investigation of twisted monofilament cord properties made of nylon 6.6 and polyester

8
Fibers and Polymers 2011, Vol.12, No.8, 1091-1098 1091 Investigation of Twisted Monofilament Cord Properties Made of Nylon 6.6 and Polyester Berrin Yilmaz Kordsa Global Endustriyel Iplik ve Kord Bezi San. ve Tic. A.S, Izmit, Kocaeli-41310, Turkey (Received January 11, 2011; Revised May 13, 2011; Accepted June 22, 2011) Abstract: A tire is a composite of rubber and reinforcing materials. Polymeric materials used as reinforcing components are usually synthetic yarns. These synthetic yarns have high tenacity, they are made of continuous multifilaments. The yarns are converted in the cord form to provide desired mechanical, thermal and adhesion properties by a series of conversion processes. Besides of multifilament synthetic cords, there are some specific areas in which single ply monofilament cords have been utilized as a reinforcing element. In this study, new cord structures have been developed by using monofilament yarns and by imitating multifilament cords. New cord structures exhibited some very interesting cord properties compared to both single ply monofilament cord and multifilament cords. Monofilament yarns having diameter between 0.23 and 0.50 mm have been twisted together from 3 to 6 plies based on mixed Taguchi model to form cords. Nylon 6.6 and Polyester monofilament yarns have been selected because of common application of their multifilament counterpart yarns in tire carcass and capply. The twisted monofilament cords have been adhesive treated to produce cords ready to adhere rubber. The mechanical properties, thermal stability, adhesion with rubber, fatigue properties under dynamic conditions, retention of properties after curing and microscopic analysis of the cords have been analyzed. The cords have been found to possess some benefits for tire carcass, breaker, belt and belt protective layer applications with their superior fatigue performance, cut resistance, stiffness, ligth weigth etc. Keywords: Monofilament, Nylon 6.6, Polyester, Tire cord Introduction High tenacity Nylon 6.6 and Polyester synthetic continuous multifilament yarns are well known reinforcing materials for tire applications. Tire cords made of Nylon 6.6 synthetic yarns are usually utilized in the cap ply zone of tire. The cap ply cord structure, such as linear densities, ply numbers, twist levels, mechanical and thermal property are adjusted according to the type of tire and design of cap ply in the tire etc. Polyester synthetic yarn is one of the basic materials for radial passenger car tires as a carcass member. In recent years, it seems that developments, particularly in adhesive systems, make Polyester tire cords a candidate as a cap ply of some specific tires. The application of steel in radial tires in Europe goes back to the 1940s and then now steel has became one of the basic reinforcing materials in radial tires as a carcass and belt member over many years. The monofilament cords have very limited and special tire applications. The literature related to monofilament cords and its tire applications are limited to patent applications. The applications of monofilament cords in heavy duty off- the-road (OTR) tires have been patented [1]. Since OTR tires run on very harsh road conditions, sharp rocky objects and uneven terrain cause the chipping and the chunking of the tire. In order to improve the chip resistance of OTR tires monofilament cords were applied over the belt and under the tread of the tire. These monofilament cords have at least 2000 denier, 3,5 g/denier tenacity and adhesive treated with an epoxy sub-coat and Resorcinol Formaldehyde Latex (RFL) top-coat. The obround shaped monofilament cord application in radial medium truck tires has also been patented [2]. The puncture of tire by any object from the road surface may be deep enough causing the exposure of the steel belt package to water and air. The presence of moisture causes the corrosion of steel in the belt package and if extensive corrosion happens, the tire is then scrapped. Therefore, the replacement of at least one layer of steel belt with a non- corrosive polymeric monofilament material has been investigated. The results and observations of tires with monofilament cords in belt package have been summarized and were compared to reference tires. The analyses have shown that there were no worn difference and no evidence to reduce tire protection. Also, damage stayed localized when reached to monofilament layer and monofilament layer could be easily removed by rasping of tire. Providing a thin and light weight reinforcing belt for pneumatic tires by using non-metallic monofilament cords having elongated cross-sections has been patented [3]. The elongated cross-sectional cords have been expected to improve the handling performance of tire by resisting lateral movement and developing higher cornering force. The useful life of the tire has been extended tire by providing lighter reinforcing belt and less heat build-up. Tires carcass reinforced with polymeric monofilament cords have been investigated and patented [4]. Monofilament cords with flat cross-section have comprised a plurality of sub-monofilaments. Each sub-monofilament have circular *Corresponding author: [email protected] DOI 10.1007/s12221-011-1091-3

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Page 1: Investigation of twisted monofilament cord properties made of nylon 6.6 and polyester

Fibers and Polymers 2011, Vol.12, No.8, 1091-1098

1091

Investigation of Twisted Monofilament Cord Properties Made of

Nylon 6.6 and Polyester

Berrin Yilmaz

Kordsa Global Endustriyel Iplik ve Kord Bezi San. ve Tic. A.S, Izmit, Kocaeli-41310, Turkey

(Received January 11, 2011; Revised May 13, 2011; Accepted June 22, 2011)

