CA1205780A

CA1205780A - Ion beam deposition or etching re rubber-metal adhesion

Info

Publication number: CA1205780A
Application number: CA000430426A
Authority: CA
Inventors: David A. Benko
Original assignee: Goodyear Tire and Rubber Co
Current assignee: Goodyear Tire and Rubber Co
Priority date: 1982-07-23
Filing date: 1983-06-15
Publication date: 1986-06-10
Also published as: US4446197A; BR8303688A; EP0102310A2; EP0102310A3; JPS5929145A

Abstract

ABSTRACT

Metal to rubber adhesion is improved by metal substrates having a coating thereon such as brass, copper, and the like. The coating is applied by an ion beam sputter deposition or, in the alterna-tive, such a coating is partially removed through ion beam etching. The present invention is particu-larly useful in tire cord construction, metal rein-forced belts and hoses, and the like, since articles made therefrom have superior and unexpected moisture aged rubber-to-metal adhesion properties.

Description

'7~t ION BEAM DEPOSITION OR ETCHING
R~ RUBBER-M~TAL AD~SIO~I
__ BACKGROUND ART

The present invention relates to unexpected rubber-m~tal adhesion improvement for metal substrates which were prepared using ion beam etchin~ and deposi-tion.
Heretofore, wire used as reinforcement in rubber articles has been manufactured by coating the wire with a non-ferrous metal using conventional electroplating techniques. The coating material can consist, for example, of a layer of a brass alloy which is often used for ~he purpose mentioned. The specific composition and thickness of the coating material of t~le wire are restricted by manufacturing considerations.
For example, a brass alloy coated on a reinforcing wire must contain at least 63 percent copper and be at least 1000 A thickl.
It has been observed that moisture is generally very harmful for the adhesion between the steel rein-forcement and the rubber article. For example, United States Patent No. 3,749,558 notes that copper-plated steel wires display considerably higher adhesion failures after exposure to a 60 percent relative humidi-ty environment than when exposed to a dry air environ-ment. This has been of particular concern in recent years in which a strong demand is made of the safety and waterproofness of wire reinforced tires.
A number of methods have been described that prevent loss of rubber adhesion to conventionally pre pared wires after moisture exposure. For example, United States Patent No. 3~846,160 claims a process whereby the s~eel wire coated with brass alloy is i~nersed in a mineral nil so]ution prior to vulcaniza-tion. Another solution to the moisture problem calls for the use of a low copper content brass alloy as clescribed in Brltish Patent 1,250,419. A third method to prevent adhesive degra.dation under corrosive condi-tions involves the use of ternary brass alloys contain-ing copper, zlnc, and cobalt as described in British Pa~ent 2,011,501A and 2,306,278. Finally, United States Patent No. 3,749,558 describes the use of copper-nickel and copper-zinc-nickel alloy coatings on ~ire to prevent adhesion loss.
However, none of these patents relate to the use of ion beam deposition or etching or to improved rub~er moisture age adhesion.
Ion beam sputter deposition and etching are rela~ively new teclmiques. For example J in an article "Adherence of Ion Beam Sputtered Deposited Metal Films on H-13 Steel" by Michael Mirtich, Lewis Research Center, prepared for the 27th National ~merican Vacuum Society Symposium, Detroit, Michigan, October 14 17, 1980, it is.noted that die Iife can be increased by sputter depositing molybdenum or chro~ium upon a cast-ing die. Moreover, the tables set forth various other 25 materials and the adherence thereof to a steel sub-strate.
In an article entitled "Advances in Low-Energy Ion Beam Technology," by W. Laznovsky, Research and Development, Augus-~ 1975, pa~es ~7-5S, ion beams have been set forth as having been utilized for the etching of microcircuits, surface wave device con-tacts, and the like, in essence, whenever high resolu-tion (in.the submicrometer range) is required.
"Ion Beam Techniques for Thin and Thiclc Film Deposition," by C. Weissmantel, H. Erler, and G. Reisse, :

