Technical Information (Revised 2005.6)

TOYOBO CO., LTD.

ZYLON®(PBO ) Technical Information (2005)

Contents 1. Basic properties 2. Comparison with other high-performance 3. Influence of twist on tensile properties 4. Creep properties 5. Thermal behavior 5.1 TGA Analysis 5.2 Isothermal weight loss 5.3 Strength retention after thermal treatment 5.4 Strength retention at high temperature with humidity 5.5 Effect of temperature on strength and modulus 5.6 Hot air shrinkage 5.7 Flame resistance 5.8 Combustion products 6. Light resistance 7. Chemical resistance 7.1 Organic mediums 7.2 Inorganic mediums 7.3 Seawater 8. Moisture pick-up 9. Miscellaneous 9.1 Compressive strength 9.2 Knot and loop strength 9.3 Thermal expansion coefficient 9.4 Heat capacity 9.5 Abrasion resistance between fiber and metal

2

1. Basic Properties ®(PBO fiber) is the next generation super fiber with strength and modulus almost doubles that of p- fiber. ZYLON® shows 100°C higher decomposition temperature than p-Aramid fiber. The limiting oxygen index is 68, which is the highest among organic super fibers. There are two types of fibers, AS (as spun) and HM (high modulus). HM is different from AS in modulus, moisture regain and etc.

ZYLON®AS ZYLON®HM Filament decitex 1.7 1.7 Density (g/cm3) 1.54 1.56 Tensile Strength (cN/dtex) 37 37 (GPa) 5.8 5.8 (kg/mm2) 590 590 Tensile Modulus (cN/dtex) 1150 1720 (GPa) 180 270 (kg/mm2) 18000 28000 Elongation at break(%) 3.5 2.5 Moisture regain(%) 2.0 0.6 Decomposition Temp.(°C) 650 650 LOI 68 68 Thermal expansion coefficient - -6x10-6

2. Comparison of mechanical properties with other fibers ZYLON® has the highest tensile strength and tensile modulus among high-performance fibers.

Elonga- Moisture Heat Tenacity Modulus Density LOI tion Regain Resistance*

cN/dtex GPa cN/dtex GPa % g/cm3 % C

Zylon® AS 37 5.8 1150 180 3.5 1.54 2.0 68 650

Zylon® HM 37 5.8 1720 270 2.5 1.56 0.6 68 650

p-Aramid(HM) 19 2.8 850 109 2.4 1.45 4.5 29 550

m-Aramid 4.5 0.65 140 17 22 1.38 4.5 29 400

Steel Fiber 3.5 2.8 290 200 1.4 7.8 0

HS-PE 35 3.5 1300 110 3.5 0.97 0 16.5 150

PBI 2.7 0.4 45 5.6 30 1.4 15 41 550

Polyester 8 1.1 125 15 25 1.38 0.4 17 260

*Melting or Decomposition Temperature

3

The stress-strain curves of ZYLON® compared with other high-performance fibers are shown below.

6

5

4

3

Stress(GPa) 2 Zylon AS Zylon HM p-Aramid 1 p-Aramid HM copoly-Aramid Carbon 0 0123456 Strain (%) 3. Influence of twist on tensile properties ZYLON® is shipped with zero twist. A certain twist has to be applied in order to measure its correct tensile strength. These figures show the influence of twist factor on tensile strength and modulus for 555 dtex ZYLON® yarn. For different dtex yarns, optimum twist level can be estimated by using twist factor. Twist factor is defined by the following formula.

Twist factor (TF) = 0.124 x (turns per inch) x (dtex)0.5

45 1400 45 2000

40 1200 40 1800

35 1000 35 1600 Tenacity(cN/dtex) Strength(cN/dtex) 30 800 Modulus(cN/dtex) 30 1400 Modulus(cN/dtex)

Zylon AS 555dtex Zylon HM 555dtex 25 600 25 1200 0 5 10 15 20 0 5 10 15 20 Twist Factor Twist Factor

4

4. Creep Properties ZYLON® has superior creep resistance to p-Aramid fibers. (Creep means a non-recoverable strain after prolonged static loading.) When a certain load is applied to yarn, recoverable strain (initial strain) and non-recoverable strain are observed. For ZYLON® HM, non-recoverable strain after 100 hours under 50% of breaking load (Safety factor (SF)=2) is less than 0.03%.