Abstract: A tire is a composite of rubber and reinforcing materials. Polymeric materials used as reinforcing components areusually synthetic yarns. These synthetic yarns have high tenacity, they are made of continuous multifilaments. The yarns areconverted in the cord form to provide desired mechanical, thermal and adhesion properties by a series of conversionprocesses. Besides of multifilament synthetic cords, there are some specific areas in which single ply monofilament cordshave been utilized as a reinforcing element. In this study, new cord structures have been developed by using monofilamentyarns and by imitating multifilament cords. New cord structures exhibited some very interesting cord properties compared toboth single ply monofilament cord and multifilament cords. Monofilament yarns having diameter between 0.23 and 0.50 mmhave been twisted together from 3 to 6 plies based on mixed Taguchi model to form cords. Nylon 6.6 and Polyestermonofilament yarns have been selected because of common application of their multifilament counterpart yarns in tirecarcass and capply. The twisted monofilament cords have been adhesive treated to produce cords ready to adhere rubber. Themechanical properties, thermal stability, adhesion with rubber, fatigue properties under dynamic conditions, retention ofproperties after curing and microscopic analysis of the cords have been analyzed. The cords have been found to possess somebenefits for tire carcass, breaker, belt and belt protective layer applications with their superior fatigue performance, cutresistance, stiffness, ligth weigth etc.

Keywords: Monofilament, Nylon 6.6, Polyester, Tire cord

Introduction

High tenacity Nylon 6.6 and Polyester synthetic continuous

multifilament yarns are well known reinforcing materials for

tire applications. Tire cords made of Nylon 6.6 synthetic

yarns are usually utilized in the cap ply zone of tire. The cap

ply cord structure, such as linear densities, ply numbers,

twist levels, mechanical and thermal property are adjusted

according to the type of tire and design of cap ply in the tire

etc. Polyester synthetic yarn is one of the basic materials for

radial passenger car tires as a carcass member. In recent

years, it seems that developments, particularly in adhesive

systems, make Polyester tire cords a candidate as a cap ply

of some specific tires. The application of steel in radial tires

in Europe goes back to the 1940s and then now steel has

became one of the basic reinforcing materials in radial tires

as a carcass and belt member over many years.

The monofilament cords have very limited and special tire

applications. The literature related to monofilament cords

and its tire applications are limited to patent applications.

The applications of monofilament cords in heavy duty off-

the-road (OTR) tires have been patented [1]. Since OTR

tires run on very harsh road conditions, sharp rocky objects

and uneven terrain cause the chipping and the chunking of

the tire. In order to improve the chip resistance of OTR tires

monofilament cords were applied over the belt and under the

tread of the tire. These monofilament cords have at least

2000 denier, 3,5 g/denier tenacity and adhesive treated with

an epoxy sub-coat and Resorcinol Formaldehyde Latex (RFL)

top-coat.

The obround shaped monofilament cord application in

radial medium truck tires has also been patented [2]. The

puncture of tire by any object from the road surface may be

deep enough causing the exposure of the steel belt package

to water and air. The presence of moisture causes the

corrosion of steel in the belt package and if extensive

corrosion happens, the tire is then scrapped. Therefore, the

replacement of at least one layer of steel belt with a non-

corrosive polymeric monofilament material has been

investigated. The results and observations of tires with

monofilament cords in belt package have been summarized

and were compared to reference tires. The analyses have

shown that there were no worn difference and no evidence to

reduce tire protection. Also, damage stayed localized when

reached to monofilament layer and monofilament layer

could be easily removed by rasping of tire.

Providing a thin and light weight reinforcing belt for

pneumatic tires by using non-metallic monofilament cords

having elongated cross-sections has been patented [3]. The

elongated cross-sectional cords have been expected to

improve the handling performance of tire by resisting lateral

movement and developing higher cornering force. The

useful life of the tire has been extended tire by providing

lighter reinforcing belt and less heat build-up.

Tires carcass reinforced with polymeric monofilament

cords have been investigated and patented [4]. Monofilament

cords with flat cross-section have comprised a plurality of

sub-monofilaments. Each sub-monofilament have circular*Corresponding author: [email protected]

DOI 10.1007/s12221-011-1091-3

Page 2: Investigation of twisted monofilament cord properties made of nylon 6.6 and polyester

1092 Fibers and Polymers 2011, Vol.12, No.8 Berrin Yilmaz

cross-section and interconnected radially to form a rectangular

shape. Those types of monofilament cords have exhibited

better adherence to rubber and have shown better resistance

to the separation from the rubber.

In this study, the properties of monofilament cords made

of nylon 6.6 and polyester have been investigated. The effect

of monofilament yarn diameter and linear density, number of

yarn plies to form a cord has been investigated based on a

type of Taguchi design. The properties of the cords have

been analyzed. The idea behind this study is to improve new

cord structures to fulfill some deficient properties of both

single ply monofilament cord and multifilament cords.

Patent literatures summarized above are related to the tire

application of either round shaped or obround shaped single

ply monofilament cords. On the other hand, the reinforcement

of tire rubber with multifilament cords is well known. The

twisted monofilament cords were developed as a novel cord

structures to fill the gap between single ply monofilament

cords and multifilament cords. The new cord structures have

a resemblance to single ply monofilament cords because

they are made of monofilament yarns. At the same time, the

new cord structures have a resemblance to multifilament

cords because of being composed of more than one ply of

monofilament yarns. On the other hand, although similarities

are available they are neither single ply monofilament cords

nor multifilament cords; they have different geometries and

properties. One of the weaknesses of single ply monofilament

cord is the fretting through the bulk of polymer matrix in the

presence of any deformation. Even though good adhesion

can be obtained between RFL coated cord surface and

rubber, the fretting from bulk of polymer of monofilament

creates an open and non-RFL coated cord section. As a

result, defect points created on the surface may cause further

degradation of single ply monofilament cord. Another weak

point is the possibility of crack propagation in a single ply

monofilament cords may proceed up to the cord breakage if

damaged by sharp objects. Thus, cord loses its reinforcing

properties. However, in case of twisted monofilament cords

the crack propagation is limited to only one of the plies and

even if after ply breakage the other plies retain reinforcing

property to a certain extent. Compared to the multifilament

cords, multiply monofilament cords have less frictional

surfaces because of limited amount of plies, this may bring

some fatigue advantages to the tire by positively effecting

the longevity of it. The replacement of one layer of belt ply

by a layer of monofilament cord for special tires decreases

the weight of the tire, thus reducing the rolling resistance

and contributing to less oil consumption.