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Sur:~ace Science 86 (1979~, North-Holland Publi.sh-ing Company, pages 207-.~10, relates to various techniques for sputtered depvsiting films of various metals or alloys.
An article entitled "Ion Beam Texturing7' by Wayne Hudson of the I~ASA, Lewis Research Genter, Cleveland, ~hio, published in the Journal of Vacuum Society Technology, in Volume 14, No. 1, January and February ]977, pages 286-287, rel2tes to the use of texturing many surfaces such as stainless steel, ti-tanium, aluminum, copper and silicon by ion beam sput-tering in an attempt to provide a suitable optical coating.
In Optical Properti.es of Ion Beam Textured Materials by ~Eudson, Weigand, and Mirtich, Lewis Re-search Center, in a paper presented to the Sixth Annual Symposium on Applied Vacuum Scien.ce and Technology, Tampa, Florida, February 14-16, 1977, ion beams are used to coat a solar apparatus.
In an article entitled "Ion Beam Sputtering of ~luoropolymers" by Sovey, NASA Lewis Research Center, Cleveland, Ohio, published in the Journal .of Vacuum Science and Tec~mology, March-April, 1979, t~e etching : and deposition of fluoropolymers is described.
Finally, the article entitled " Character-istics of Ion-Beam-Sputtered ~lin Films," by Kane and A~m of IBM, published in the Journal of Vacuum Science and Technology, March-April, 1979, pages 171-172, relates to the thin films of various metals which have been prepared by ion beams sputtering with such films having excellent adhesion to a ~etal substrate.
Although the preceding representative arti-cles describe ion beam sputtering or etching techniques, none relate to or even teach or suggest that adhesion . of rubber to copper or brass-coated metals, such as ~21~

those used in ~ire cord construction, rubber hoses, and with regard to any r~ire reinforced rubber article, would be improved.

DISCLOSURE OF INVENT-LON
- _ It is therefore an aspect of the present in~-vention to provide improved rubber~to-metal adhesion.
It is yet another aspect of the present invention to provide improved rubber~o-metal adhesion, as above, with regard to an~ me~al reinforcecl rubber article.
It is yet another aspect of the pre~ent in-vention to provide improved rubber-to-metal adhesion, as abo~e, wherein ion beam sputter deposition or etch-ing is utilized to either apply a metallic coating or to remove a portion of a coating.
It is yet another aspect o~ the present in-vention to provide improved rubber-~o-metal adhesion, as above, wherein various metals such as copper and/or zinc are utilized as the coating on the ~etal sub-strate.
It is yet another aspect of the present in-vention to provide improved rubber-to-metal adhesion, as above, wherein the coating is from abou~ 5.0 to about 4,000 angstroms in thickness.
It is yet another aspect of the present in vention to provide improved rubber-to-metal adhesion, as above, wherein superior rubber-to-metal long term moisture aging is achieved.
It is yet another aspect of the present in-vention to provide improved rubber-to-metal adhesion, as above, wherein said metal substrate can be in the form of wire and the like and exists as a tire cord.
It is yet another aspect of the present in-vention to provide improved rubber-to-metal adhesion, i as above, including a process for preparing any of the above noted i~ems of achieving metal-to-rubber adhesion, These and other aspects or forms of the in-vention will become apparent from the Eollowing detailed specification.
In general, a process for preparing a metal surface for adhesion to rubber, comprises the steps of: applying an ion beam sputter deposition metal to a metal substrate, applying said deposition metal to said metal substrate until a coating of from about 5 to about 4,000 angstrom units is obtained and forming the metal surface, and wherein said deposition metal is selected from the group consisting o steel, zinc, copper, iron, nickel, alu~inum, cobalt, and alloys thereof including brass.
Additionally, a process for preparing a metal surface for adhesion to rubber, comprises the s~eps of: sputter etching with an ion beam a coated metal surface, etching said surface so that a coating of from about 5 to about 4,000 angstrom units is obtained, and wherein said coating surface is selected from the group consisting of steel, zinc, copper, brass, iron, nickel, aluminum, cobalt, and alloys ~hereof including brass.
In general, a metal item having rubber adhered to a surface thereof, co~prises: the metal item, said metal surface treated by an ion beam sputter deposition metal or sputter etching; the rubber adhered to said treated metal surface.
BEST MOD FOR CARRYING OUT THE I~ENTlON