2.00 100

1.75 90 1.50 80 1.25

Strain(%) 70 1.00 Zylon AS Zylon HM

0.75 load) of breaking Stress(% 60 p-Aramid Zylon HM SF=2 p-Aramid HM 19 years 0.50 50 2 3 4 5 6 7 0.10 1 10 100 1000 11 10 10 10 100 10 1000 10000 10 10000010 100000 10 100000 10 0 00 Time(hr) Time to Failure(min) Creep Parameter Creep parameters (slope of straight line in above figure) are compared with p-Aramid fibers. ZYLON® shows less than half of creep parameter of p-Aramid fiber. Creep strain is measured under 50% of the breaking load for each fiber. Note that the actual load applied to ZYLON® is almost double that of p-Aramid fiber.

Creep parameter under 50% of breaking strength

Zylon AS Zylon HM p-Aramid p-Aramid HM

3.2×10-4 1.1×10-4 5.0×10-4 2.5×10-4

Time to failure After a certain loading time, yarn breakage may occur. The above figure shows the relationship between time to failure and applied load level (ZYLON®HM). Based on the extrapolation, 107 minutes (19 years) of time to failure can be estimated under 60% of the breaking strength.

5

5. Thermal properties 5.1 Decomposition Temperature ZYLON® has a 100°C higher decomposition temperature than p-Aramid fibers. Thermal gravimetric analysis charts in air and argon gas are shown below. The heating rate is 20°C/min.

100 100

80 80

60 60

in air in Ar 40 40 Zylon AS Zylon AS Zylon HM Zylon HM Residual Weight(%) Residual Weight(%) Residual p-Aramid p-Aramid 20 20 p-Aramid HM p-Aramid HM copoly-Aramid copoly-Aramid 0 0 0 100 200 300 400 500 600 700 0 100 200 300 400 500 600 700 Temperature(℃) Temperature(℃)

5.2 Isothermal weight loss A significant difference of weight loss behavior is observed at 500°C between ZYLON® and Aramid fibers.

100 100 500℃ 80 80

60 60

40 40 Zylon AS Zylon HM Zylon AS Residual Weight(%) Residual Weight(%) Zylon HM 20 p-Aramid 20 p-Aramid p-Aramid HM 400℃ p-Aramid HM copoly-Aramid copoly-Aramid 0 0 0 50 100 150 200 0 50 100 150 200 Time(min) Time(min)

6

5.3 Strength retention after thermal treatment These figures show the effect of thermal treatment in air on residual strength. ZYLON®HM shows a little higher heat resistance than ZYLON®AS.

100 100 Zylon AS 200℃ Zylon HM 200℃

80 80

250℃ 60 250℃ 60

40 40 300℃

Strength Retention(%) 300℃ Strength Retention(%) 20 20 400℃ 350℃ 400℃ 350℃

0 0 1 10 100 1000 1 10 100 1000 Time(hr) Time(hr)

Strength retention after thermal treatment is compared with Aramid fibers at several temperatures.

100 100 250℃

80 80

60 60

40 40 Zylon AS Zylon HM ZYLON AS Strength Retention(%) Strength Retention(%) ZYLON HM p-Aramid 20 20 p-Aramid p-Aramid HM p-Aramid HM copoly-Aramid 200℃ copoly-Aramid 0 0 0 250 500 750 1000 0 200 400 600 Time(hr) Time(hr)

7

100 100 Zylon AS Zylon AS Zylon HM p-Aramid Zylon HM 80 p-Aramid HM 80 p-Aramid copoly-Aramid p-Aramid HM copoly-Aramid 60 60

40 40 Strength Retention(%) Strength Retention(%) 20 20 ℃ 300℃ 350 0 0 0102030 0 50 100 150 Time (hr) Time(hr)

100 100 Zylon AS Zylon HM p-Aramid HM 80 copoly-Aramid 80

400℃ 60 60

40 40 500℃ Strength Retention(%) Strength Retention(%) Zylon AS 20 20 Zylon HM p-Aramid p-Aramid HM 0 0 0 5 10 15 20 0306090120 Time (hr) Time(sec)

8

5.4 Strength retention at high temperature with humidity The strength of ZYLON® decreases in the condition of high temperature and high humidity. The residual strength after a 50 hours treatment with saturated steam at 180°C is 40-50%, which is between p-Aramid and copoly-Aramid fiber.

100 100 Zylon AS Zylon HM 80 80 p-Aramid copoly-Aramid 250℃ 60 60

40 40

Strength Retention(%) Zylon AS

20 Zylon HM Strength Retention(%) 20 p-Aramid 180℃ copoly-Aramid 0 0 0 1020304050 0 1020304050 Time(hr) Time(hr)

The strength of ZYLON® gradually decreases even at the temperature of less than 100°C in high humidity condition. ZYLON® fiber should be stored free from high humidity at normal room temperatures.

