CA1081555A

CA1081555A - Vapor treatment of metal tire cord

Info

Publication number: CA1081555A
Application number: CA264,917A
Authority: CA
Inventors: Grover W. Rye; Karol Marencak
Original assignee: Goodyear Tire and Rubber Co
Current assignee: Goodyear Tire and Rubber Co
Priority date: 1975-12-29
Filing date: 1976-11-04
Publication date: 1980-07-15
Also published as: AU505625B2; FR2337031A1; GB1559385A; JPS5282986A; FR2337031B1; IT1069985B; NL7614545A; BE849929A; MX145884A; AU1976576A; JPS578187B2; ZA766704B; NL183533B; DE2652420A1; NL183533C; DE2652420C2

Abstract

INVENTORS: Grover W. Rye and Karol Marencak INVENTION: VAPOR TREATMENT OF METAL TIRE CORD

Abstract of the Disclosure Brass coated steel tire cord is treated with vaporized benzotriazole and/or other treatment agents to promote corrosion resistance and cord to rubber adhesion retention.

Description

~081~i55 This invention relates to the treatment o~ brass coated steel cord to prevent corrosion of the cord and to improve cord/rubber adhesion retention.
Pneumatic vehicle tires are often reinforced by means oP cords prepared from brass coated steel filaments.
This tire cord is frequently high carbon steel or high carbon steel cord with a thin layer of alpha brass. The cord may be a monofilament, but normally is prepared from several filaments which are stranded together. The fila- -ment is coated with brass, cold drawn and then stranded to form the cord. In most instances, normally depending upon the type of tire being reinforced, the strands of filaments are further cabled to form the final cord.
Brass plated steel wire tire cords are subject to corrosion of the steel structure and oxidation of the brass plating if improperly handled prior to incorporation into a tire. Corrosion and oxidation can result in poor adhe-sion between the cord and rubber and more importantly in a deterioration of the physical properties of the cord.
Various chemical reagents such as benzotriazole (BTA) have been proposed to protect such wire against corrosion and oxidation. These reagents normallly have been applied by immersing the wire in a water solution of the reagent. The wire is then dried to remove the water.
The reagents react with wire to offer it protection agains-t oxidation and/or corrosion. For example, BTA reacts with the copper to~form a polymer layer. This layer must be sufficiently thin to allow a sulfur/copper bond to be formed between the wire and the adjacent rubber within the - ,. .
I` ~ . . .. .

O~lSS5 tire, and yet the film must be of such a con-tinuous uni-formity as to facilita-te resistance to corrosion.
Water application of reagents such as BTA re-quires lengthy immersion and drying times which can be 5 expensive in commercial operations. The poor wetability of metal cord contributes to the length of the immersion time.
The porosity of the brass coating presents the possibility that water may be occluded and therefore di~ficult to re-move by drying. There is also the possibility -that i-t will 10 be difficult for the water to penetrate the porous openings because of surface tension effects. Where the tire filament is freshly drawn, the filament is cooled by the water immersion thereby requiring expensive reheating of the cord both to dry the cord and to promote the reaction be-15 tween the reagents and the cord. It is therefore necessary that a method be found which does not require the use of expensive equipment and which permits the rapid treatment of the cord.
It is desirable to provide an efficient 7 low cost 20 method of applying protective agents to brass coated steel wire, said method being capable of rapidly treating the wire J
and reaching even remote surfaces of the wire. It is also desirable to provide a method which will not require the use } drying equipment or other expensive and time consuming 25 follow-up treatmentsO It is further desirable to provide treated brass coated steel tire cord possessing effective corrosion resistance.
The invention can be ~', 8~l5SS
accomplished, in general terms, by trea-ting the cord during the course of its preparation or thereafter with reagents capable of promoting and/or retaining adhesion between the metal cord and adjacent vulcanized rubber and/
or capable of improving the resistance of the cord to corrosion prior to incorporation into the tire during and after incorporation into the tire, said reagent being in a gaseous state, either saturated or unsaturated. Said reagents include compounds capable of preventing the oxidation of the steel substrate and/or capable of prevent-ing the corrosion of the brass.
In accordance with this invention, in a proeess of treating a filament of steel having a brass coating thereon with a reagent reactive with the brass and/or any exposed surface of the steel filament, the improvement is characterized by (A) continuously passing a steel filament having a microscopically porous brass coating thereon through the vapors of molten benzotrialzole and (B) subjecting the treated filament to a water vapor treatment; wherein said benzotriazole vapor is heated to a temperature of up to about 180C., to form primarily a monomolecular coating on said filament so as to promote both corrosion resistance to ~-said filament and aged adhesion between a cord thereof of such stranded filaments and adjacent, adherent sulfur vulcanized rubber.
In further accordance with this invention, in a process of treating a stranded cord comprised of filaments of steel having a brass coa-ting thereon with a reagent reactive with the brass and/or any exposes surface of the steel filaments, the improvement is characterized by (A) continually passing a cord of stranded steel filaments - .

