CA1115607A - Metal wire cord - Google Patents
Metal wire cordInfo
- Publication number
- CA1115607A CA1115607A CA318,626A CA318626A CA1115607A CA 1115607 A CA1115607 A CA 1115607A CA 318626 A CA318626 A CA 318626A CA 1115607 A CA1115607 A CA 1115607A
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- Canada
- Prior art keywords
- weight
- metal wire
- cobalt
- ternary alloy
- zinc
- Prior art date
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- Lining Or Joining Of Plastics Or The Like (AREA)
- Chemically Coating (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Tires In General (AREA)
- Ropes Or Cables (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A metal wire cord which comprises a metal wire and a ternary alloy of Cu-Zn-Co coated on the surface of said metal wire. The wire cord has high drawability, excellent adhesion to rubber and is highly resistant to corrosion by saline water.
A metal wire cord which comprises a metal wire and a ternary alloy of Cu-Zn-Co coated on the surface of said metal wire. The wire cord has high drawability, excellent adhesion to rubber and is highly resistant to corrosion by saline water.
Description
- l~lS6~7 METAL WIRE CORD
This invention relates to a metal wire cord and more particularly to a metal wire cord having drawability and good adhesion to rubber in saline water. The cord are particularly useful in tire reinforcement.
A tire cord hitherto used consists of a steel wire whose surface is plated with brass containing 63.5 to 72~ by weight of copper. This type of wire is required to be free from drawbacks such as breakage during the drawing process or peeling of a plated layer during that process. Par-ticularly in recent years, a strong demand has been made for the safety and waterproofness of a steel-reinforced tire.
Importance is further attached not only to the original bonding force of the steel cords to rubber but also to the bonding force of the steel cords to rubber under heat and in water.
Generally, the adhesion of steel cords to rubber is improved by reducing the copper content of the brass plated on the steel wires. However, a smaller copper content than 63~ by weight has the drawback that the~ phase having a body centered cubic (b.c.c.) lattice structure precipitates in the ~ phase having a face centered cubic (f.c.c.) lattice structure in the brass. As a result, steel wire is often broken during the drawing process following the plating process in steel cord manufacture. There is a decrease in the life of the drawing dies, and noticeable irregularities appear on the surface of the plated layer.
'q~`
Accordingly, this invention seeks to provide a metal wire which, during the drawing process, is free of the prior art problems but has good adhesion to rubber.
According to the invention, there is provided a metal wire cord comprising a metal wire, and a coating layer coated on the surface of said metal wire and formed of a ternary alloy of cooper, zinc and cobalt containing 0.1 to 50~ by weight of cobalt.
This invention will be more fully understood when taken in conjunction with the appended drawing, in which:
Figure l shows the equilibrium phase diagram of a ternary alloy of Cu-Zn-Co; and Figure 2 schematically illustrates the process of testing the adhesivity of a metal wire to rubber.
This invention is based on the discovery that addition of cobalt (Co) to brass as a third component elevates the drawability of said brass when plated on a steel wire without reducing the adhesivity of said brass to rubber.
As seen from Figure 1 showing the equilibrium phase diagram of a ternary alloy of Cu-ZnCo, addition to Co to a binary alloy of Cu-Zn causes a line along which the ~ phase precipitates to be shifted toward a region where the Cu/Zn ratio has a small value, thereby restricting the preci-pitation of the ~ phase and supposedly elevating the draw-ability of said ternary alloy. A ternary l~S6e}7 alloy of Cu-Zn-Co has a higher adhesivity to rubber than any composition of a binary alloy of Cu-Zn even under a highly corrosive condition such as that in which saline water is present, and enables rubber compounds, which are to be bonded to said ternary alloy,to be selected over a broader range. This advantageous effect is supposed to arise from the fact that a cobalt-containing metal sulfide formed in an interface between the ternary alloy of Cu-Zn-Co and adjacent vulcanized rubber remains appreci-ably stable physically as well as chemically. Further, the above-mentioned metal sulfide may contribute to the fact that the ternary alloy of Cu-Zn-Co has the higher resistance to corrosion by saline water than that of the . binary alloy of Cu-Zn.