100 100

80 80

60 60

40 40

Room temperature and Strength Retention (%) Strength Retention(%) 80℃ humidity at warehouse 20 20 60℃ 40ºC 80%RH 40℃ 80% RH Zylon AS 555dtex 0 0 0 20406080100 0 200 400 600 800 1000 Time(day) Time (day)

9

5.5 Effect of temperature on strength and modulus The relative strength of ZYLON® decreases from room temperature to 500°C. ZYLON® retains 40% of the room temperature strength even at 500°C.

The temperature dependence of modulus is shown below. Even at 400°C, ZYLON® retained 75% of modulus at room temperature.

100 100

80 80

60 60

40 40

Relative Strength(%) Zylon AS Relative Modulus(%) Relative Zylon AS 20 Zylon HM 20 p-Aramid Zylon HM p-Aramid HM p-Aramid HM 0 0 0 100 200 300 400 500 0 100 200 300 400 Temperature(℃) Temperature(℃)

5.6 Hot air shrinkage Shrinkage (permanent) after hot air treatment for 30 minutes without load was measured. ZYLON® shows very low shrinkage as compared with other super fibers.

2.5 Zylon AS Zylon HM 2 p-Aramid copoly-Aramid

1.5

1 Shrinkage(%)

0.5

0 0 100 200 300 400 Temperature(℃)

10

5.7 Flame resistance ZYLON® shows extremely high flame resistance. In a vertical flame test (JIS L1091 A-4), char length is almost zero.

Zylon p-Aramid m-Aramid warp fill warp fill warp fill Char length(cm) <0.5<0.53266 After flame(sec) 000000 After glow(sec) 11161622 LOI 68 29 29

Plain woven fabrics with 20's spun yarn

5.8 Combustion products Generated gases at the temperature of 750°C were measured according to Japanese Industrial Standard(JIS). The amount of toxic gases such as HCN, NOx and SOx from ZYLON® is very small compared with p-Aramid fiber.

Temp. CO CO2 NH3 HCN HCl NOx SOx

Zylon 500 6.9 35.8 0.35 1.48 <0.01 0.15 <0.01

750 1> 2660 0.05> 0.57 <0.01 0.16 0.1

p-Aramid 500 107 1230 3.95 14.8 <0.01 1.00 1.40

750 112 2010 0.05> 25.1 <0.01 0.47 1.04 mg/g

Decomposition gases at 500°C were also measured. In the process of glass molding or aluminum extrusion, cushion materials such as felt are heated sometimes up to about 500°C. The amount of toxic gases from ZYLON® was also small at that temperature.

11

6. Light resistance The strength of ZYLON® decreases with exposure to sunlight. Light resistance of ZYLON® was evaluated using Xenon light weather-ometer. As shown below, the strength decreases sharply at the initial stage of exposure. End products of ZYLON for outdoor use have to be protected by covering materials. The residual strength of ZYLON® after 6 months exposure to daylight is about 35%.

100 120 83℃ Zylon AS 100 80 Zylon HM

80 60 60 40 40 Zylon AS Strength Retention(%) 20 Zylon HM Retention (%) Strength 45°south p-Aramid 20 Ohtsu, p-Aramid HM 97/6 - 97/11 Xenon wether-ometer 0 0 0 100 200 300 400 500 0123456 Time (hr) Time (month)

ZYLON® should be protected not only from ultraviolet light but also from visible light. These data show strength retention after exposure to fluorescent lamp.

100

80

60

40 Strength Retention(%) 20 Fluorescent lamp (35W x 2) ZYLON AS 150 cm from lamp ZYLON HM 0 0 200 400 600 800 Time(hr)

12

7. Chemical resistance 7.1 Organic mediums ZYLON® is stable with most of organic mediums. Strength retention(%) after immersion for 500 hrs at room temperature

Chemicals Zylon AS Zylon HM

Methylethylketone 100 99

Dimethylformamide 100 97

Methanol 100 99

Gasoline 100 95 Brake Fluid 100 96

7.2 Inorganic mediums Exposure to strong acids causes strength losses. However, ZYLON® is more stable than p-Aramid. 100 100

80 80

60 60

40 40

Zylon AS Strength Retention(%) Zylon HM Strength Retention(%) Zylon AS 20 20 Zylon HM p-Aramid H SO 60% p-Aramid HM 2 4 p-Aramid HCl 20% p-Aramid HM copoly-Aramid 25℃ 25℃ copoly-Aramid 0 0 0 100 200 300 400 500 0 100 200 300 400 500 Time(hr) Time(hr) 100

80

60

40

Zylon AS Strength Retention(%) 20 Zylon HM p-Aramid HNO3 20% p-Aramid HM ℃ copoly-Aramid 25 0 0 100 200 300 400 500 Time(hr)

13

ZYLON® is stable to alkaline at room temperature. NaClO (bleach) does not cause strength loss for ZYLON® at room temperature.

