modulus of un- coated) . Generally speaking the thicker the metal coating, the greater the flexural modulus ratio between the uncoated and coated OP part .

For use as LCs, it is also important in many instances that the plated OP composition be tough, for ex- ample be able to withstand impacts. It has surprisingly been found that some of the metal plated OP compositions of the present invention are surprisingly tough. It has previously been reported (M. Corley, et al., Engineering Polyolefins for Metallized Decorative Applications, in Proceedings of TPOs in Automotive 2005, held June 21-23, 2005, Geneva Switzerland, Executive Conference Management, Plymouth, MI 48170 USA, p. 1-6) that unfilled or lightly filled polyolefin plaques have a higher impact energy to break than their Cr plated analog. Indeed the impact strength of the plated plaques range from 50 to 86 percent of the impact strength of the unplated plaques. As can be seen from Examples 2-8 below, the impact maximum energies of the plated plaques are much higher than those of the unplated plaques. It is believed this is

due to the higher filler levels of the OP compositions used, and in the present parts it is preferred that the OP composition have at least about 25 weight percent, more preferably about 35 weight percent, especially pref- erably at least about 45 weight percent of filler/reinforcing agent present. A preferred maximum amount of filler/reinforcing agent present is about 65 weight percent. These percentages are based on the total weight of all ingredients present. Typical reinforcing agents/fillers include carbon fiber, glass fiber, aramid fiber, particulate minerals such as clays (various types) , mica, silica, calcium carbonate (including limestone) , zinc oxide, wollastonite, carbon black, titanium dioxide, alumina, talc, kaolin, microspheres, alumina trihydrate, calcium sulfate, and other minerals.

It is preferred that the ISO179 impact energy (see below for procedure) of the metal plated LC be 1.2 times or more the impact energy of the unplated OP composition, more preferably 1.5 times or more. The test is run by making bars of the OP composition, and plating them by the same method used to make the LC, with the same thickness of metal applied. If the LC is metal plated on both sides (of the principal surfaces) , the test bars are plated on both sides, while if the LC is plated on one side (of the principal surfaces) the test bars are plated on one side. The impact energy of the plated bars are compared to the impact energy of bars of the unplated LC.

Another often important property of LCs is their burst strength, that is the amount of internal pressure they can withstand without failure. This is important to their function as liquid conduits, and also often an important item for safety because spillage of the liquid may cause a hazard, such as a fire hazard from the fail-

ure of fuel line, or a lack of braking from the failure of a brake line.

Preferably the metal coating will about 0.010 mm to about 1.3 mm thick, more preferably about 0.025 mm to about 1.1 mm thick, very preferably about 0.050 to about 1.0 mm thick, and especially preferably about 0.10 to about 0.7 mm thick. It is to be understood that any minimum thicknesses mentioned above may be combined with any maximum thickness mentioned above to form a different preferred thickness range. The thickness required to attain a certain flexural modulus is also dependent on the metal chosen for the coating. Generally speaking the higher the tensile modulus of the metal, the less will be needed to achieve a given stiffness (flexural modulus) . Preferably the flexural modulus of the uncoated OP composition is greater than about 200 MPa, more preferably greater than about 500 MPa, and very preferably greater than about 2.0 GPa.

Example 1 Zytel® 70G25, a nylon 6,6 product containing 25 weight percent chopped glass fiber available from E.I. DuPont de Nemours & Co., Inc. Wilmington, DE 19898 USA, was injection molded into bars whose central section was 10.0 mm wide and 4.0 mm thick. Before molding the poly- mer composition was dried at 80 ⁰ C in a dehumidified dryer. Molding conditions were melt temperature 2800-300 ⁰ C and a mold temperature of 80 ⁰ C. Some of the bars were etched using Addipost® PM847 etch, reported to be a blend of ethylene glycol and hydrochloric acid, and obtained from Rohm & Haas Chemicals Europe. Less than 1 μm of copper was then electrolessly deposited on the surface, followed by 8 μm of electrolytically deposited copper, followed by 100 μm of nickel, on all surfaces. The flexural modulus

was then determined, as described above, on the uncoated and metal coated bars. The uncoated bars had a flexural modulus of 7.7 GPa, and the metal coated bars had a flexural modulus of 29.9 GPa. Examples 2-7

Ingredients used, and their designations in the tables are:

Filler 1 - A calcined, aminosilane coated, kaolin, Polarite® 102A, available from Imerys Co., Paris, France.

Filler 2 - Calmote® UF, a calcium carbonate available from Omya UK, Ltd., Derby DE21 6LY, UK.

Filler 3 - Nyad® G, a wollastonite from Nyco Minerals, Willsboro, NY 12996, USA. Filler 4 - M10-52 talc manufactured by Barretts

Minerals, Inc., Dillon, MT, USA.

Filler 5 - Translink® 445, a treated kaolin available from BASF Corp., Florham Park, NJ 07932, USA.

GF 1 - Chopped (nominal length 3.2 mm) glass fi- ber, PPG® 3660, available from PPG Industries, Pittsburgh, PA 15272, USA.

