Corrosion-and chip-resistant coatings for high tensile steel

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Reexamination Certificate

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C428S220000, C428S318600, C428S319300, C428S328000, C428S332000, C428S416000, C428S418000, C427S195000, C427S202000, C427S203000, C427S375000, C427S386000, C427S388200

Reexamination Certificate

active

06677032

ABSTRACT:

BACKGROUND OF THE INVENTION
Steel coil springs in the wheel assemblies of automobiles and other vehicles are subjected to very corrosive conditions. Conventional steel springs were expected to rust, and to allow for such rusting, conventional coil springs were formed of appropriately thick steel.
To improve the steering and ride control of automobiles, it is desirable to move the wheels outward, toward the corners of the vehicle. This increases torsional stress on the automobile body structure which must be nullified using a stronger frame assembly or weight reduction of the suspension components moved toward the comers. Reduced diameter, high tensile steel, coil springs weigh less than conventional automotive suspension coil springs, so they offer means to reduce the weight of these components. Super high tensile steel offers the promise of further weight reduction.
Herein, high tensile steel is defined as having MPa) (megapascal (N/m
2
) ranging from 1800 Mpa to 2100 Mpa; this includes super high tensile steel from 1950 Mpa to 2100 Mpa or above.
High tensile steel,.coil springs are scratch and notch sensitive, so they require protection from impact damage caused by flying stones and gravel encountered during driving on paved or unpaved roads. Also, to maintain desired metallurgical properties and prevent premature flex damage failure, the high tensile steel cannot be heated beyond 325° F. (163° C.).
Conventional “E” coat primers and/or epoxy powder coatings used on strut type automotive suspension springs are unacceptable at inhibiting flying stone damage as determined by low temperature gravelometer testing followed by accelerated scab corrosion testing of high tensile springs. Neither layer applied alone will provide the chip and corrosion protection required.
A current approach to providing corrosion and chip resistance to high tensile steel is described in U.S. Pat. No. 5,981,086, filed Oct. 8, 1996, the teachings of which are incorporated herein by reference. This patent application describes a dual layer coating including a zinc rich, thermoset, epoxy base coat which provides corrosion resistance and a thermoplastic outer coating which provides chip-resistance. The particular thermoplastic resin taught in U.S. Pat. No. 5,981,086 is an ethylene/acrylic acid copolymer, a relatively expensive material. Polyolefins can be substituted for ethylene/acrylic acid copolymer, and although polyolefins are less expensive materials, thicker layers are required to provide the requisite chip-resistance. Also, processing of thermoplastics is expensive. A general disadvantage of such a dual layer coating is that two separate coating operations are required and two separate heating cycles are required, the first to fuse and cure, at least in part, the epoxy resin of the base coat and a second to fuse the thermoplastic resin of the outer coat plus complete curing of the epoxy base coat. Both the material of the base coat and the outer coat must be cycled at a temperature below that thereat the steel would lose its high tensile strength; accordingly the choice of suitable resins systems for the two layers is limited.
It is accordingly an object of the present invention to provide coatings for high tensile steel which are less expensive than the coatings currently in use and which can be processed with a single heat cycle.
SUMMARY OF THE INVENTION
In accordance with the invention, chip- and corrosion-resistant coatings for high tensile steel are provided in which the resin component is entirely a “toughened” epoxy resin. Corrosion-resistance is provided by high zinc loading, particularly in the portion of the coating in contact with the high tensile steel.
As one method of toughening the epoxy resin, the epoxy is adducted to (chemically bound to) between about 5 and about 25 wt % (based on total weight of the epoxy component and the elastomer component) of an elastomer having a glass transition temperature (T
g
) of −30° C. or below, preferably a T
g
of −40° C. or below. A particularly suitable elastomeric component is carboxyl-terminated butadiene/acrylonitrile (CTBN) rubber. The elastomeric component flexibilizes the resin and remains flexible down to temperatures to which the component part may be subjected to in cold weather conditions.
In accordance with another method of toughening the epoxy resin, the epoxy resin is chemically bound as an outer shell to a soft rubber core having a T
g
of about −30° C. or below, preferably about −40° C. or below, for example an acrylic rubber core having carboxylic acid functionality by which the epoxy resin of the shell is bound. Such acrylic rubbers might be formed from (meth)acrylic acid and (meth)acrylic esters In the fused and cured coating provided by such a powder, the acrylic rubber cores are believed to act to terminate any fracturing of the coating which may begin due to impact. In the core/shell resins which are used to form the coating powder, the acrylic rubber comprises between about 5 and about 20wt % of the resin based on total of epoxy shell and acrylic rubber core, and the epoxy of the shell the remaining about 80 to about 95 wt %.
In accordance with another method of toughening the epoxy resin, the epoxy resin is cured with a multi-hydroxy functional curing agent having a hydroxyl equivalent weight of at least 200, preferably at least about 300, up to about 500. The distance between hydroxyl groups of such a curing agent provides flexibility to the cured epoxy resin. This toughening method may be used alone or in conjunction with either of the two above-discussed toughening methods.
Although, each of the above-described hardened epoxies exhibit chip-resistance, such chip resistance is insufficient to meet the requirements for high tensile steel springs. However, as noted above, the hardened epoxies are zinc-loaded, i.e., with at least 75 parts per hundred resin (based on total of epoxy resin, hardening resin if present, and epoxy cross-linker), preferably at least about 150 phr zinc, and more preferably at least about 200 phr zinc. Surprisingly, and unexpectedly, the zinc, added for corrosion resistance, further toughens the epoxy that: is toughened by any of the three above-discussed methods. Accordingly, a toughened, zinc-loaded epoxy, at a fused and cured thickness of between about 12 and about 20 mils, preferably at least about 15 mils, may be applied as a single coat to high tensile steel, including high tensile steel springs, and meet present day commercial requirements for chip and corrosion-resistance.
A single coat of toughened, zinc-loaded epoxy has the advantage of simplicity, being applicable in a single powder coating operation and then processed through a single heating cycle to heat and cure the epoxy resin.
On the other hand, a single coat of toughened, zinc-loaded epoxy is wasteful of zinc in that only the zinc in close proximity to the high tensile steel affords corrosion protection. As zinc is a relatively expensive material, there is provided in accordance with the invention a dual coat embodiment in which an inner coat between about 1.5 and about 3 mils thick is one of the toughened, zinc-loaded epoxies described above with respect to the single coat embodiment, and an outer coat, between about 10 and about 15 mils thick, is of the same toughened epoxy as the inner coat, but without the zinc.
As noted above, any of the above-described toughened epoxies provide chip resistance, but, insufficient chip resistance to meet current requirements for high tensile steel springs. Accordingly, the zinc-free outer coat is further toughened. One method of further toughening the outer layer is to add fibers to the outer coat formed of a material, such as glass, aramid or carbon, which does not melt or degrade at the processing temperatures to which the coating powder is subjected. Useful fibers have diameters between about 5 and about 20 &mgr;m, and are used at between about 20 and about 80 phr of the resin used to form the outer coat. Another method of further toughening the outer coat is to add a

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