In the production of rubber articles such as hose, pneumatic tires or power transmission belts such as V-belts, too-thed posltive drive belts, etc., lt is generally necessary to reinforce the rubber or elasto-merîc product. In the past, textile materials have been employed for this purpose. ~lowever, wire cord has been fo-und to be more desirable under certain conditions of use, for example, in pneumatic tires of the radial ply type. Mc~ximum reinforce~.ent of the rubber is obtained when maximum adhesion is produced and retained between the laminate of rubber and the metal reinforcing element as used to form a unitary~
structure. Of equal importance is the requirement that, for example, the laminate of the reinforcing metal element and rubber remain in a bonded relation-ship with each other throughout the useful life of the reinforced structure in which the lamina-te is used.
It has now been found that improved rubber-to-metal adhesion is achieved by applying or directing an ion beam onto a metal surface to which rubber is to be adhered. ~enerally, any metal substrate can be utilized to which rubber is to be adhered including iron, nickel, aluminum, and the like, with steel being the preferred substrate. The metal substrate can generally be in any form such as tiré cords, tire beads, reinforcing material in conveyor belts, rein-forcing material in hoses, belts, and the like. To improve adhesion of the rubber to a metal, the sub-strate preferably has a metallic coating thereon.
Examples of coating metals, or substrate metals if no coating metals are utilized, include iron, steel, zinc, copper, nickel, aluminum, cobalt, and alloys thereof such as brass, with brass or copper being preferred. By brass, it is meant essentially a copper-zinc alloy containing from about 60 percent to about 75 percent by weigh~ of copper and accordingly from about 25 to about 40 percent by weight of zinc. A
desired amount of copper ranges from about 60 to about 70 percent by weight.

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The ion beam is utilized in one of two manners in which to produce a desired finish or treat-ment upon the metal. The first procedure relates to ion beam sputter deposition, that is wherein the ion beam is direc-ted upon a metallic target such as copper or zinc and then the ions formed thereof directed to the substrate to be treated. In this embodiment, the thickness of the coating applied can range up to about 4~000 angstroms, as from abotlt S
angstroms, desirably from about 200 to abo~lt 2,000 angstroms and preferably from about 500 to about 1,000 angstroms.
The second ion beam treatment relates to an etching of the metallic article. That is, in this treatment or process, a coating or the surface of the metallic item is actually removed. Thus, a metallic substrate is ~enerally coated with any of the above metals in any conventional manner as by electroplat-ing, electroless plating, and the like The ion beam is then directed onto the substrate and utilized to partially remove a portion of the coating or to etch it. The application is continued until a desired surface is obtained. The coating can be continuous or discontinuous as when a specific pattern or design is made, as for example using an obstruction to mask par~
of the ion beam. The thickness of the remaining coat-ing can be the same as set forth above.
It is understood that the term "ion beam"
does not relate to conventional plasma deposition processes such as RF sputt~ring or electron-b~am evaporation. An ion beam deposition or etch relates to a narrow beam directed at a specific target, be it the coating material or the ob~ject to be etched.
Furthe~more, the ion beam technique offers several advantages over the conventional p].asma treatments.

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These include bet~er adhesion of the target to the substrate, purer deposits with fewer gas inclusions, minimal substrate heating and a larger variety of target materials that can be ion-beam sputtered.
The preparation of an ion beam or use there-of can be in accordance with any kno~m structure or technique such as those set Forth in the literature.
Of course, to apply a continuous coating or etching, the substrate or a~ticle can be moved back and forth, rotated, or.the like, such that a consistent or uni-form ion beam treatment thereof is made. The litera-ture which is hereby fully incorporated by reference with regard to utilizing an ion beam deposition or etching technique is as follows:
"Adherence of Ion ~eam Sputtered Deposited Metal Films on H-13 Steel" by Michael Mirtich, Lewis Research Center prepared for the 27th National American Vacuum Society Symposium, Detroit, Michigan, October 14-17, 2Q 1980;