Copper, zinc and cobalt constituting the ternary alloy used in this invention preferably have such.pro- :
portions as substantially suppress the precipitation of ;~
the ~ phase, in other words, allow for the presence of the a phase alone in view of the drawability of the metal wire.
The Zn content of the ternary alloy of the Cu-Zn-Co used in.this inyention generally falls within the range of 10% to 45% by weight, preferably 20~ to 40% by weight.
The Co content of said ternary alloy generally stands at 0.1% to 50% by weight, preferably 0.5% to 30% by weight, .more preferably 1% to 20% by weight and most preferably 1% to 10~ by weight. The balance is Cu.
The metal wire of this invention is manufactured by ` ' _ 4 _ 1~156~7 coating the above-mentioned ternary alloy of Cu-Zn-Co on, for example, a steel wire. Said coating may be carried out by chemical, electrical, or fusion plating.
In addition to the direct plating of said ternary alloy, it is possible initially to plate the components separate-ly one atop another and thereafter thermally diffuse the components uniformly throughout the whole mass, thereby providing a desired ternary alloy.
The convenient coating ~rocess is to plate on the steel wire Cu, Zn and Co in the order mentioned by an ordi-nary electrical plating method and diffuse the metals into each other under heat and time sufficient to provide the ternary alloy of Cu, Zn and Co. The diffusion may be con-yeniently carried out at 400QC to 60QC for 5 to 20 seconds.
The metal wire of this invention thus manufactured can be drawn by the ordinary wire-drawing machine to produce fine wires for reinforcement of rubber, for example, steel tire cords. The wire is generally drawn at such rate that the initial cross sectional area of a drawn wire reduces by 85 to 97~.
This invention will be more fully understood from the following examples. Throughout the examples, all percenta~es are by weight, unless otherwise expressly indicated.
Example 1 The surface of a steel wire having a diametér of 1.24mm was coated by electrical plating with Cu, Zn and Co separately in the order mentioned to produce a 3-ply ..
. . .
11156~7 plated layer. Thereafter, the components were thermally diffused uniformly throughout the platedmass at 550C for 5 to 30 seconds to provide ternary alloys of Cu-Zn-Co, 1~ thick, having the compositions of the samples Nos. 1 to 2 shown in Table 1 below.
Table l Composition and Drawability of Plated Alloy Cu(%) Co(%) Zn~%) (a/~a~))xlQQ(%~ Drawability 65.46.3 28.3 100 Higher
This invention relates to a metal wire cord and more particularly to a metal wire cord having drawability and good adhesion to rubber in saline water. The cord are particularly useful in tire reinforcement.
A tire cord hitherto used consists of a steel wire whose surface is plated with brass containing 63.5 to 72~ by weight of copper. This type of wire is required to be free from drawbacks such as breakage during the drawing process or peeling of a plated layer during that process. Par-ticularly in recent years, a strong demand has been made for the safety and waterproofness of a steel-reinforced tire.
Importance is further attached not only to the original bonding force of the steel cords to rubber but also to the bonding force of the steel cords to rubber under heat and in water.
Generally, the adhesion of steel cords to rubber is improved by reducing the copper content of the brass plated on the steel wires. However, a smaller copper content than 63~ by weight has the drawback that the~ phase having a body centered cubic (b.c.c.) lattice structure precipitates in the ~ phase having a face centered cubic (f.c.c.) lattice structure in the brass. As a result, steel wire is often broken during the drawing process following the plating process in steel cord manufacture. There is a decrease in the life of the drawing dies, and noticeable irregularities appear on the surface of the plated layer.
'q~`
Accordingly, this invention seeks to provide a metal wire which, during the drawing process, is free of the prior art problems but has good adhesion to rubber.
According to the invention, there is provided a metal wire cord comprising a metal wire, and a coating layer coated on the surface of said metal wire and formed of a ternary alloy of cooper, zinc and cobalt containing 0.1 to 50~ by weight of cobalt.
