Fibers and Polymers 2013, Vol.14, No.4, 647-652 DOI 10.

1007/s12221-013-0647-9

Development of UV Protective Sheath for High Performance Fibers for High

Altitude Applications
Jessica Won, Magdi A. Said1, and Abdel-Fattah M. Seyam2*
Hyosung Corporation, Anyang 431-080, Korea
1
National Aeronautics and Space Administration, Wallops Island, VA, USA
2
College of Textiles, NC State University, Raleigh, North Carolina, USA
(Received June 1, 2012; Revised August 10, 2012; Accepted September 5, 2012)

Abstract: High performance fibers have distinguished properties such as high tensile strength, good thermal and chemical
resistance, dimensional stability, lightweight, and high electrical conductivity. Due to these superior properties, high
performance fibers made it to the scene of broad range of applications such as aerospace, automotive, windmill, fiber
reinforced composites, high strength tethers, tendons for scientific balloon, tension structures, protective clothing, and
marine. Examples of such fibers are Zylon®, Kevlar®, and Vectran®. However, the fibers lose their strength significantly upon
exposure to Ultraviolet (UV) and visible light. In this research, UV protective films from extruded low density polyethylene
(LDPE) loaded with different content of UV stabilizers (TiO2 nanoparticles and White PE CC®) were investigated. To assess
the degree of UV blockage of each extruded protective film, their transmittance to UV and visible (UV-VIS) light was
measured. Additionally, Zylon® braids were sheathed with the protective films and the strength of the braids and yarns
raveled from braids was measured before and after UV exposure for different number of days. LDPE loaded with White PE
CC® and 10 % TiO2 showed the least transmittance to UV-VIS and their yarns and braids exhibited highest strength retention
after exposure to artificial UV. Strength retention of braids was higher than that of individual yarns due to weak link effect
and braid structure assistant.
Keywords: High performance fibers, Ultraviolet and visible light, Low density polyethylene, Zylon®

Introduction which is the most important mechanical property of high

performance fibers [2-5]. Additionally, previous work at
The demand for materials with high flexibility, high strength NCSU supported by NASA Scientific Balloon Program
to weight ratio, high thermal and chemical resistance, good showed that chemically coating the fiber surface with a thin
dimensional stability, and high abrasion resistance has led to film containing UV blockers does not provide required
the development of high performance fibers. Numerous high protection due to the lack of durability of the coating
performance fibers have established themselves in high tech materials and the lack of uniformity of the coat along the
applications such as aerospace, automotive, windmill, fiber yarn as well as between and within the filaments. The work
reinforced composites, high strength tethers, tendons for revealed that physical coverings with thin film gave better
scientific balloon, tension structures, protective clothing, and protection compared to chemical treatments [6].
marine. Examples of high performance fibers include Zylon®, This work was undertaken to develop suitable protective
Kevlar®, Spectra®, and Vectran®. systems for high performance fibers from UV radiation. In
However, high performance fibers are generally sensitive this work, protective films were developed from extrusion of
to light exposure since the light has enough energy to break low density polyethylene (LDPE) loaded with different
polymeric structure especially UV radiation. High performance content of TiO2 and white pigment. One of the promising
fibers lose their strength significantly, which is the most high performance fibers for the use as tendon to support
important characteristic of such fibers, upon exposure to UV scientific balloon structure, Zylon, was used for this study.
light. To overcome such undesired characteristics, many While Zylon is the best high performance fiber that meets
researches have been undertaken to protect high performance the characteristics required for supporting scientific balloon
fibers form UV and visible light and showed the efficacy in structure, it loses its strength dramatically upon exposure to
reducing the photo degradation such as loading with UV UV [6]. Our ultimate goal is to develop UV protective layers
stabilizers, coating with surface finish systems containing for Zylon tendon (braid) in order to preserve its high strength
UV stabilizers, and sheathing with protective layers loaded to weight ratio to achieve long duration of flight of NASA
with UV stabilizers. scientific balloon.
However, loading and coating with UV stabilizers to most
of high performance fibers during spinning is not applicable Experimental
due to the harsh conditions of spinning process [1]. Also,
adding UV blocker/absorber may cause loss of strength, Materials
Films were extruded from compounded polymer made of
*Corresponding author: [email protected] low density polyethylene (LDPE) in pellet form loaded with

647
648 Fibers and Polymers 2013, Vol.14, No.4 Jessica Won et al.