"Advances in Low ~nergy Ion Beam Technology," by W.
Laznovsky, published in Research and Development, August 1975, pages 47-55;
"Ion Beam Techniques for Thin and Thick Film 3eposi-tion,'~ by C. Weissmantel, H. Erler, and G. Reisse, Surface Science 86 (1979), North-Holland Publish-ing Company, pages 207-210;

"Ion Beam Texturing" by Uayne Hudson of the NASA
Lewis Research Center, Cleveland, Ohio, published in the Journal of Vacuum Technology, Volume I4, No. 1, January and February 1977, pages 286-287;

5~

_g "Optical Properties of Ion Beam Textured Materials"
by Hudson, Weigand, and Mirtich, Lewis Research Center, in paper presented to the Sixth Annual Symposium on Applied Vacuum Science and Technology, Tampa, Florida, February 14-16, 1977;

"Ion Beam Sputtering of Flouropolymers" by Sovey, NASA
Lewis Research Center, Cleveland, Ohio, published in the Journal of Vacuum Science and Technology, March-April, 1979, pages 813-814; and "Characteristics of Ion-Beam-Sputtered Thin Films,"
by Kane and Ahn of IBM, published in the Journal of Vacuum Science and Technology, March-April, 1979, pages 171-172.

With regard to improved rubber adhesion, the ion beam is generally from an argon source. In general, the ion beam diameter can range from about 1 to about 30 centimeters with a diameter of from about 3 to about 30 centimeters being preferred. The ion source can operate at beam energies of from about 100 to about

2, oob electron volts with from about 500 to about 1,500 electron volts being preferred. Beam current density can range up to 2 milliamperes per cubic cen~
meter with about 0.5 milliampere per cubic centimeter to 1.0 milliamperesper cubic centimeter being preferred.
Examples of a specific ion beam machine includes those made by Veeco Industries, Inc., such as Model No. 3"
Microetch*17471 equipped with ~odel No. 0313-060-00 ion beam deposition assembly.
In the use of an ion beam deposition pro-cedure, the argon ions are generally directed upon a target so that the target material is released and directed through the use of focusing devlces to the * Trade Mark i7~

--~ o metal to be coated, be it a wire, a plate, or the like.
With regard to the etching treatment, a previously coated article is inserted in the path of the ion beam and rotated or moved until a desirable amount of the coating is removed. In general, ~he rate o~ rernoval and resulting surface texture is de~ermined by the ion beam energy and current denslty and by the angle with which the ion beam strikes the coated article. In addition, masking devices may be placed in the path of the ion beam prior to striking the coated article such that a pattern is etched into the remaining coating.
The present invention relates to the use of any common or conventional type of rubber or elastomer which is readily available or known to those skilled in the art. Generally, the rubber can be made from dienes having from 4 to 12 carbon atoms or from multi-ple dienes such that copolymers, terpolymers, etc.
thereof are made. Additionally, another class of rubber compounds includes those made from the reaction of dienes having from 4 to 12 carbon atoms wi~h a vinyl substituted aromatic compound having from 8 to 12 carbon atoms. A typical example is styrene-butadiene copolymer. Still other rubbers include nitrile rubber, polychloroprene, ethylene-propylene-diene rubber (EPDM), and the like. A preferred class of rubber compounds include cis-1,4-polyisoprene, either synthe-tic or natural, polybutadiene, the copolymer of styrene-butadiene, and the like. With regard to the rubbers, they are prepared in conventional and well known manners and thus have conventional amounts of various additives therein such as fillers, e.g., carbon black, accelera--tors, curing agen-ts, stabilizers such as antioxidants, resins, metal salts, and the like. Such rubber com-~7æ~

pounds, as noted, are w211 known to the rubber in-dustry and are conventional. The rubber compound or elastor.ler is made up according to any conventlonal manner and then applied in a conventional manner to the steel item or subs~r~te, be it a tire cord, reinforce-ment for a conveyor belt or hose, or the like.
It has been ~expectedly found that the ion beam-treated mekal yields greatly improved rubber adhesion and improved moisture aged adhesion thereto as to untreated surfaces.
Specific uses for the present invention in-clude the application of rubber to tire cord, wherein the tires can be passenger tires, off-the-road tires, truck tires, and the like. Another utility of the present invention relates to metal wire reinforced rubber such as belts, hoses, conveyor belts, and the like. In fact, the present invention relates to any wire rubber reinforced article.
The invention will be better understood by reference to the following examples.