This invention will be more fully understood when taken in conjunction with the appended drawing, in which:
Figure l shows the equilibrium phase diagram of a ternary alloy of Cu-Zn-Co; and Figure 2 schematically illustrates the process of testing the adhesivity of a metal wire to rubber.
This invention is based on the discovery that addition of cobalt (Co) to brass as a third component elevates the drawability of said brass when plated on a steel wire without reducing the adhesivity of said brass to rubber.
As seen from Figure 1 showing the equilibrium phase diagram of a ternary alloy of Cu-ZnCo, addition to Co to a binary alloy of Cu-Zn causes a line along which the ~ phase precipitates to be shifted toward a region where the Cu/Zn ratio has a small value, thereby restricting the preci-pitation of the ~ phase and supposedly elevating the draw-ability of said ternary alloy. A ternary l~S6e}7 alloy of Cu-Zn-Co has a higher adhesivity to rubber than any composition of a binary alloy of Cu-Zn even under a highly corrosive condition such as that in which saline water is present, and enables rubber compounds, which are to be bonded to said ternary alloy,to be selected over a broader range. This advantageous effect is supposed to arise from the fact that a cobalt-containing metal sulfide formed in an interface between the ternary alloy of Cu-Zn-Co and adjacent vulcanized rubber remains appreci-ably stable physically as well as chemically. Further, the above-mentioned metal sulfide may contribute to the fact that the ternary alloy of Cu-Zn-Co has the higher resistance to corrosion by saline water than that of the . binary alloy of Cu-Zn.
Copper, zinc and cobalt constituting the ternary alloy used in this invention preferably have such.pro- :
portions as substantially suppress the precipitation of ;~
the ~ phase, in other words, allow for the presence of the a phase alone in view of the drawability of the metal wire.
The Zn content of the ternary alloy of the Cu-Zn-Co used in.this inyention generally falls within the range of 10% to 45% by weight, preferably 20~ to 40% by weight.
The Co content of said ternary alloy generally stands at 0.1% to 50% by weight, preferably 0.5% to 30% by weight, .more preferably 1% to 20% by weight and most preferably 1% to 10~ by weight. The balance is Cu.
The metal wire of this invention is manufactured by ` ' _ 4 _ 1~156~7 coating the above-mentioned ternary alloy of Cu-Zn-Co on, for example, a steel wire. Said coating may be carried out by chemical, electrical, or fusion plating.
In addition to the direct plating of said ternary alloy, it is possible initially to plate the components separate-ly one atop another and thereafter thermally diffuse the components uniformly throughout the whole mass, thereby providing a desired ternary alloy.
The convenient coating ~rocess is to plate on the steel wire Cu, Zn and Co in the order mentioned by an ordi-nary electrical plating method and diffuse the metals into each other under heat and time sufficient to provide the ternary alloy of Cu, Zn and Co. The diffusion may be con-yeniently carried out at 400QC to 60QC for 5 to 20 seconds.
The metal wire of this invention thus manufactured can be drawn by the ordinary wire-drawing machine to produce fine wires for reinforcement of rubber, for example, steel tire cords. The wire is generally drawn at such rate that the initial cross sectional area of a drawn wire reduces by 85 to 97~.
This invention will be more fully understood from the following examples. Throughout the examples, all percenta~es are by weight, unless otherwise expressly indicated.
Example 1 The surface of a steel wire having a diametér of 1.24mm was coated by electrical plating with Cu, Zn and Co separately in the order mentioned to produce a 3-ply ..
. . .
11156~7 plated layer. Thereafter, the components were thermally diffused uniformly throughout the platedmass at 550C for 5 to 30 seconds to provide ternary alloys of Cu-Zn-Co, 1~ thick, having the compositions of the samples Nos. 1 to 2 shown in Table 1 below.