or without UV stabilizer. LDPE was used since it is resistant Table 1. Experimental design
to UV and temperature that is suitable for high altitude. Variable Levels
Rutile TiO2 and White PE CC® were used as UV stabilizers None (or Bare Braid)
with different amount. The TiO2, product of Nanostructure PE sheath without UV stabilizers
& Amorphous Materials, Inc., is nanoparticle with 4.17 g/ml Type of sheath PE sheath loaded with 5 % TiO2
and cylindrical shape with diameter of 10 nm and length of PE sheath loaded with 10 % TiO2
40 nm. White PE CC®, product of PolyOne Corporation, is PE sheath with 12 % White CC®
PE compounded with Calcium Carbonate, Silica (amorphous), Exposure time (days) 0, 1, 2, 3, 4, 6
and TiO2 of standard size. PolyOne Corporation, Avon Lake,
Ohio, USA did not reveal the content of this product.
To assess the effectiveness of the proposed UV protective TiO2 (PE 10 % TiO2), and (4) LDPE extruded films loaded
layers, a braid which is the load carrying member “tendon” with 12 % White PE CC® (PE 12 % White CC®).
for the NASA Super Pressure Balloon “SPB” was used in
this study. The tendon (braided structure) is made from Experimental Design
Zylon®, which is p-phenylene-2,6-benzobisoxazole (PBO), Full factorial design with two variables namely type of
and has the highest strength and modulus among the sheath (5 levels) and time of exposure to simulated UV (6
currently available high performance fibers. The tendon levels) was structured to find out which sheath provides the
(48,000 denier) is a hollow 2×2 braid formed by 16 carrier most protection for the Zylon® braid from UV. In total 30
braiding machine. Each carrier supplied a strand of 2 yarns runs (5×6) samples are required to execute the design. Table 1
of 1500 denier each and thus the total braid denier is 48,000 shows the experimental design variables along with their
denier. The braid was manufactured at Cortland Cable levels. The unsheathed braid (control) and the braids with
Company, Cortland, New York, USA. four types of extruded polyethylene films were exposed to
UV and visible light for 0, 1, 2, 3, 4, and 6 days.
Formation of Extruded Films The responses (dependent variables) considered for the
In this research, extrusion of LDPE film loaded with UV experiment include UV-VIS transmittance and tensile
blockers was adopted as physical covering procedure for properties of braids and yarns raveled from braids to identify
protecting the braids from UV and visible light since the the best protective candidate for high performance fibers.
extrusion procedure has been commercially available for
electric wires for many years. Polymer extrusion technology Testing and Evaluation
is one of the proven methods to integrate, insulate, and The UV-VIS transmittance assessment for sheaths taken
protect different materials including, electrical wires, braids, from the sheathed braids was conducted on the four sheathes
and optic fibers from surrounding environment. of Table 1 using Varian Cary® 300 UV-VIS spectroscopy.
Extrusion process was performed in industrial scale at For the current measurement, the sphere sample holder was
Cortland Cable Company. The reason behind the industrial used to simulate high altitude conditions. Measurements
trial (rather than controlled research lab trial) is the need of were done at intervals of 1 nm in the wavelength range from
large quantity of the NASA Scientific Balloon (about 80 km 200 to 800 nm.
of braid/balloon). Untreated braid was fed into extrusion die Samples were exposed to artificial UV and visible light
to apply the compounded polymers. During sheathing, the using Atlas Ci3000+ Weatherometer. Xenon lamp and quartz/
braid was fed through the extruder head and the extruded quartz (Q/Q) filters were used to simulate extraterrestrial
film covered (surrounded) the tubular braid. Right after solar radiation (~40 km, ~20-30 oC) which has an extremely
sheathing, the sheathed braid was passed through cold water high output of radiant power throughout the UV, visible, and
bath to chill the sheath and prevent the polymer from infrared regions. With this setup the lamp emits radiation
penetrating through the braid. The sheath added weight was starting from 230 nm in the UV range up to 750 nm in the
approximately 2.7 g/meter braid. After extrusion the braids visible range [8,9]. Spectral power distribution of the Xenon
became more circular with higher density (2.9 mm diameter arc source with quartz/quartz filter is shown in Figure 1.
and 5.45 g/m linear weight) since the sheath was tightly The maximum time of exposure of six days was decided
surrounding the braid. More details on physical characteristics based on our previous work which showed that after such
(Energy Dispersion X-ray Analysis (EDX) by SEM, Thermal time no further strength loss occurred for high performance
Gravimetric Analysis (TGA), and Transmission Electron fibers tested (Zylon®, Spectra®, Kevlar®, and Vectran®) [10].
Microscopy (TEM)) are reported in reference 7. Tensile testing of braids was performed using Instron 8800
Four types of sheathes were produced and evaluated: (1) Servo-Hydraulic system. All tendons were spliced to 157.48 cm
LDPE extruded film without UV blockers (Unloaded PE, PE (62 inches) eye to eye. The eyes were 12.7 cm (5 inches) and
0 % TiO2), (2) LDPE extruded films loaded with 5 % TiO2 each bury was 45.72 cm (18 inches). The actuator displacement
(PE 5 % TiO2), (3) LDPE extruded films loaded with 10 % was set to operate at a rate of 2.54 cm/min (1 inch/min).
UV Protective Sheath Fibers and Polymers 2013, Vol.14, No.4 649