GF 2 - Chopped (nominal length 3.2 mm) glass fiber, PPG® 3540, available from PPG Industries, Pittsburgh, PA 15272, USA. HSl - A thermal stabilizer containing 78% KI,

11% aluminum distearate, and 11% CuI (by weight) .

HS2 - A thermal stabilizer contain 7 parts KI, 11 parts aluminum distearate, and 0.5 parts CuI (by weight) . Lube - Licowax® PE 190 - a polyethylene wax used as a mold lubricant available from Clariant Corp. Charlotte, NC 28205, USA.

Polymer A - Polyamide-6, 6, Zytel® 101 available from E.I. DuPont de Nemours & Co . , Inc. Wilmington, DE 19810, USA.

Polymer B - Polyamide-6, Durethan® B29 available from Laxness AG, 51369 Leverkusen, Germany.

Polymer C - An ethylene/propylene copolymer grafted with 3 weight percent maleic anhydride. Polymer D - A copolyamide which is a copolymer of terephthalic acid, 1, 6-diaminohexane, and 2-methyl-l, 5- diaminopentane, in which each of the diamines is present in equimolar amounts.

Polymer E - Engage®8180, an ethylene/1-octene co- polymer available by Dow Chemical Co., Midland, MI, USA. Wax 1 - N, N' -ethylene bisstearamide Wax 2 - Licowax® OP, available from Clariant Corp. Charlotte, NC 28205, USA.

The organic polymer compositions used in these exam- pies are listed in Table 1. The compositions were made by melt blending of the ingredients in a 30 mm Werner & Pfleiderer 30 mm twin screw extruder.

Table 1

The test pieces, which were 7.62x12.70x0.30 cm plaques or ISO 527 test bars, 4 mm thick, gauge width 10 mm, were made by injection molding under the conditions given in Table 2. Before molding the polymer compositions were dried for 6-8 hr in dehumidified air under the temperatures indicated, and had a moisture content of <0.1% before molding.

Table 2

These test specimens were then etched in sulfochro- mic acid or Rohm & Haas Chrome free etching solution, and rendered conductive on all surface by electroless deposition of a very thin layer of Ni. Subsequent galvanic deposition of 8 μm of Cu was followed by deposition of a 100 μm thick layer of fine grain N-Fe (55-45 weight) using a pulsed electric current, as described in US Patent 5,352,266 for making fine grain size metal coatings.

The samples were tested by one or both of the following methods :

ISO 6603-2 - Machine Instron® Dynatup Model 8250, Support Ring 40 mm dia, Hemispherical Tup 20 mm dia, Ve- locity 2.2 m/s, Impacter weight 44.45 kg, Temperature

23°C, Condition dry as made. Test were run on the plaques described above.

ISO 179-leU - Sample Unnotched, Pendulum energy 25 J, Impact velocity 3.7 m/s, Temperature 23°C, Condition dry as made. Tests were run on the gauge part of the ISO 527 test bars described above.

Testing results are given in Table 3.

Table 3

Example 8

A tube of the composition of Example 3, with an outer diameter of _2.82 cm, a wall thickness of 0.25 cm, and a length of 14.0 cm was formed by injection molding. Electrolytic deposition of Ni was accomplished by etching in sulfochromic acid for 5-20 min at 50-80 ⁰ C, rinsing four times with water, Neutraliziing with Rohm & Haas Neutral- iser PM955, rinsing, GRZ etching, rinsing, predipping in 10% HCl, Activating in Conductron® DP (35 ppm Pd) , rinsing, using Accelerator PM964, rinsing, coating elec- trolessly with Cu, and then coating with 100 μm thick Ni. It is believed the Ni is fine grained (<100 nm average grain size) .

The testing apparatus was a jig that sealed the ends of the tube with end plates, one end plate having a connection for pressurized water, and the other having a pressure gauge attached. The end plates could be tight- ened against the tube by tightening nuts attached to threaded rods passing through the end plates. If the test was done at room temperature, the tube to be tested was sealed in the jig and water pumped in so that the test pressure was reached. Before testing any loose or jagged edges were removed from the metal coated tubes, and all of the tubes were squared off at the ends in order to achieve good seals with the jig. The tube was

checked periodically for failure (leakage) . If the. test was done at an elevated temperature, the jig was placed in an oven at the test temperature and checked periodically for failure (leakage) . A tube which had no metal coating failed when the pressure reached 5.5 MPa (800 psi) as the pressure was slowly raised at room temperature. A similar but metal coated tube as described above had no leaks at 8.3 MPa (1200 psi) after 1 hour at room temperature. An uncoated tube was tested at 3.5 MPa (500 psi) at 150 ⁰ C and failed in less than 10 min. A similar metal coated tube as described above was tested at 3.5 MPa (500 psi) at 150 ⁰ C and had no failure after 1 hr. At 180 ⁰ C and 3.5 MPa pressure a metal coated tube leaked after 30-40 minutes.