Table l Composition and Drawability of Plated Alloy Cu(%) Co(%) Zn~%) (a/~a~))xlQQ(%~ Drawability 65.46.3 28.3 100 Higher
2 64.69.7 25.7 100 Higher
3 62.74.9 32.4 100 Higher
4 60.810.0 29.2 100 Higher S0.030.0 20.0 100 High 6 55.19.8 35.1 100 Higher 7 44.220.3 35.5 100 High 8 41.234.6 24.2 100 High 9 34.940.0 25.1 100 High Control 10 64.0 _ 36.0 85* Low Control 11 60.8 _ 39.2 70 Low The plated steel wire was drawn 19 times on a continuous wet-type drawing machine, until the diameter wa~ reduced to 0.25mm. A commercially available alloy die was used. The rate of drawing was chosen to be 700m/min at a point where the wire passed the final die.
During the drawing process, the drawability of the plated wire was determined from the frequency at which ,.,~, , . . ~ , .
, ll~S6~7 the plated wire was broken and a decline in the effective life of the drawing die, the results being set forth in Table 1 above. The frequency of breakage was determined from the number of times one ton of a plated steel wire was broken, before the diameter was reduced to 0.2~mm.
The effective life of the drawing die was measured from the quantity of a plated steel wire which was drawn through the die. The term "higher" given under the item of drawability of Table 1 above denotes the case where the frequency of breakage was lower than 5 times/ton and more than 600 kg of a plate steel wire was drawn through the die. The term "high" represents the case where the frequency of breakage was 6 to 19 times/ton, and lG0 to 600 kg of a plated steel wire was drawn through the dieO
The term "low" indicates the case where the frequency of breakage was more than 20 times/ton and less than 100 kg of a plated steel wire was drawn through the die. The rate of drawing and the life of a drawing die are generally largely affected by the type of a die and the kind of a drawing lubricant. In this example, therefore, comparison was made between the drawabilities of the respective samples by applying the same type of a die, the same kind of a lubricant and the same type of a drawing machine.
Steel wires plated with the prior art binary alloy of Cu-Zn were tested as controls (samples Nos. 10 and 11 in Table 1). The drawability of these plated steel wires 1~156~7 was determined in the same manner as described above, the results being also indicated in Table 1.
Sample No. 10 represents the plating of brass, in which a plurality of plating baths of the same cyanide type were used. It has been experimentally proved that even where plating is carried out quite uniformly, a lower Cu content in the plating bath than 63% results in the precipitation of the ~ phase. Where any slight change occurred in the operatin~ condition of the above-mentioned plural platin~ baths, then the ~ phase sometimes precipitated in some of said baths whose Cu content was even slightly over 63%, thus giving rise to a plated structure in which the ~ and ~ phase was co-present. It has been experienced that a plated layer having such structure falls in drawability. The above-mentioned sample No. 10 decreased in drawability to support this fact.
Example 2 The surface of steel wires having diameters of 0.97mm, l.lOmm, 1.24mm and 1.60mm respectively were coated with Cu, Zn and Co separately in the order mentioned to provide a 3-ply plated layer. The three components were thermally diffused throughout the plated mass to form a ternary alloy of Cu-Zn-Co. The samples were drawn and twisted together to produce a steel cord plated with the ternary alloy of Cu-Zn-Co (hereinafter referred to as "a tire cord") having the structure and composition "
:,.,,^.,,~.. .
- . 11156~
indicated in Table 2.
Table 2 Tire cords manufactured for trial by plating the ~urface with a ternary alloy of Cu-Zn-Co Structure Diameter of Original dia-l 1 _ , --a drawn wire meter of a Cu Co Zn C~mL wire before ~] (%) ~) drawn ~mm~
. .. . ,. ... .. ..... . , .... , . .. . _ . _ . . . _ _ 2+7(Q.221+1 0.22 1.10 159.5 3.4 Remainder lx5(0.25~ 0.25 1.24 63.3 4O4 ., 3(0 20~l 1 0 20 1 0 9~7 ~6~ 3 ~1.2 To examine the adhesivity to rubber of the tire cords thus prepared, the samples of tire cords were inserted, as illustrated in Fig. 2 showing a test apparatus, in various rubber compounds in a vertical direction to the extent of 12.7mm length as measured from the lower end in conformity to the ASTM D222g. Thereafter, the rubber compounds were vulcanized. Each vulcanized rubber com-pound into which the samples of tire cords were vertically inserted was dipped in a 5% solution of sodium chloride at room temperature (18 to 25C) to the extent of about half the thickness of the rubber compound. After 4 or
During the drawing process, the drawability of the plated wire was determined from the frequency at which ,.,~, , . . ~ , .