its opaqueness.
Transmittance percentage was calculated by averaging all
the transmittance percentage in each range of wavelength
and the results are depicted in Figure 2. In the UV region PE
5 % TiO2, PE 10 % TiO2, PE with White PE CC® showed
excellent protection with less than 1%, which means sheaths
can block most of UV light. PE with White PE CC® showed
the best protection in the visible light range. As seen in
Figure 2, for most of the UV spectrum the transmission
curve of 5 % TiO2 and 10 % TiO2 are very close, however, in
the wavelength range of 390-400 nm, the transmission in
case of 5 % TiO2 is significantly higher (as much as 2 times)
compared to 10 % TiO2. Also, for wavelengths greater than
400 nm, the transmission in case of 5 % TiO2 is as much as
Figure 1. Spectral power distribution for xenon arc source in Atlas 30 % higherthan 10 % TiO2. The results suggest that the
Ci3000+ Weatherometer [7]. relationship between transmission and amount of UV blockers
added varies in different ranges of wavelength.
Transmission curves in Figure 2 also show that in the
Specimen was attached to 22.24 kN (5,000 lbs) load cell. wavelength range of 400-425 nm, the transmission in case of
Tensile testing of individual 2-ply yarns was performed White PE CC® is higher compared than 10 % TiO2. Even
according to ASTM D 2256 using MTS Renew machine though the transmission in the case of White PE CC® is only
with 5 kN load cell. Gauge length was 25 cm and cross head slight higher, it is not known whether it would result in any
speed was 30 cm/min. Pneumatic jaws were used to be able significant increase in degradation. Further research is
to grip such high performance fibers and grip pressure was warranted to clearly understand these phenomena.
0.552-0.689 MPa (80-100 psi).
Assessment of Protective Sheathes in Terms of Tendon
Results and Discussion Strength
Tensile tests were conducted on PBO braids with and
UV-VIS Transmittance without protective films and before and after exposure to
Figure 1 shows the result of transmittance of the four types UV and visible light for 1, 2, 3, 4, and 6 days. The results of
of extruded polyethylene films. Unloaded PE was transparent the breaking load are presented in Figure 3. The error bar in
and could not block most of UV and visible rays. PE 10 % the figure is the standard error of the mean which is the
TiO2 and PE 5 % TiO2 showed similar behavior which could standard deviation of the sampling distribution of the mean.
block most of UV light and some of visible light. PE 10 % Some of the error bar not appeared in the figure due to high
TiO2 showed better protection than PE 5 % TiO2 as it was uniformity of the individual observations. Each data point on
expected, but there was no significant improvement despite the figure is the mean of five braid specimens.
of twice amount of TiO2. Similar to the PE loaded with TiO2, The PBO braids before exposure showed some differences.
PE loaded with White PE CC® could block most of UV Before exposure, the braid with no protection showed slightly
light. However, PE with White PE CC® transmittance to higher strength than the braids sheathed with protective
visible light was the lowest among the four sheathes due to

Figure 3. Tendon breaking load of the PBO braids before and after
Figure 2. UV-VIS transmittance of extruded polyethylene films. exposure.
650 Fibers and Polymers 2013, Vol.14, No.4 Jessica Won et al.