100 100

80 80

60 60

40 NaClO 5% 40 25℃ Zylon AS Strength Retention(%) Zylon AS Zylon HM Strength Retention(%) 20 20 Zylon HM p-Aramid NaOH 20% p-Aramid p-ramid HM 25℃ p-Aramid HM copoly-Aramid copoly-Aramid 0 0 0 100 200 300 400 500 0 100 200 300 400 Time(hr) Time(hr)

At higher temperatures, the strength of ZYLON® AS staple fiber decreases in acid and also in alkaline.

100 100

Zylon p-Aramid 80 80 m-Aramid PPS PBI

60 60

40 40 Strength Retention(%) Strength Retention(%) 20 20 Staple Fiber Zylon p-Aramid Staple Fiber 5% H2SO4, 75℃ m-Aramid PPS 10%NaOH 75℃ PBI 0 0 0 50 100 150 200 250 0 50 100 150 200 250 Time(hr) Time(hr)

14

7.3 Seawater resistance Seawater simulation shows similar strength loss to high humidity condition.

100

80

60

40

Strength Retention(%) 20 30°C Zylon AS 3.5%NaCl p-Aramid 0 0 100 200 300 400 500 Time (day)

8. Moisture pick-up The moisture regain of ZYLON® at 20°C, 65%RH is 2.0% for AS and 0.6% for HM. The moisture regain of ZYLON® HM is far less than p-Aramid.

5 Zylon AS Zylon HM 4 20℃

3

2 Moisture Regain(%) 1

0 0 20406080100 Relative Humidity(%)

15

9. Miscellaneous 9.1 Compressive strength The compressive strength of ZYLON® is much less than the tensile strength same as para-Aramid fiber.

Sample Critical Strain Tensile Modulus Compressive Strength (%) (GPa) (GPa) ZYLON AS 0.217 216 0.469 ZYLON HM 0.227 247 0.561 Aramid HM 0.633 118 0.749 (Bending Beam Method)

9.2 Knot and loop strength Knot and loop strength of ZYLON® is 30-40% of its tensile strength. This is almost the same as p-Aramid fiber.

Yarn dtex Knot strength Loop strength

percentage(%) of tensile strength ZYLON AS 1110 32 45 ZYLON HM 1090 26 34

9.3 Thermal expansion coefficient Coefficient of thermal expansion of ZYLON® is negative. The dimension along fiber direction decreases with increasing temperature. CTE of ZYLON®HM is around –6ppm/°C.

16

9.4 Heat capacity

2.5 Zylon AS Zylon HM 2.0

） 1.5

Data from

Cp (kJ/kgK 1.0 Data from Univ.

0.5 Dr. Kazuya Saito, et.al., Osaka University Journal of Polym. Sci., Polym. Phys., Vol.38, p.1584 0.0 0 200 400 600 800 Temperature (K)

9.5 Abrasion resistance between fiber and metal Abrasion resistance of ZYLON® is higher than p-Aramid fiber under the same load, but much lower than or high molecular weight fiber.

150000 Load : 0.9g/dtex 120000

90000

60000

Cycle to Breakage 30000

0

e r E M t e P H a ryl Aramid Nylon6 lyest Mw ON - lya o H p P U ZYLON AS ZYL Po

17

NOTICE: The information in this brochure, to the best of our knowledge, is accurate and correct. However, Toyobo Co., Ltd. makes no warranty and assumes no liability whatsoever in connection with any use of this information. Users determine for themselves the suitability for their intended use of the material. The brochure is subject to revision as new information becomes available.

The materials are to be stored free from exposure to light, high temperature and humidity.

ZYLON is a registered trademark of Toyobo Co., Ltd. in Japan.

TOYOBO CO., LTD.

ZYLON DEPARTMENT 2-2-8 Dojima-Hama Kita-Ku OSAKA 530-8230 JAPAN Phone +81-6-6348-3130 Fax +81-6-6348-3413 http://www.toyobo.co.jp

F0739K(2005.6)

18