~ 3 .. .. .. . ... ..

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having a microscopically porous brass coa-ting thereon through the vapors of molten benzotriazole and (B) subjecting the treated stranded cord to a water vapor -treatment; wherein said benzotriazole vapor is heated to a temperature o~ up to about 180C., to form primarily a monomolecular coating on the filaments of said cord so as to promote both corrosion resistance thereto and aged adhesion between said cord and an adherent sulfur vulcanized rubber.
The process of the present invention can be used to treat the filament after drawing but before stranding, after stranding to form the cord, in the form of woven fabric or as multiple ends such as may be used at a creel calendering operation. In fact, the method can be used at any point in the manufacture of the cord and even subse-quent thereto, the only requirement being that the cord be treated at some point before it becomes a reinforcing element in the tire or other rubber product.
Any reagent which can be vaporized can be used within the practice of the present invention including, but not limited to, reagents selected from the group con- `~
sisting of precipitation compounds, oxidizing compounds, and compounds having the following structural formula ~A

N /
H
wherein the adjacent carbon atoms are joined -to form a benzene ~r nephthyleze ring, said ring being substi-tuted ., ~

~ ~ 8 ~ 5 S S
(for example, with a single methyl group) or unsubstituted and wherein A and B are selected from the group consisting of -N- or -CH-, with the proviso that A and B are never both -CH-, said agent being in the ~orm of a gas. The precipitation compounds include compounds selected ~rom the group consisting of organic borates~ organic phosphate and organic metaphosphates. The oxidation compounds in-clude organic nitrites.
The precipitation compounds of~er their protec-; 10 tion through an indirect oxidizing (buffering) mechanism. The oxidation compounds offer protection by directly oxidizing metallic ions in the substrate surface.
Examples of organic compounds which can be usedin the practice of the present invention include organic alkyl~ cycloalkyl and aryl derivatives of m-boric acid, o- boric acid and pyro-boric acid as well as m-g o-, pyro-and hypo-phosphoric acid.
Preferably the vapor contains some moisture since water enhances the ability of the agents to prevent corro-sion and to provide improved aged adhesion, that is, toretain to some measure the original adhesion. Said moisture can be introduced~ for example~ by introducing steam into the gaseous atmosphere in a catalytic amount. Another embodiment involves exposing the cord to an atmosphere having a high moisture content subsequent to the vapor treatment.
The vapor technique has the advantage of per-mitting the reagent to reach the furthest recesses of the stranded cord even when wrapped upon a spool~ It also permits the reagent to enter the microscopic pores of the ~ ~ .

brass coating.
An~ manner of exposing the cord to the vapors will result in some improvement in corrosion or oxidation resistance.
The cord can be treated while at room temperature or after being heated. For example, a filament or a cord can be preheated to a temperature higher than the temper-ature of the vapor to which it is exposed, for the time necessary to provide the required degree of reaction. This results in a reaction in the gaseous phase only~ and there-~ore the only reactive material deposited is that which reacts with the available copper or steel on the wire surface. It is theorized that monomolecular films may be deposited in this fashion. The resulting thin fllms thereby create a minimum amount of interference with the sulfur reaction required for bonding the wire to rubber.
Concentration of the vapor, temperature of the vapor, and temperature of the wire determine the time required for the reactions to occur. Optlmum condi-tions can be routinely determined for each system.
In one embodiment of the present invention, a wire or cable with a temperature below the temperature of the vapor is passed through the chamber, and the reagent is condensed on the surface of the wire reacting simultan-eously therewith. The amount deposited will depend upon the vapor concentration, vapor temperature, time exposed and the incoming and exiting temperatures of the wire.
Again, optimum conditions can be routinely determined.
This wire can be used as treated or subsequently heated to vaporize excess reactants and/or to continue the reaction , `~