, ll~S6~7 the plated wire was broken and a decline in the effective life of the drawing die, the results being set forth in Table 1 above. The frequency of breakage was determined from the number of times one ton of a plated steel wire was broken, before the diameter was reduced to 0.2~mm.
The effective life of the drawing die was measured from the quantity of a plated steel wire which was drawn through the die. The term "higher" given under the item of drawability of Table 1 above denotes the case where the frequency of breakage was lower than 5 times/ton and more than 600 kg of a plate steel wire was drawn through the die. The term "high" represents the case where the frequency of breakage was 6 to 19 times/ton, and lG0 to 600 kg of a plated steel wire was drawn through the dieO
The term "low" indicates the case where the frequency of breakage was more than 20 times/ton and less than 100 kg of a plated steel wire was drawn through the die. The rate of drawing and the life of a drawing die are generally largely affected by the type of a die and the kind of a drawing lubricant. In this example, therefore, comparison was made between the drawabilities of the respective samples by applying the same type of a die, the same kind of a lubricant and the same type of a drawing machine.
Steel wires plated with the prior art binary alloy of Cu-Zn were tested as controls (samples Nos. 10 and 11 in Table 1). The drawability of these plated steel wires 1~156~7 was determined in the same manner as described above, the results being also indicated in Table 1.
Sample No. 10 represents the plating of brass, in which a plurality of plating baths of the same cyanide type were used. It has been experimentally proved that even where plating is carried out quite uniformly, a lower Cu content in the plating bath than 63% results in the precipitation of the ~ phase. Where any slight change occurred in the operatin~ condition of the above-mentioned plural platin~ baths, then the ~ phase sometimes precipitated in some of said baths whose Cu content was even slightly over 63%, thus giving rise to a plated structure in which the ~ and ~ phase was co-present. It has been experienced that a plated layer having such structure falls in drawability. The above-mentioned sample No. 10 decreased in drawability to support this fact.
Example 2 The surface of steel wires having diameters of 0.97mm, l.lOmm, 1.24mm and 1.60mm respectively were coated with Cu, Zn and Co separately in the order mentioned to provide a 3-ply plated layer. The three components were thermally diffused throughout the plated mass to form a ternary alloy of Cu-Zn-Co. The samples were drawn and twisted together to produce a steel cord plated with the ternary alloy of Cu-Zn-Co (hereinafter referred to as "a tire cord") having the structure and composition "
:,.,,^.,,~.. .
- . 11156~
indicated in Table 2.
Table 2 Tire cords manufactured for trial by plating the ~urface with a ternary alloy of Cu-Zn-Co Structure Diameter of Original dia-l 1 _ , --a drawn wire meter of a Cu Co Zn C~mL wire before ~] (%) ~) drawn ~mm~
. .. . ,. ... .. ..... . , .... , . .. . _ . _ . . . _ _ 2+7(Q.221+1 0.22 1.10 159.5 3.4 Remainder lx5(0.25~ 0.25 1.24 63.3 4O4 ., 3(0 20~l 1 0 20 1 0 9~7 ~6~ 3 ~1.2 To examine the adhesivity to rubber of the tire cords thus prepared, the samples of tire cords were inserted, as illustrated in Fig. 2 showing a test apparatus, in various rubber compounds in a vertical direction to the extent of 12.7mm length as measured from the lower end in conformity to the ASTM D222g. Thereafter, the rubber compounds were vulcanized. Each vulcanized rubber com-pound into which the samples of tire cords were vertically inserted was dipped in a 5% solution of sodium chloride at room temperature (18 to 25C) to the extent of about half the thickness of the rubber compound. After 4 or
5 days, the tire cord was pulled out at the rate of 100 m/min. Determination was made of the percentage adhesivity (0 to 100%) of rubber to the tire cord, the results being indicated ln Table 3 below. The rubber compounds used consisted of commercially available tire ,_ .