Experimental

Material

Twisted monofilament cords were prepared by using

nylon 6.6 type G183 and polyester type L183 and K183

(Nexis Fibers, Switzerland). The thickness of G183 type

monofilaments were 0.23- 0.30- 0.40- 0.50 mm and the

corresponding dtex levels were 475, 810, 1420, 2240

respectively. Type L183 with 0.25 and 0.30 mm thickness

levels and type K183 with 0.40 and 0.45 mm thickness

levels were utilized in cord preparation. The dtex levels of

polyester monofilaments were 680, 970, 1730, and 2200.

Machine and Method

The twisting of monofilament cords were made by using

laboratory scale twisting machine (Oerlikon Saurer, Germany).

Monofilament yarns were twisted by combining from 3 to

6 plies with a 50 twist per meter (tpm) level to obtain desired

cord structure determined by the experimental design. The

twisted cords were heat treated by using laboratory scale

single end cord dipping machine (C. A. Litzler, Cleveland,

Ohio). During heat treatment water based RFL [5] solution

was used for nylon 6.6 cords. The dipping of polyester cords

was made first by using epoxy and isocyanate solution with

a solid content of 5 %, followed by RFL based adhesive

solution. The curing temperature applied during dipping

were 225oC for nylon 6.6, 235 oC and 225 oC for polyester

cord dipping.

Mechanical properties of samples were analyzed by using

Instron Mechanical Testing Instrument (Instron, Norwood,

MA). Mechanical tests were carried out in accordance with

ASTM D885, the grip distance was 254 mm and the grip

speed was 300 mm/min.

Thermal shrinkage of the yarns and cords were analyzed

by using Testrite instrument (Testrite Ltd., W. Yorkshire,

England). The cords were hold in the testrite instrument at

177oC for 2 min in the presence of 0.045 g/dtex pretension.

The dimensional change along the yarn axis was recorded as

thermal shrinkage of the yarns and cords. The shrinkage

force of the samples was also measured under the same

temperature, time, pretension conditions; 177 oC, 2 min,

0.045 g/dtex, respectively.

The bending stiffness of cords was measured by using

Instron equipment. A 3 cm cord in length was placed on a

platform where there was a hole in the middle. A hook was

placed on the cord through the hole. While the hook was

pulling down the cord, a force was exerted on the cord to

bend it. The force at a point where the cord began to bend

was recorded as bending stiffness force.

The pull adhesion test was carried out to measure the

adhesion strength of the adhesive treated cords. Each sample

was embedded into the rubber by 0.60-1.00 cm and cured at

143 oC, for 20 min at the pressure of 10.5 kg/cm2. After

curing was completed, the samples were cooled for 30 min

and then the adhesion of the cords was measured by pulling

out the cords from the rubber.

The dynamic performance of rubberized cords was carried

out by using dynamic flex fatigue tester (Wallace Instruments,

Redhill Surrey, England). It was a tire simulation test to

Page 3: Investigation of twisted monofilament cord properties made of nylon 6.6 and polyester

Nylon 6.6 and Polyester Twisted Monofilament Cords Fibers and Polymers 2011, Vol.12, No.8 1093

measure the fatigue performance of the cord under dynamic

conditions at which the rubberized cord sample blocks were

flexed around a pulley for a predetermined cycle [6]. The

fatigue testing was carried out at 70 oC for 150000 cycles. At

the end of the test, the adhesion and breaking strength of un-

flexed and flexed samples were measured by using Instron

equipment. The test results of the flexed samples were

compared with the test results of un-flexed samples. The

ratio of flexed sample test result to the un-flexed sample test

result was reported as % retained property.

The mechanical retention properties of cords after

rubberizing were analyzed by curing the cords in rubber test

in which cords were embedded in a rubber and cured at

177oC for 20 min at the pressure of 21 kg/cm2. The cords

were then pulled out from the rubber matrix. The retained

mechanical properties of the rubberized cords were tested by

using Instron instrument. The test results were compared

with the results of un-rubberized cord samples. The ratio of

un-rubberized to the rubberized samples was recorded as %

retained property.

The microscopic cross sectional analysis of the cords were

carried out by using Leica MZFIII microscope (Leica

Microsystems GmbH, Germany).

Experiments were designed by using Minitab statistical

program. Mixed Taguchi method was used as a design of

experiment technique. The orthogonal array used in this

study was L16 (24 12) involving 3 factors, 16 experiment.

The factors were chosen as material thickness (or dtex),

material ply number and material itself. First two factors

were designed with 4 levels whereas the last factor was

designed with 2 levels. Experimental layout of this design

was given in Table 1. Each array referred to an experiment

with predetermined factors and their levels. Factor A was

denoted as thickness of single monofilament yarn where the

thickness levels were explained above in material section.

Factor B was the number of monofilament plies to make

cords, the levels of design was 3, 4, 5 and 6. Factor C is the

monofilament yarn materials, the levels were nylon 6.6 and

Polyester. The test results of experimental design set were

analyzed by using the same statistical program. The main

effect factors and their levels on the cord properties were

determined based on the delta values of statistical analysis.

