WO2009045429A1 - Roues de véhicule - Google Patents

Roues de véhicule Download PDF

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Publication number
WO2009045429A1
WO2009045429A1 PCT/US2008/011356 US2008011356W WO2009045429A1 WO 2009045429 A1 WO2009045429 A1 WO 2009045429A1 US 2008011356 W US2008011356 W US 2008011356W WO 2009045429 A1 WO2009045429 A1 WO 2009045429A1
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WO
WIPO (PCT)
Prior art keywords
metal
wheel
wheels
coated
composition
Prior art date
Application number
PCT/US2008/011356
Other languages
English (en)
Inventor
Andri E. Elia
Michael R. Day
Robert Espey
Glenn Steed
Andrew Wang
Daniel Woloshyn
Original Assignee
E. I. Du Pont De Nemours And Company
Morph Technologies, Inc.
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 E. I. Du Pont De Nemours And Company, Morph Technologies, Inc. filed Critical E. I. Du Pont De Nemours And Company
Publication of WO2009045429A1 publication Critical patent/WO2009045429A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60B—VEHICLE WHEELS; CASTORS; AXLES FOR WHEELS OR CASTORS; INCREASING WHEEL ADHESION
    • B60B5/00—Wheels, spokes, disc bodies, rims, hubs, wholly or predominantly made of non-metallic material
    • B60B5/02—Wheels, spokes, disc bodies, rims, hubs, wholly or predominantly made of non-metallic material made of synthetic material

Definitions

  • Organic polymers which are metal plated are useful for vehicular wheels.
  • TECHNICAL BACKGROUND Vehicles such as automobiles, trucks, motorcycles, airplanes, 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 . 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 rea- sons. 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 the they are not stiff and/or strong enough, or have other property deficiencies compared to metal .
  • 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 metal plated polymeric gudgeon pin for an internal combustion engine.
  • US Patent 6,595,341 describes an aluminum plated plastic part for a clutch. Neither of these patents mentions wheels.
  • This invention concerns a vehicular wheel, comprising an organic polymer composition which is coated at least in part by a metal .
  • This invention also concerns a vehicle, comprising a wheel which comprises an organic polymer composition which is coated at least in part by a metal .
  • organic polymer composition a composition which comprises one or more organic polymers.
  • one or more of the organic polymers is the continuous phase.
  • organic polymer OP
  • OP organic polymer
  • OP 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.
  • 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) .
  • TPP is meant a polymer which is not crosslinked and which has a melting point and/or glass transition point above 30°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.
  • TSP is meant a polymeric material which is crosslinked, i.e., is insoluble in solvents and does not melt.
  • 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.
  • composition 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) .
  • coated with a metal is meant part or all of one or more surfaces of the wheel is coated with a metal.
  • the metal does not necessarily directly contact a surface of the organic polymer composition.
  • 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) .
  • 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 .
  • Wheels are important parts of vehicles, including aircraft especially when on the ground. Typically a rubber tire is mounted on the wheel. The wheels must be able to withstand static loads when the vehicle is stationary, and dynamic loads when the vehicle is moving.
  • OP composition wheels are not usually useful because the wheels must be massive to withstand the dynamic forces and heat (from brakes) the wheels must undergo.
  • metal coated OP wheels are useful, having the requisite properties.
  • Preferred vehicles for the wheels described herein are aircraft, all terrain vehicles (ATVs), motorcycles, scooters, small utility vehicles, golf carts, and automobiles, and aircraft, motorcycles, scooters, small utility vehicles, golf carts, and all terrain vehicles are more preferred.
  • 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(l,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.
  • LCP Thermotropic liquid crystalline polymer
  • 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 composition 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.
  • Another 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 should preferably not soften significantly at the expected maximum operating temperature of the wheel. 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 wheel .
  • 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.
  • vacuum deposition including various methods of heating the metal to be deposited
  • electroless plating electroplating
  • chemical vapor deposition metal sputtering
  • electron beam deposition electron beam deposition
  • electroless plating and electroplating and a combination of the two.
  • 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.
  • 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.
  • Useful metals and alloys to form the metal coating include copper, nickel, iron-nickel, cobalt, cobalt - nickel, and chromium, and combinations of these in dif- ferent 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.
  • grain size of the metal deposited may be controlled by the electroplating conditions, see for instance U.S. Patents 5,352,266 and 5,433,797 and U.S. Patent Publications 20060125282 and 2005020525, all of which are hereby included by reference.
  • 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.
  • the metal has an average grain size of at least 500 nm, preferably at least about 1000 nm, and/or an average maximum grain size of about 5000 nm.
  • 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 providing 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.
  • the flexural modulus of the metal coated wheel is at least about twice, more preferably at least about thrice, the flexural modulus of the uncoated OP composition. This is measured in the following 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 wheels 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 wheel .
  • the thickness of the metal coating on the bars is the same as on the wheel. If the thickness on the wheel varies, the test bars will be coated to the greatest metal thickness on the wheel.
  • 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 uncoated) .
  • flexural moduli flexural modulus of coated/ flexural modulus of uncoated
  • the plated OP composition be tough, for example 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, Madison, 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.
  • 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.
  • 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.
  • the ISO179 impact energy (see below for procedure) of the metal plated wheel be 1.2 times or more the impact energy of the unplated OP compo- sition, 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 wheel , with the same thickness of metal applied. If the wheel is metal plated on both sides (of the principal surfaces) , the test bars are plated on both sides, while if the wheel 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 OP composition.
  • 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. Generally speaking the higher the tensile modulus of the metal, the less will be needed to achieve a given stiffness (flexural modulus) .
  • 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 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 polymer composition was dried at 80 0 C in a dehumidified dryer. Molding conditions were melt temperature 280-300 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.
  • 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.
  • 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.
  • GF 2 - Chopped (nominal length 3.2 mm) glass fiber PPG ® 3540, available from PPG Industries, Pitts- burgh, 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) .
  • Polymer A - Polyamide-6 , 6 , Zytel ® 101 available from E.I. DuPont de Nemours & Co., Inc. Wilmington, DE 19810, USA.
  • 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/l-octene co- polymer available by Dow Chemical Co., Midland, MI, USA.
  • Wax 2 - Licowax ® OP available from Clariant Corp. Charlotte, NC 28205, USA.
  • the organic polymer compositions used in these examples 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
  • 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
  • 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 ⁇ m of Cu was followed by deposition of a 100 ⁇ m 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.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Compositions polymères organiques à plaquage métallique convenant pour la fabrication de roues de véhicule. De telles roues peuvent être plus légères que des roues classiques.
PCT/US2008/011356 2007-10-04 2008-10-01 Roues de véhicule WO2009045429A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US99761807P 2007-10-04 2007-10-04
US60/997,618 2007-10-04