EXA~IPLE 1 A. Test sample preparation.
The composition of the rubber compound used for wire adhesion testing is described in Table I.
This composition was prepared by mixing the rubber in a Banbury with carbon black and other ingredients as specified in Table I. Sulfur, accelerator, and the cobalt carb~xylate were then milled into the black stock. The resulting composition was sheeted out to 0.80 centimeters for use in fabrication of wire ad-hesion test pieces.
Adhesion was evaluated using the Tire Cord ~. ~

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Adhesion Test (TCAT). Sanples were prepared and tested according to the procedures described by A. W. Nicholson, D. I. Livingston, and G.S. Fielding-Russell, Tire Science and Technolo~y (1973) 6, 114; G. S. ~ielding-_ Russel.l and D.I~ Livingston, Rubb_r Chemistry~
Technology (1980) 53, 950; and R. L. Rongone, D. W.
Nicholson and R. E. Payne, U. S. Patent No. 4,095,465 (June 20, 1978)~
Test samples were cured 56 minutes at 135C.
Adhesion tests were perEo~med with-in 24 hours after curing and after aging by submersion in 90C water.

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B. Wire Preparation Three 30 centimeter sections of 0.10 centimeter diameter steel wires containing 3~000 angstrom brass (66 percent copper, 34 percent æinc) coatings were rotated in the path of a 10 centimeter argon ion beam. The ion energy and current density were adjusted such that after lO minutes, 500 angstroms of the original coating remained. A pressure of 3.9 x 10 2 Pa was maintained in the vacuum chamber at all times during the etching.
Sections of 6.3 centimeter length were cut from each treated wire and used to prepare the adhesion test samples. Table II compares the adhesion thus obtained with the ion beam etched wires to those obtained with untreated wire. The numbers in the table represent the average of two test values.
From the adhesion data, it can be seen that the ion beam etched wire displayed a substantial ad-vantage in aged adhesion over the untreated brass wire.

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A copper disk, 13 centimeters in diameter, was placed in the path of a lO centimeter argon ion beam and cleaned for 0.5 hour using ,a beam energy of 1,000 ~ V. and a current density of 2 mA/cm . Three 30 centimeter sections of O.lO centlmeter steel wires were inserted into the -vacuum chamber and rotated in the ion beam for 0.5 hour using the above conditions.
Tl~e ion beam was then directed onto the copper target such that copper was removed and re-deposited on the steel wire. This was continued until a 600 angstrom coatin~ of copper had deposited on the wire.
Test pieces were prepared and tested as described in Example l. Table III compares the ad-hesion for the ion beam plated wire with that from an electroplated brass wire and the bare steel wire. It can be seen that the sputter deposited copper-plated displayed an improvement in adhesion over the steel wire and an improvement in aged adhesion over the electroplated brass wire.

E ~ ~PLE 3 Following the procedures in Example l, three 30 centimeter sections of 4 x 0,22 millimeter brass (63 percent copper, 37 percent zinc) plated steel wire cables were rotated in a lO centimeter argon ion beam sourceO The original brass plating of 2 J 200 angstroms was etched to 500 angstroms. Table IV com-pares the adhesion values for the etched wire with those for the untreated wire. It can be seen that improved aged adhesion was obtained with the etched wire.

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~l8-Following the procedures cf Example 2, three 30 centimeter sections of steel 4 x 0.25 millimeter wire cables were coated USillg sputter deposition with 500 angstroms of copper. Table V compares the adhesion values for the sputter deposited wire with those for the base steel wire and electroplated brass wire.
I~ can be seen that the spu~ter deposited wire gave improved adhesion over the steel wire and improved aged adhesion over the electroplated brass wire.

Ha~ing described the best mode and preferred embodiments of the invention in detail, in accordance with ~he patent statutes, the scope of the invention is measured by the scope of the attached claims.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for preparing a metal surface for adhesion to rubber, comprising the steps of:
applying an ion beam sputter deposition metal to a metal substrate; and applying said deposition metal to said metal substrate until a coating of from about 5 to about 4,000 angstrom units is obtained and forming the metal surface;
wherein said deposition metal is selected from the group consisting of steel, zinc, copper, iron, nickel, aluminum, cobalt, and alloys thereof including brass.