Delta values corresponded to the difference between the

mean values of two different levels. As delta value increased

the effect of the factor on the desired property also increased [7].

Results and Discussion

The tensile and thermal properties of monofilament yarns

were given in Table 2. The load-elongation (%) curve of

0.30 mm diameter Nylon 6.6 and Polyester yarns were given

in Figure 1. All yarns had similar load-elongation (%)

behavior therefore only one of them, 0.30 mm diameter, was

selected as an example. The breaking strength of the Nylon

6.6 monofilament yarns were between 3.3 and 13.7 kg

depending on the linear density (dtex) of the material. The

Table 1. Experimental layout of Mixed Taguchi L16 type design

Cord

number

Experiment

no

Factor A

(thickness)

Factor B

(ply number)

Factor C

(material)

Cord 1 1 1 1 1

Cord 2 2 1 2 1

Cord 3 3 1 3 2

Cord 4 4 1 4 2

Cord 5 5 2 1 1

Cord 6 6 2 2 1

Cord 7 7 2 3 2

Cord 8 8 2 4 2

Cord 9 9 3 1 2

Cord 10 10 3 2 2

Cord 11 11 3 3 1

Cord 12 12 3 4 1

Cord 13 13 4 1 2

Cord 14 14 4 2 2

Cord 15 15 4 3 1

Cord 16 16 4 4 1

Table 2. Tensile, thermal properties of Nylon 6.6 and Polyester monofilament yarns

MaterialThickness

(mm)Dtex

Breaking strength

(kgf)

Elongation at

break (%)

Lase 3 %

(kgf)

Lase 5 %

(kgf)

Breaking energy

(kgf-mm)

Thermal

shrinkage (%)

Avg/std Avg/std Avg/std Avg/std Avg/std Avg/std

NY 0.23 475 3.34 / 0.038 27.9 / 0.78 0.38 / 0.01 0.51 /0.01 119 / 6.0 2.53 / 0.08

NY 0.30 810 5.10 / 0.06 27.0 / 0.58 0.58 / 0.01 0.80 / 0.01 176 / 7.6 2.60 / 0.06

NY 0.40 1420 8.37 / 0.14 23.0 / 0.44 1.04 / 0.01 1.45 / 0.02 236 / 13.9 2.80 / 0.06

NY 0.50 2240 13.72 / 0.15 22.9 / 0.48 1.78 / 0.02 2.59 / 0.02 423 / 17.1 3.35 / 0.08

PET 0.25 680 2.61 / 0.03 35.8 / 1.05 0.71 / 0.02 0.81 / 0.01 152 / 7.8 -

PET 0.30 970 3.75 / 0.05 37.7 / 1.59 1.0 / 0.05 1.15 / 0.01 233 / 13.5 -

PET 0.40 1730 6.62 / 0.08 39.9 / 0.96 1.70 / 0.02 1.84 / 0.01 380 / 16.1 -

PET 0.45 2200 8.23 / 0.06 37.5 / 0.89 2.31 / 0.02 2.49 / 0.02 512 / 19.3 -

NY: Nylon 6.6, PET: Polyester, and Lase 3 % and Lase 5 %: Load at specific elongation (3 and 5 %).

Page 4: Investigation of twisted monofilament cord properties made of nylon 6.6 and polyester

1094 Fibers and Polymers 2011, Vol.12, No.8 Berrin Yilmaz

tenacity (breaking strength (g)/dtex) values of the Nylon 6.6

yarns were in the range of 6.0-7.0 g/dtex. The breaking

strength of polyester monofilament yarns were between 2.6-

8.2 kg within 680-2200 dtex range. The tenacity values of

polyester monofilament yarns were around 3.8 g/dtex.

Although the linear densities of both type of monofilament

yarns were close to each other at equivalent thickness levels,

the tenacity of polyester monofilaments were low. Elongation at

break values of Nylon 6.6 monofilament yarns was within

23-28 % range, whereas that of polyester monofilament

yarns had higher breaking elongations such as 36-39 %. The

initial elongations of Polyester monofilament were lower

than Nylon 6.6 monofilament yarn. For instance, 0.30 mm

Polyester needed 1 kg load to elongate by 3 %, whereas

Nylon 6.6 needed 0.58 kg load for the same percent

elongation. Up to 5-8 % elongation Polyester required more

load to elongate at the same percentage. After this point the

elongation behavior of the monofilaments was reversed. The

breaking energy of Nylon 6.6 and Polyester monofilament

yarns were between 119-423 kg-mm and 152-512 kg-mm,

respectively. The toughness of the material (breaking energy

divided by linear density) 0.17-0.25 kg-mm/dtex for Nylon

6.6 and 0.22-0.24 kg-mm/dtex for Polyester monofilament

yarns. Nylon 6.6 exhibited a decrease in toughness with

increased thicknesses; on the other hand Polyester possessed

more consistent values within a thickness range. Thermal

shrinkage of Nylon 6.6 monofilaments were within 2.5-3.3 %.

Polyester monofilaments did not have any retraction in the

fiber direction, instead elongated under thermal shrinkage

testing conditions.