i;SS

between the reagent and the cord to the desired state of completion, if the desired state has not already been reached.
The agents can be used alone or in combination.
Likewise a series of units can be used9 each containing a different agent. It is pre~erred that one stage of the treatment involve the use of a BTA-type chemical agent.
If the agents are to be used in combination, one must naturally consider vapor pressure effects 7 miscibility effects~ potential interaction between the agents in liquid or vapor form at the temperatures being used~ etc. None of these remarks are intended to ~e limitations upon the process of the present invention but are intended only to be used as guidelines.
The brass coated steel cord which can benefit by the practice of the present invention includes cord treated by methods or with material other than described herein, but which are still susceptible to oxidation and/or corro-sion.
If moisture is desired, it can be introduced, for example, by the introduction of steam into the reaction area, the addition of water to the molten agents, etc. The manner by which the water is introduced is not critical.
There is no reason why the present method can not be combined with other methods. For example, the wire can be first treated in an aqueous solution of one reagent followed by treatment with the BTA type material in vapor ~ form.
t~ In selecting agents~ order of treatment, etc., one should consider that film formation with compounds such as ~ ~ .

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~'~

~o~sss BTA can possibly cover the exposed steel so as to minimize contact thereof with other agents.
It is believed that a reduction of the porosity~
for example by film formation on the cord sur~ace, may result in improved corrosion resistance and adhesion retention As a guideline, but not a limitation~ one can measure the porosity of the wire by immersing it in a potassium ferrocyanide solution. The darker the resulting cord~ the grèater its porosity. In this way the degree of porosity can be estimated before, during, and after treat-ment.
It should be noted that the vapor phase need not be formed strictly from the molten form of the agent. For example, if the agent tends to sublime, that is, passes from the solid to the gaseous stage without passing through the liquid stage7 it can still be used in the vapor treat-ment method, the only critical factor of said method being that the wire is exposed to the vapor of the agentO Like-wise, whether an agent that is a liquid or a solid at roomtemperature is not critical so long as it is contacted with the wire in its vapor state.
The brass coating of a typical brass coated steel cord is microscopically porous, thereby exposing small areas of steel surface to any surrounding environment. It is believed that BTA interacts with copper in a brass coating to form a polymeric complex o~ BTA plus copper.
This polymeric complex is insoluble in most solvents and serves as a protective barrier to any environmental degra-dation of the underlying brass. On the other hand~ anions ~.', ~- .
:;

~8~SS~;

from the precipitation and oxidation compounds, it is theorized~ interact with iron and iron oxide from steel sur~aces e~posed through microscopic pores to form an adherent oxide film which protects the steel. It is not necessary that the barrier layers of polymeric complexes adsorbed be extremely thick. In fact~ as mentioned ear-lier, such layers should not be so -thick as to inter~ere ~th the sulfur reaction required for bonding the wire to the rubber~ the adhesion of rubber to metal cord requiring the formatio~ of copper-sulfur bonds.
The practice of the present invention results in increased surface protection of brass coated steel prior to rubber encapsulation and improved aged adhesion of Yulcan-ized brass coated steel/rubber composites. It also pre-vents cord failure due to excessive corrosion during theuse of the product, e.g. 9 a tire being reinforced with the cord.
The rubber surrounding the metal can be any rubber, preferably diene rubbers such as natural rubber, rubbery copolymers of butadiene with styrene or acrylo nitrile~ polybutadiene and polyisoprene.
The fact that the adhesion between the copper in the brass and the adjacent rubber is dependent upon the presence of sulfur requires the use in the adjacent rubber of either free sulfur or a compound capable of donating sulfur such as 2-(morpholinodithio)benzothiazole.
Aged metal to rubber adhesion is particularly poor when the rubber contains oxygen, molsture, and an amine resin capable of releasing ammonia. For example, rubbers containing hexamethylenetetramine (HMTA) such as in a resorcinol/HMTA in situ resin system, where oxygen and moisture levels are suff~ciently high, can tend to have poor aged-adhesion to brass or brass coated steel~ The use of the present process is particularly beneficial in such systems. Further~ coatings on in-process wire protect the wire from deleterious effects of moisture (humidity) and oxidation, i.e., improve factory storage life.
By the term ~high-carbon~ steel as used in the present specification and claims~ applicant is referring to what is known as carbon steel, also called ordinary steel, also called straight carbon steel or plain carbon steel~ e.g., American Iron and Steel Institute Grade 1070 high-carbon steel (AISI 1070). Such steel owes its proper-ties chiefly to the presence of carbon without substantial amounts of other alloying elements. In this respect see Metals Handbook~ The American Society for Metals, Metals Park~ Cle~eland, Ohio.
The term "brass" includes a but is not limited to, alpha brass or compositions in which the major component is alpha brass7 i.e., which contain from about 65 to 75 percent copper and 35 to 25 percent zinc, respectively. `
The following examples contain illustrations of, but do not limit the practice of the present invention.
Example 1 A chamber 30 centimeters long was mounted at the exit of a wire drawing machine operating at a speed of 900 r meters per minute.
BTA was vaporized in this chamber with the melt temperature being maintained at 120 C. Drawn f~laments (brass coated steel) were passed through this chamberO

_9_ .. . . ....