11156~7 _ 9 _ rubber compounds A to G of different kinds shown in Table 3 below.
Table 3 Results of testing the resisiance of tire cords to vulcanized rubber in saline water bber compound A ~B C D -E F G
~ _ \ Day 5 5 4 4 4 4 4 Steel Tire Co ~
_ _ Control lx5(0.25~ A(66.7Cu-Zn) 7% 5% 13% 27% 40% 33% 40%
.. ~- B(66.3Cu-Zn) 8 17 10 _ 30 15 _ .. .. C(67.4Cu-Zn) 12 0 10 47 30 37 45 .. .. D(68.2Cu-Zn) 63 56 10 13 70 43 50 .. . E(63.7Cu-Zn) 43 7 17 30 0 30 70 . .. F(67.lCu-Zn) 8 20 3 33 40 30 40 .. .- G(70.5Cu-Zn~ 3 23 20 40 30 35 50 r _ _____.
Invention lx5(0.25) ~u-Zn-Co 63 63 37 53 50 45 45 2+7(0.22)+r 78 72 87 95 50 35 70 3+6(0.35)1 63 ~ ~ 85 ~ 63 80 Note: Numerals given in Table 3 above show the area of the surface of tire cords to which rubber adhered after the tire cords were dipped in saline water and thereafter pulled out.
~1156~7 Vulcanization was carried out at such temperature and pressure and for such length of time as are speci-fically defined for the rubber compounds used. As used herein, the term "vulcanization" is defined to mean the so-called original vulcanization.
Tire cords produced by plating steel wires with the prior art binary alloy of Cu-Zn IControls A to G of Table 3 above) were tested for rubber adhesivity re-sistant to corrosion by saline water, the results being set forth in Table 3 above.
As apparent from Examples l and 2, a metal wire plated with a ternary alloy of Cu-Zn-Co embodying this invention has a higher drawability and rubber adhesivity resistant to corrosion by saline water than a metal wire plated with the prior art binary alloy of Cu-ZnO
Example 3 According to the procedure of Example 2, tire cords of lx5~0.25) were prepared from steal wires plated with Cu-Zn-Co alloys containing 62% of Cu, different amounts o Co indicated in Table 4 and the balance of Zn. The adhesivity of the tire cords to a rubber compound was tested as in Example 2. Results are shown in Table 4 below.
" v " ~ . . . . . . . . ..
ll~S6~7 Table 4 , \ A d h e s i v i t ~
\ Initial* ~n saline water In saline water \ (after 3 daysl (after 7 daysL
\ ~ ling Percentage Pulling Percentage Pulling Percentage \ strength adhesivity strength adhesivity stren~th adhesivity ~ _ Sample Co(%) (Kg) (%) ~K~ C%) ~KgL ~L
_ _ No. 12 Q.l 40.8 90 36.2 84 30.8 63 No. 13 1 43.2 25 3~.6 87 35.7 77 No. 14 3 44.0 23 4a.Q 20 34.2 71 No. 15 5 44.2 95 41.2 91 38.3 80 No. 16 10 41.3 95 4Q.Q 83 37.0 75 No. 17 20 40.0 88 36.2 75 35.Q 69 No. 18 25 35.0 80 34.0 6~ 28.3 43 ~o. lq none 41.5 90 2~.0 53 15.0 10 Note: * Adhesivity to vulcanized rub~er compound after 1 day.
** Pulling strength (Kg/12.7 mm) at a pulling rate of lOQ mm~min.
As apparent from Table 4, Cu-Zn-Co alloys con-taining 0.1 to 20~ by weight of Co are particularly effective in improving the adhesivity of tire cords to rubber compound in saline water.
11156~7 _ 9 _ rubber compounds A to G of different kinds shown in Table 3 below.