As mentioned in experimental sections the cords were

prepared based on Table 1 arrays and the test results of these

cords were given in Table 3(a). The load elongation curve of

5 plies 0.25 mm twisted monofilament Nylon 6.6 and 4 plies

0.30 mm Polyester cords were given in Figure 2 as a typical

example. These two cord structures were selected particularly

out of the 16 cord samples because of having linear densities

close to each other. All Polyester and Nylon 6.6 twisted

monofilament load-elongation curves were similar to that of

given in Figure 2. Taguchi main effect analysis (Figure 3)

showed that, the breaking strength of the cords increased

Figure 1. Load/elongation curves of nylon 6.6 and polyester

monofilament yarns having 0.30 mm thickness.

Table 3. (a) Properties of adhesive treated twisted Nylon 6.6 and Polyester monofilament cords prepared in accordance with mixed Taguchi

design

Cord

number

Cord

definition*

Breaking strentgh

(kg)

Elongation at

break (%)

EASL 44N

(%)

LASE 3 %

(kg)

LASE 5 %

(kg)

Avg / Std Avg / Std Avg / Std Avg / Std Avg / Std

Cord 1 0.23×3, ny 8.98 / 0.10 23.2 / 0.64 11.6 / 0.04 0.9 / 0.00 1.5 / 0.01

Cord 2 0.23×4, ny 12.36 / 0.05 22.7 / 0.42 9.2 / 0.07 1.4 / 0.02 2.1 / 0.03

Cord 3 0.25×5, pet 12.41 / 0.07 12.6 / 0.47 2.6 / 0.09 1.9 / 0.12 2.56 / 0.17

Cord 4 0.25×6, pet 14.70 / 0.33 10.9 / 0.31 2.1 / 0.09 2.7 / 0.12 2.62 / 0.16

Cord 5 0.30×3, ny 14.46 / 0.17 20.4 / 0.35 7.4 / 0.05 1.8 / 0.01 2.8 / 0.02

Cord 6 0.30×4, ny 19.46 / 0.20 21.5 / 0.40 5.9 / 0.03 2.4 / 0.01 3.7 / 0.02

Cord 7 0.30×5, pet 17.59 / 0.09 24.1 / 1.2 1.7 / 0.05 6.9 / 0.08 9.5 / 0.05

Cord 8 0.30×6, pet 21.10 / 0.17 24.2 / 0.56 1.4 / 0.08 8.3 / 0.16 11.4 / 0.12

Cord 9 0.40×3, pet 20.49 / 0.12 24.0 / 0.66 1.6 / 0.11 7.3 / 0.16 10.0 / 0.1

Cord 10 0.40×4, pet 27.13 / 0.16 24.0 / 0.69 1.3 / 0.10 9.3 / 0.25 13.0 / 0.18

Cord 11 0.40×5, ny 43.10 / 0.23 20.7 / 0.36 1.9 / 0.07 5.7 / 0.08 8.61 / 0.11

Cord 12 0.40×6, ny 51.49 / 0.43 21.2 / 0.51 1.6 / 0.04 6.8 / 0.05 10.2 / 0.10

Cord 13 0.50×3, pet 25.81 / 0.19 23.4 / 0.63 1.1 / 0.11 9.6 / 0.27 13.1 / 0.19

Cord 14 0.50×4, pet 33.71 / 0.16 23.1 / 0.68 1.0 / 0.14 12.3 / 0.44 17.1 / 0.30

Cord 15 0.50×5, ny 67.37 / 0.32 21.1 / 0.45 1.4 / 0.16 8.8 / 0.22 13.3 / 0.33

Cord 16 0.50×6, ny 80.66 / 0.37 20.1 / 0.28 1.2 / 0.10 11.0 / 0.22 16.8 / 0.35*Monofilament yarn thickness×ply number, material.

Page 5: Investigation of twisted monofilament cord properties made of nylon 6.6 and polyester

Nylon 6.6 and Polyester Twisted Monofilament Cords Fibers and Polymers 2011, Vol.12, No.8 1095

with increasing thickness and ply number. The thickness had

highest influence (delta 7.90), then followed by ply number

(delta 3.94) and finally material type (delta 0.82). Different

breaking strength values could be interchangeable obtained

either by changing the thickness of monofilament yarn or the

ply number. For instance, 4 ply 0.23 mm Nylon 6.6 twisted

monofilament cord (cord 2) gave 12,4 kg breaking strength,

the same breaking strength was achieved by using 5 ply

0.25 mm Polyester monofilament cord (cord 3). The flexibility

of obtaining the same breaking strength with different

combinations seemed to be advantageous for a cord design.

The tenacity of the twisted monofilament cords were

calculated by dividing the total breaking strength of the cord

to the total linear density (dtex) of the same cord. Thickness

and ply number did not have any influence on the tenacity.

The tenacity values of the cords were driven by material

type, i.e. the values of Nylon 6.6 cords were between 6.6-

7.2 g/dtex, whereas that of Polyester cords were between

3.6-3.9 g/dtex (Table 3(a)).