2. A process according to claim 1, wherein the thickness of said coating is from about 500 to about 1,000 angstrom units.

3. A process according to claim 1 or 2, including applying rubber to said coated metal surface.

4. A process according to claim 1, wherein rubber is applied to said coated metal surface, said rubber being selected from the group consisting of dienes having from 4 to 12 carbon atoms, and interpolymers thereof, interpolymers made from dienes having from 4 to 12 carbon atoms and vinyl substituted aromatics having from 8 to 12 carbon atoms, nitrile rubber, EPDM, poly-chloroprene, and combinations thereof.

5. A process according to claim 4, wherein said metal item is a tire cord, or a tire bead, and wherein said rubber is selected from the group consisting of natural or synthetic cis-1,4-poly-isoprene, polybutadiene, or styrene-butadiene rubber, and wherein said coating is copper.

6. A process for preparing a metal surface for adhesion to rubber, comprising the steps of:
sputter etching with an ion beam a coated metal surface;
etching said surface so that a coating of from about 5 to about 4,000 angstrom units is obtained, and wherein said coating surface is selected from the group consisting of steel, zinc, copper, brass, iron, nickel, aluminum, cobalt, and alloys thereof including brass.

7. A process according to claim 6, wherein the thickness of said coating layer is 500 to 1,000 angstrom units.

8. A process according to claim 6 or 7, including applying a rubber to said treated surface and obtaining good adhesion and good moisture aged adhesion.

9. A process according to claim 6, including applying a rubber to said treated surface and obtaining good adhesion and good moisture aged adhesion said rubber being selected from the group consisting of dienes having from 4 to 12 carbon atoms, and interpolymers thereof, interpolymers made from dienes having from 4 to 12 carbon atoms and vinyl substituted aromatics having from 8 to 12 carbon atoms, nitrile rubber, polychloroprene, EPDM, and combinations thereof.

10. A process according to claim 9, wherein said rubber adhered item is a tire cord or a tire bead, and wherein said rubber is selected from the group consisting of natural or synthetic cis-1,4-polyisoprene, polybutadiene, or styrene-butadiene rubber, and wherein said coating is copper.

11. A metal item having rubber adhered to a surface thereof, comprising:
the metal item, said metal surface treated by an ion beam sputter deposition metal or sputter etching;
the rubber adhered to said treated metal surface.

12. A metal item according to claim 11, wherein said treatment is said ion beam deposition of a coating metal, wherein said coating metal is selected from the group consisting of copper, steel, zinc, nickel, aluminum, cobalt, iron, and alloys thereof including brass, and wherein the thickness of said coating metal ranges from about 5 to about 4,000 angstrom units.

13. A metal item according to claim 11, wherein said rubber is selected from the group consisting of dienes having from 4 to 12 carbon atoms, and interpolymers thereof, interpolymers made from dienes having from 4 to 12 carbon atoms and vinyl sub-stituted aromatics having from 8 to 12 carbon atoms, nitrile rubber, polychloroprene, EPDM, and combinations thereof.

14. A metal item according to claim 13, wherein said item is a tire cord, or a tire bead, and wherein said coating is copper.

15. A metal item according to claim 11, wherein said metal surface coating is selected from the group consisting of copper, steel, zinc, iron, nickel, aluminum, cobalt, and alloys thereof including brass, wherein said treatment is said sputter etching, and wherein the thickness of said coating ranges from about 5 to about 4,000 angstrom units.

16. A metal item according to claim 11, wherein said rubber is selected from the group consisting of dienes having from 4 to 12 carbon atoms, and interpolymers thereof, interpolymers made from dienes having from 4 to 12 carbon atoms and vinyl sub-stituted aromatics having from 8 to 12 carbon atoms, nitrile rubber, polychloroprene, EPDM, and combinations thereof.

17. A metal item according to claim 16, wherein said item is a tire cord, or a tire bead, and wherein said coating is copper.