Table 3 Results of testing the resisiance of tire cords to vulcanized rubber in saline water bber compound A ~B C D -E F G
~ _ \ Day 5 5 4 4 4 4 4 Steel Tire Co ~
_ _ Control lx5(0.25~ A(66.7Cu-Zn) 7% 5% 13% 27% 40% 33% 40%
.. ~- B(66.3Cu-Zn) 8 17 10 _ 30 15 _ .. .. C(67.4Cu-Zn) 12 0 10 47 30 37 45 .. .. D(68.2Cu-Zn) 63 56 10 13 70 43 50 .. . E(63.7Cu-Zn) 43 7 17 30 0 30 70 . .. F(67.lCu-Zn) 8 20 3 33 40 30 40 .. .- G(70.5Cu-Zn~ 3 23 20 40 30 35 50 r _ _____.
Invention lx5(0.25) ~u-Zn-Co 63 63 37 53 50 45 45 2+7(0.22)+r 78 72 87 95 50 35 70 3+6(0.35)1 63 ~ ~ 85 ~ 63 80 Note: Numerals given in Table 3 above show the area of the surface of tire cords to which rubber adhered after the tire cords were dipped in saline water and thereafter pulled out.
~1156~7 Vulcanization was carried out at such temperature and pressure and for such length of time as are speci-fically defined for the rubber compounds used. As used herein, the term "vulcanization" is defined to mean the so-called original vulcanization.
Tire cords produced by plating steel wires with the prior art binary alloy of Cu-Zn IControls A to G of Table 3 above) were tested for rubber adhesivity re-sistant to corrosion by saline water, the results being set forth in Table 3 above.
As apparent from Examples l and 2, a metal wire plated with a ternary alloy of Cu-Zn-Co embodying this invention has a higher drawability and rubber adhesivity resistant to corrosion by saline water than a metal wire plated with the prior art binary alloy of Cu-ZnO
Example 3 According to the procedure of Example 2, tire cords of lx5~0.25) were prepared from steal wires plated with Cu-Zn-Co alloys containing 62% of Cu, different amounts o Co indicated in Table 4 and the balance of Zn. The adhesivity of the tire cords to a rubber compound was tested as in Example 2. Results are shown in Table 4 below.
" v " ~ . . . . . . . . ..
ll~S6~7 Table 4 , \ A d h e s i v i t ~
\ Initial* ~n saline water In saline water \ (after 3 daysl (after 7 daysL
\ ~ ling Percentage Pulling Percentage Pulling Percentage \ strength adhesivity strength adhesivity stren~th adhesivity ~ _ Sample Co(%) (Kg) (%) ~K~ C%) ~KgL ~L
_ _ No. 12 Q.l 40.8 90 36.2 84 30.8 63 No. 13 1 43.2 25 3~.6 87 35.7 77 No. 14 3 44.0 23 4a.Q 20 34.2 71 No. 15 5 44.2 95 41.2 91 38.3 80 No. 16 10 41.3 95 4Q.Q 83 37.0 75 No. 17 20 40.0 88 36.2 75 35.Q 69 No. 18 25 35.0 80 34.0 6~ 28.3 43 ~o. lq none 41.5 90 2~.0 53 15.0 10 Note: * Adhesivity to vulcanized rub~er compound after 1 day.
** Pulling strength (Kg/12.7 mm) at a pulling rate of lOQ mm~min.
As apparent from Table 4, Cu-Zn-Co alloys con-taining 0.1 to 20~ by weight of Co are particularly effective in improving the adhesivity of tire cords to rubber compound in saline water.
Claims (16)
1. A metal wire cord comprising-a metal wire, and a coating layer coated on the surface of said metal wire and formed of a ternary alloy of copper, zinc and cobalt containing 0.1 to 50% by weight of cobalt.
2. The metal wire cord according to claim 1, wherein the ternary alloy consists of-such proportions of copper, zinc and cobalt as substantially suppress the precipi-tation of the .beta. phase.
3. The metal wire cord according to claim 1, wherein the zinc content of the ternary alloy ranges between 10%
by weight and 45% by weight.
by weight and 45% by weight.
4. The metal wire cord according to claim 1, wherein the zinc content of the ternary alloy ranges between 20%
by weight and 40% by weight.
by weight and 40% by weight.