Elongation at break values of both Nylon 6.6 and

Polyester twisted monofilament cords were very close to

each other. The breaking elongations of materials as a yarn

form were above 35 and 23 %, for Polyester and Nylon 6.6

respectively. After heat and adhesive treatment the breaking

Table 3. (b) Properties of adhesive treated twisted Nylon 6.6 and Polyester monofilament cords prepared in accordance with mixed Taguchi

design

Cord

number

Cord

definition*

Breaking energy

(kgf mm)

Shrinkage

(%)

Bending stiffness

(g)

Thickness

(mm)

Adhesion strength

(kg)

Avg / Std Avg / Std Avg / Std Avg / Std Avg / Std

Cord 1 0.23×3, ny 280 / 13.7 3.4 / 0.00 39.0 / 2.0 0.43 / 0.01 12.8 / 0.61

Cord 2 0.23×4, ny 364 / 12.1 3.4 / 0.01 53.0 / 2.0 0.48 / 0.01 17.4 / 1.06

Cord 3 0.25×5, pet 562 / 30.6 1.9 / 0.06 130 / 23 0.53 / 0.01 14.6 / 1.53

Cord 4 0.25×6, pet 569 / 82.9 2.0 / 0.06 243 / 62 0.67 / 0.01 18.2 / 0.99

Cord 5 0.30×3, ny 385 / 6.16 3.4 / 0.06 89.0 / 2.0 0.58 / 0.01 16.8 / 1.47

Cord 6 0.30×4, ny 585 / 23.2 3.5 / 0.00 117 / 2.0 0.63 / 0.01 17.6 / 1.78

Cord 7 0.30×5, pet 789 / 52.7 2.0 / 0.06 206 / 15.0 0.72 / 0.01 15.0 / 0.68

Cord 8 0.30×6, pet 953 / 29.6 2.0 / 0.06 292 / 50.0 0.83 / 0.06 15.2 / 0.71

Cord 9 0.40×3, pet 872 / 31.3 2.3 / 0.06 335 / 28.0 0.74 / 0.01 14.7 / 0.93

Cord 10 0.40×4, pet 1137 / 41.3 2.4 / 0.00 387 / 18.0 0.82 / 0.01 17.1 / 2.15

Cord 11 0.40×5, ny 1223 / 90.0 3.6 / 0.07 334 / 8.0 0.97 / 0.01 19.4 / 0.86

Cord 12 0.40×6, ny 1598 / 66.6 3.6 / 0.01 419 / 10.0 1.15 / 0.01 20.2 / 1.03

Cord 13 0.50×3, pet 1084 / 42.1 2.4 / 0.06 428 / 16.0 0.85 / 0.30 10.8 / 1.19

Cord 14 0.50×4, pet 1399 / 50.5 2.4 / 0.00 548 / 26.0 0.94 / 0.20 27.9 / 6.25

Cord 15 0.50×5, ny 2124 / 71.6 3.3 / 0.12 830 / 40.0 1.48 / 0.01 43.8 / -

Cord 16 0.50×6, ny 2327 / 115 2.8 / 0.15 1050 / 27.0 1.49 / 0.01 41.5 / -*Monofilament yarn thickness ×ply number, material.

Figure 2. Load/elongation curves of nylon 6.6 (0.25 mm×5 plies)

and polyester (0.30 mm×4 plies) twisted monofilament cords. Figure 3. Main effect analysis for the mean values of breaking

strength of the cords prepared in accordance with mixed Taguchi

design.

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1096 Fibers and Polymers 2011, Vol.12, No.8 Berrin Yilmaz

elongations were stabilized within 21.3-24.2 % range for

Polyester cords and 20-23.2 % range for Nylon 6.6 cords

(Table 3(a)). Heat treatment conditions influenced Polyester

elongation values more than that of Nylon 6.6. The ranking

of parameters based on main effect analysis was obtained as

material type, ply number and thickness in the decreasing

order of delta values (2.19, 1.13 and 0.91) respectively.

Referring to the values given in Table 3(a) and curves

given in Figure 2, partial load elongation at 4.5 kg of

Polyester and Nylon 6.6 twisted monofilament cords had

significantly different values. Polyester twisted monofilaments

had very high initial modulus, low elongations compared to

Nylon 6.6 under the same load. Polyester twisted cord

retained its lower elongating character up to 10 %

elongation. After that point Nylon 6.6 twisted monofilament

cords exhibited higher modulus values than Polyester

twisted monofilament cords. The main effect analysis of

elongation at 4.5 kg of all cords proved that thickness of

monofilament (delta: 5.17) has the highest influence. Ply

number (delta: 3.88) and material type (delta 3.44) had

almost very similar influence on partial load elongations. As

the thickness of monofilament, ply number increased, partial

load elongation at 4.5 kg decreased. Load at specific elongation

at 3 and 5 % values also supported this difference. As the

thickness increased, the load required to elongate the cord by

3 or 5 % also increased. The ply number also caused the

similar change, as the ply number of cord increased, the load

for 3 and 5 % elongations increased. If the cord was made of

polyester, the cord had higher load for the same elongation

values. The ranking of delta values of main effect analysis

for load at 3 and 5 % elongations pointed out the following

decreasing order; thickness, ply number and material type.

Ductile behavior of twisted monofilaments was calculated

by dividing the elongation at break and elongation at partial

loads to the total linear density of the cords separately. Main

effect analysis denoted that the thickness of the monofilament,

ply number of the cord and Polyester material reduced the

ductile behavior per unit linear density. For instance; the

ranking of delta values driven from the main effect analysis

of elongation at partial load 4.5 kg was in the order of

thickness, ply number and material (0.34, 0.27 and 0.198),

respectively. The mean values of ductility cords for 0,25 mm

and 0.50 mm thickness monofilaments were 0.35 and 0.012

respectively. The mean values of ductility for 3 plies and 6

plies cords were 0.29 and 0.025, respectively. The mean

values of ductility of Nylon 6.6 was higher than Polyester

monofilament cords (0.23 versus 0.3).