Publications (1)

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WO2009045429A1 true WO2009045429A1 (fr) 2009-04-09

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2524817A1 (fr) * 2011-05-20 2012-11-21 Carbotec Industrial Co., Ltd Jante de roue de bicyclette et procédé de production de la production de celle-ci
CN102795053A (zh) * 2011-05-25 2012-11-28 莹信工业股份有限公司 自行车轮圈及其制造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4816324A (en) * 1986-05-14 1989-03-28 Atlantic Richfield Company Flexible photovoltaic device
US5636906A (en) * 1992-06-25 1997-06-10 Lacks Industries, Inc. Chromium-plated composite wheel
US20060135282A1 (en) * 2004-12-17 2006-06-22 Integran Technologies, Inc. Article comprising a fine-grained metallic material and a polymeric material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4816324A (en) * 1986-05-14 1989-03-28 Atlantic Richfield Company Flexible photovoltaic device
US5636906A (en) * 1992-06-25 1997-06-10 Lacks Industries, Inc. Chromium-plated composite wheel
US20060135282A1 (en) * 2004-12-17 2006-06-22 Integran Technologies, Inc. Article comprising a fine-grained metallic material and a polymeric material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2524817A1 (fr) * 2011-05-20 2012-11-21 Carbotec Industrial Co., Ltd Jante de roue de bicyclette et procédé de production de la production de celle-ci
CN102795053A (zh) * 2011-05-25 2012-11-28 莹信工业股份有限公司 自行车轮圈及其制造方法
CN102795053B (zh) * 2011-05-25 2015-11-18 莹信工业股份有限公司 自行车轮圈及其制造方法

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