5. The metal wire cord according to claim 1, wherein the cobalt content of the ternary alloy ranges between 0.5% by weight and 30% by weight.
6. The metal wire cord according to claim 1, wherein the cobalt content of the ternary alloy ranges between 1% by weight and 10% by weight.
7. The metal wire cord according to claim 1, wherein the coating layer is an electrically plated layer.
8. The metal wire cord according to claim 1, wherein the coating layer is a thermally diffused layer of copper, zinc and cobalt.
9. A method of manufacturing a metal wire cord, which comprises the steps of:
forming on the surface of a metal wire a coating layer formed of a ternary alloy of copper, zinc and cobalt con-taining 0.1 to 50% by weight of cobalt to produce a metal wire; and drawing said metal wire.
forming on the surface of a metal wire a coating layer formed of a ternary alloy of copper, zinc and cobalt con-taining 0.1 to 50% by weight of cobalt to produce a metal wire; and drawing said metal wire.
10. The method according to claim 9, wherein the metal wire is drawn until the cross sectional area is reduced by 85% to 97%.
11. The method according to claim 9, wherein the process of forming the coating layer comprises plating copper, zinc, and cobalt separately in the order mentioned on said surface in the form of a multiply layer, and heating said multiply layer to cause copper, zinc and cobalt to be uniformly diffused throughout said layer.
12. The method according to claim 9, wherein the ternary alloy contains such proportions of copper, zinc and cobalt as suppress the precipitation of the phase.
13. The method according to claim 9, wherein the zinc content of the ternary alloy ranges between 10% by weight and 45% by weight.
14. The method according to claim 9, wherein the zinc content of the ternary alloy ranges between 20% by weight and 40% by weight.
15. The method according to claim 9, wherein the cobalt content of the ternary alloy ranges between 0.5% by weight and 30% by weight.
16. The method according to claim 9, wherein the cobalt content of the ternary alloy ranges between 1%
by weight and 10% by weight.
by weight and 10% by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP159908/77 | 1977-12-27 | ||
| JP15990877A JPS5489940A (en) | 1977-12-27 | 1977-12-27 | Brass plated steel wire having food drawability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1115607A true CA1115607A (en) | 1982-01-05 |
Family
ID=15703786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA318,626A Expired CA1115607A (en) | 1977-12-27 | 1978-12-27 | Metal wire cord |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS5489940A (en) |
| CA (1) | CA1115607A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6030543B2 (en) * | 1979-08-20 | 1985-07-17 | 住友ゴム工業株式会社 | Steel cord for tires with improved adhesion |
| JPS5845365B2 (en) * | 1979-12-05 | 1983-10-08 | 株式会社ブリヂストン | Tires with improved durability |
| JPS5884992A (en) * | 1981-11-14 | 1983-05-21 | Kawatetsu Kousen Kogyo Kk | Brass plated steel wire superior in drawability and adhesive property with rubber |
| JPH01104796A (en) * | 1987-10-16 | 1989-04-21 | Shinko Kogyo Kk | Formation of multicomponent alloy coating film |
| US5624764A (en) * | 1987-11-07 | 1997-04-29 | Sumitomo Rubber Industries, Ltd. | Composite material of metal and rubber for use in industrial rubber articles |
| US5200273A (en) * | 1987-11-07 | 1993-04-06 | Sumitomo Rubber Industries, Ltd. | Metal composite of rubber, benothiazole sulfenamide and copper alloy |
| JP6137587B2 (en) * | 2011-09-06 | 2017-05-31 | 栃木住友電工株式会社 | Rubber reinforcing metal wire, manufacturing method thereof and tire |
| JP2018119189A (en) * | 2017-01-26 | 2018-08-02 | 新日鐵住金株式会社 | Plated steel wire, steel cord and rubber-steel cord complex |
-
1977
- 1977-12-27 JP JP15990877A patent/JPS5489940A/en active Granted
-
1978
- 1978-12-27 CA CA318,626A patent/CA1115607A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5711392B2 (en) | 1982-03-04 |
| JPS5489940A (en) | 1979-07-17 |
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