The breaking energy of twisted cords (Table 3(b)) was

attributed to the energy absorption ability of the material

upon external disturbances. The graph related to the main

effect analysis for means of breaking strength of the Taguchi

design was given in Figure 4. As the thickness (delta 1289)

and ply number (delta 706) increased the breaking energy of

the cords increased also. Polyester twisted monofilament

cords have less breaking energy values than Nylon 6.6

twisted monofilament cords (delta 190). The breaking toughness

of twisted monofilament cords was calculated by dividing

the breaking energy to the total dtex value of the cords to

calculate the energy absorption capacity per unit linear

density. The toughness values of the cords were between

0.14 and 0.20 kg-mm/dtex. The main effect analysis proved

that the effect of material type had slightly higher influence

on toughness compared to monofilament diameter and ply

number.

The thermal shrinkage of twisted monofilament cords at

177oC, for 2 min, with 0.045 g/dtex pretention were obtained

between 1.9-3.8 % (Table 3(b)). Recalling the thermal shrinkage

of the yarn materials, Nylon 6.6 twisted monofilaments

retained their shrinkage after heat treatment. Polyester

twisted monofilament cords developed a certain level of

thermal shrinkage as an average value of approximately

2.0 %. Regarding to the statistical main effect analysis for

mean values, yarn thickness and cord ply number did not

have significant influence on thermal shrinkage. Material

type was dominating parameter, where Nylon 6.6 twisted

monofilament cords had high shrinkage, with an average

value of 3.3 %. The retraction force was measured under the

same thermal conditions. Nylon 6.6 monofilament cords

exhibited a retraction force between 0.3 and 3.2 kg, polyester

monofilament cords exhibited a retraction force between

0.4-1.5 kg depending on the composition of the cord. The

statistical analysis denoted that, as the thickness of the

monofilament yarn increased the retraction force also

increased. As the ply number of the cords increased the

retraction force decreased slowly.

The bending stiffness of twisted monofilament cords was

a distinguishing property of the cords (Table 3(b)) from the

multifilament cords. The thicker monofilament cords (delta

0.59) had higher bending stiffness values. As the ply number

increased (delta 0.28), the stiffness also increased. Twisted

Figure 4. Main effect analysis for the mean values of breaking

energy of the cords prepared in accordance with mixed Taguchi

design.

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Nylon 6.6 and Polyester Twisted Monofilament Cords Fibers and Polymers 2011, Vol.12, No.8 1097

monofilament cords had higher stiffness compared to the

equivalent dtex multifilament cord. For instance, multifilament

cord with 1400 dtex×2 ply (total dtex 2800) structure

required 0.040-0.050 kg bending strength, Cord 5 with

0.30 mm×3 ply (total dtex 2430) required 0.09 kg bending

strength. In tire belt package applications stiffer material

may contribute to the generation of handling force, better

traction and tread wear performance. The stiffness of the

monofilament cords was also adjusted by changing either

the diameter of the monofilament or by the ply number of

the cords.

The adhesion of twisted monofilament cords was one of

the critical points compared to the multifilament cords. The

adhesion values of twisted monofilaments were given in

Table 3(b). A typical example of multifilament cords is 1400

dtex which composed of 210 individual filaments. After the

RFL adhesive treatment the adhesive solution penetrated to

at most 3 to 4 filaments, thus, chemical reactions were

developed between several filaments and adhesive. Another

attribute of multifilament cords were the surface roughness

because of filamentary nature, it increased the surface area

of cord and thus increased surface contact between rubber

and cord, and also increased the mechanical interlocking.

However, monofilaments did not have filamentary structures;

their surface was quite smooth and there was no chance of

adhesive solution to be penetrated inside the monofilament,

as a consequence less contact surface area for rubber

adhesion was available. In this study it was observed that the

adhesion of twisted equivalent dtex monofilament cords and

multifilament cords had similar adhesion values. For

instance, Cord 2 had 1900 dtex linear density and 17.4 kg

adhesion strength, the adhesion strength of multifilament

cord having 1880 dtex was expected to be on average 16.0 kg.

If the adhesion behavior of twisted monofilament cord was

compared to the single ply monofilament cord, twisted

monofilament cords exhibited higher adhesion values. For

instance single ply monofilament cord made of 0.35 mm

diameter and 2240 dtex linear density possessed 15.6 kg

adhesion strength. Although the dtex of Cord 2 was smaller

than 2240 dtex, Cord 2 had higher adhesion value. On the

other hand, the circumference of Cord 2 and 0.35 mm single

ply cord was measured as 1.96 and 1.1 mm. The difference

between the adhesion values was most probably originating

from the surface area in favor of twisted monofilament

cords.

The fatigue performance of twisted monofilament cords

were carried out under extreme conditions. The fatigue

behavior of Nylon 6.6 twisted monofilament cords was

analyzed as a function of monofilament yarn thickness and

cord ply number (Figure 5). The adhesion retention after

fatigue test was influenced by ply number and thickness. As

the ply number increased, the adhesion retention decreased,

considering all cord couples as Cords 1-2, Cords 5-6, Cords

11-12, Cords 15-16 the behavior was obvious. As the

number of plies increased, more contact surface was created

and more friction was realized. Therefore, under dynamic

conditions more heat was produced and most probably the

produced heat caused adhesion degradation. The thickness

of monofilament yarns also affected the adhesion retention.