5S5i Filaments treated in this manner were formed into a 5 x .25 cable.
The resulting cable was embedded in carbon black loaded polymer~ and the polymer vulcanized. Corrosion resistance on the bare cable and adhesion data on the vulcanized composite were obtainedO The results are listed below.
Original Wet Comp~ ~ d Corrosion Adhesion Adhesion Resistance ,~ ~ ;
iV ~ kilogramsJ ~kilo~amsJ t Untreated 57.0 29.0 Poor Treated ~5 38 Excellent Example 2 A chamber 30 centimeters long and approximately 6 centimeters high was equipped with suitable heaters.
BTA was melted in the bottom of this chamber and a wire cable passed through this vapor zone~ Test results on cable treated in this manner were as follows.
Sample 1 Expo. Melt Orig. Wet Co~ Corrosion Run Speed Time Temp. Adhes. Adhes. ~ Resistance (1) 30m/m .6 180C~ 53 32 Excellent

(2) 30m/m .6 120C. 55 27 Excellent

(3) 90m/m .2 180C. 5~ 28 Excellent Untreated ~ 57 25 Fair 5 (1) - Unvulcanized rubber soaked in water before the cable was embedded therein.
Exam~le ~
The chamber used in E~ample 2 was mounted on a strander running at 90 meters per minute. Test results on cables produced when exposing the cable with the melted BTA
at a temperature of 180 C. are as follows.

lO~lSSS

Original Wet Compound Corrosion Adhesion Adhesion Resistance Treated 52 30 Excellent Untreated 48 21 Fair In everyone of the above examples the treated cord pos-sessed a higher wet compound adhesion and better corrosion resistance than the untreated cordO
Oncs the cord is plated with the brass7 treatment can begin. Treatment can occur with the reagents between the plating and drawing steps or between the drawing and stranding steps and even on the final cord prior to cal-endering. Where the vapor treatment results in film for-mation, it is preferably accomplished before drawing since drawing will naturally destroy the film continuity.
Any compound could have been substituted for BTA
type compounds, which complexes with the copper in the brass to form an insoluble film~ ~.e., insoluble in any of the environments to which the material is to be exposed.
These compounds include triazoles, imidazoles and inda-zoles. Such compounds include those compounds conforming to the structural formula recited earlier herein.
The rubber used in the earlier described working examples was a carbon black loaded natural rubber.
Any of the previous working examples could have lnvolved a subsequent heat treatment and/or exposure of the wire to water vapor.
Other materials which can be used, for example, to treat wire using the present method are triethyl phos-phate and amyl nitrite.
While certain representative embodiments and ~ D8~SSS

details have been shown for the purpose o~ illustrating the invention~ it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the spirit or scope of the invention.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. In a process of treating a filament of steel having a brass coating thereon with a reagent reac-tive with the brass and/or any exposed surface of the steel filament, the improvement characterized by (A) continuously passing a steel filament having a micro-scopically porous brass coating thereon through the vapors of molten benzotriazole and (B) subjecting the treated filament to a water vapor treatment; wherein said benzotriazole vapor is heated to a temperature of up to about 180°C., to form primarily a monomolecular coating on said filament so as to promote both corrosion resistance to said filament and aged adhesion between a cord thereof of such stranded filaments and adjacent, adherent sulfur vulcanized rubber.

2. In a process of treating a stranded cord comprised of filaments of steel having a brass coating thereon with a reagent reactive with the brass and/or any exposed surface of the steel filaments, the improve-ment characterized by (A) continually passing a cord of stranded steel filaments having a microscopically porous brass coating thereon through the vapors of molten benzo-triazole and (B) subjecting the treated stranded cord to a water vapor treatment; wherein said benzotriazole vapor is heated to a temperature of up to about 180°C., to form primarily a monomolecular coating on the filaments of said cord so as to promote both corrosion resistance thereto and aged adhesion between said cord and an adherent sulfur vulcanized rubber.