As the thickness increased, the adhesion retention decreased;

i.e. examples of cord couples such as Cords 1-5, Cords 2-6,

Cords 11-15, Cords 12-16. If the adhesion retention of

twisted monofilament cord was compared to the multifilament

cord at equal linear densities, it was observed that twisted

monofilament cords performed better by retaining their

properties more. The Cord 5 having 2430 dtex linear density

possessed approximately 79 % adhesion retention after 150000

cycle of fatigue, a multifilament cord having 1400×2

structure (total 2800 dtex) possessed approximately 43 %

adhesion retention after 130000 cycle of fatigue. The

breaking strength retention of twisted monofilament cords

realized between 80-100 %. Only 0.50 mm 5 and 6 plied cords

had low breaking strength retention, the rest of the cords

retained their breaking strength. If a comparison was made

with multifilament cord having similar linear density;

1400×2 cord retained the breaking strength by approximately

83 % after 130000 cycles, whereas Cord 5 did not show any

breaking strength loss after 150000 cycle fatigue. Twisted

monofilament Nylon 6.6 cords had superior performance

under dynamic conditions compared to multifilament cords.

However, the fatigue performance of Polyester twisted

monofilaments was not as successful as Nylon 6.6 case.

During fatigue testing, fatigue sample piece turned around a

pulley simulating shoe shine motion. Polyester cords

embedded into rubber matrix had brittle failure at the end

points of shoe shine motion. Most probably high bending

stiffness of Polyester prevented flexible movement of the

cord and as a consequence brittle failure occurred. Therefore,

a reliable fatigue data could not be obtained for twisted

monofilament cords.

The breaking strength retention of twisted monofilament

Figure 5. Adhesion strength retention and breaking strength

retention after the fatigue test of nylon 6.6 twisted monofilament

cords prepared in accordance with mixed Taguchi design.

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1098 Fibers and Polymers 2011, Vol.12, No.8 Berrin Yilmaz

cords under static conditions was analyzed by cure in rubber

test. Cords 1, 2, 3, 4 four samples were selected out of the

prepared cord samples. Cords 1, 2, 3 and 4 retained the

original braking strength; cord 4 retained approximately

90 % of its original breaking strength.

The alignment of each ply in a cord cross-section was

analyzed by using microscopic analysis. Some examples of

cross-sectional view of 3, 4, 5, 6 ply cords were given in

Figure 6(a)-(d). The appearances of these cross-sections were

very similar to steel cord cross-section, but different than

that of multifilament cord cross-sections. Twisted monofilament

cord made of 3 plies yarn has triangular cross-section, the

cord made of 4 plies yarn has rhomboid structure. The

twisted monofilament cords with 5 plies of yarn have

pentagonal structure which might not be stable. Because the

hole in the middle of plies was big enough and one of the ply

might shift to the hole, thus cord cross-section might change

to rectangular shape. In case of 6 plies twisted monofilament

cord, the cross-section had a circular shape and one of the

plies were located in the middle of the cord without leaving

a hole as in case of 5 plies.

Conclusion

In this study the properties of twisted monofilament cords

made of Nylon 6.6 and Polyester were investigated. The

twisted monofilament cords were made of monofilament

yarns and those monofilament plies were twisted together

and RFL dipped by simulating multifilament cords. Actually

twisted monofilament cords were interpreted as a cord

having properties between monofilament and multifilament

cords. It was observed that, cord properties were adjusted

flexibly by playing with monofilament diameter and the

number of plies in a cord. The load-elongation (%) behavior

of nylon 6.6 and Polyester monofilament cords were

different from each other. The breaking strength of cords

was changed proportionally between 9 and 80 kg with the

diameter of monofilament yarn and with the number of

monofilament ply. The Polyester monofilament cords exhibited

rayon like high initial modulus. The thermal shrinkage of

adhesive treated cords was almost on similar levels. The

adhesion of the designed cords was on acceptable level

compared to multifilament cords and single ply monofilament

cords. Nylon 6.6 twisted monofilament cords exhibited

prevailing fatigue performance under dynamic conditions.

High fatigue resistance was a desired property for carcass

and aircraft tire application and twisted monofilament cords

might contribute to this application. The cross-sectional

analysis showed that cord geometry was shaped by the ply

number of the monofilaments forming the cord. Since

twisted monofilament cords were made of several plies, they

had better cut resistance compared to single ply monofilament

cords for protective layer of belt package of special tires.

The bending stiffness of twisted monofilament cords was

adjustable by diameter and ply number of monofilaments.

High bending stiffness of twisted monofilaments might

contribute to the handling performance of tires. As a

replacement material of one of the steel belt layer in the belt

package of a tire, lighter tires was possible to be produced

and might contribute to less energy consumption of the tire.

Twisted monofilament cords can be a candidate for different

tire applications.

Acknowledgement

The author would like to thank all Kordsa Global R&D

Laboratory technicians for their valuable observations and

contributions.

References

1. J. Malin, S. C. Agarwal, M. J. Roon, and D. E. Wells, U.S.

Patent, 6634398B1 (2003).

2. I. M. Sinopoli, J. G. Morgan, A. Hardy, and M. Y. Susutoglu,

U.S. Patent, 5743975 (1998).

3. J. H. Gifford, U.S. Patent, 5082713 (1992).

4. T. Horikawa, T. Kogure, T. Morikawa, Y. Miyazaki, and

M. Okihara, U.S. Patent, 5221383 (1993).

5. B. Yilmaz, J. Adhesion, 86, 430 (2010).

6. B. Yilmaz, J. Adhes. Sci. Technol., 23, 1893 (2009).

7. A. Aytaç, B. Y lmaz, and V. Deniz, Fiber. Polym., in press

(accepted 2010).

i

Figure 6. Microscopic cross-sectional views of twisted monofilament

cords (a) cord made of 3 ply monofilament yarn, (b) cord made of

4 ply monofilament yarn, (c) cord made of 5 ply monofilament

yarn, and (d) cord made of 6 ply monofilament yarn.