Figure 4. Tensile strength loss of the PBO braids before and after Figure 5. Tensile strength of the PBO yarn before and after
exposure. exposure.

films of unloaded PE, PE White PE CC®, PE 5 % and 10 %

TiO2. The difference of braid strength before UV exposure
can be attributed the strength variation in the PBO braid
itself as well as varying strength loss during sheathing
process and shipping. It was noticed that the shipment was
not handled properly according to recommendation for the
high performance fibers (they must be wrapped with PE
sheets loaded with carbon black).
The results of the tendon tensile strength loss in % are
shown in Figure 4. The PBO braid with no protection lost
72 % of tensile strength after 6 days of exposure to UV and
visible light. The PBO braid sheathed with unloaded PE
showed maximum 59 % of tensile strength loss after 6 days
Figure 6. Tensile strength loss of the PBO yarn before and after
of exposure. The PBO braid sheathed with PE loaded with exposure.
White PE CC® showed maximum 37 % of tensile strength
loss after 6 days of exposure. Similarly, the PBO braid
sheathed with PE loaded with 5 % TiO2 showed maximum the braid with and without protective films before and after
43 % of tensile strength loss after 6 days of exposure. The exposure to UV and visible light for 1, 2, 3, 4, and 6 days.
PBO braid sheathed with PE loaded with 10 % TiO2 showed Tested PBO yarns were 2-ply yarn of 3,000 total denier
the best protection regardless of exposure time with maximum (1,500×2). The results of tensile strength are shown in
30 % of tensile strength loss after 6 days of exposure. Figure 5 with error bars exhibited. Each data point in Figure
The ANOVA results for multiple mean comparisons 5 is the mean of 8 observations. The corresponding results of
showed the set of means are different from each other and tensile strength loss in % are presented in Figure 6.
the breaking load of PBO braid sheathed with extruded The PBO yarn with no protective film lost 77 % of tensile
polyethylene films is affected by the type of sheath and the strength after 6 days exposure which is from 24.80 to 5.78
time of exposure. Also the interaction of type of sheath and cN/denier. The yarn sheathed with unloaded PE showed
time of exposure showed significant effect, since as time maximum 73 % of tensile strength loss after 6 days of
goes longer, the difference between types of sheath becomes exposure. The yarn sheathed with PE White PE CC® showed
larger. the best protection regardless of exposure time with maximum
However, braids sheathed with PE loaded with White PE 35 % of tensile strength loss after 6 days of exposure. The
CC® and 5 % TiO2 are not significantly different per both yarn sheathed with PE 5 % TiO2 showed maximum 59 % of
Tukey’s and Scheffe’s multiple mean comparison methods. tensile strength loss after 6 days of exposure. The yarn
Also 3 days of exposure and 4 days of exposure are not sheathed with PE 10 % TiO2 showed maximum 50 % of
significantly different from Scheffe’s method. Details of the tensile strength loss after 6 days of exposure.
statistical analyses are published in [11]. Similar to the unexposed braid tensile strength, the yarns
raveled from the unexposed braids with and without protection
Assessment of Protective Sheathes in Terms of Yarn showed variable strength due to the variability in the braids
Strength itself as well varying strength losses during sheathing
Tensile tests were conducted on PBO yarns raveled from process and shipping as discussed earlier.
UV Protective Sheath Fibers and Polymers 2013, Vol.14, No.4 651

Statistical analyses using ANOVA indicate the set of Table 2. Strength ratio of each type of protective films before and
means are significantly different from each other and the after exposure
tensile strength of PBO yarn sheathed with extruded Exposure Strength ratio
polyethylene films is affected by the types of sheath and the time No PE PE White PE 5 % PE 10 %
time of exposure. Also the interaction of type of sheath and (day) protection unloaded CC® 12 % TiO2 TiO2
time of exposure is significant. However, unprotected yarns
0 1.14 1.11 1.04 1.05 1.09
and the yarn sheathed with unloaded PE are not significantly
different per Tukey’s and Scheffe’s multiple mean comparisons. 1 1.09 1.21 0.99 1.13 1.04
Details of the statistical analyses are shown elsewhere [11]. 2 1.28 1.43 0.92 1.35 1.19
3 1.34 1.48 1.01 1.31 1.32
Effect of Braid Structure on Tensile Strength 4 1.38 1.38 1.05 1.33 1.52
The difference between the results of PBO braid and yarn 6 1.35 1.66 1.02 1.47 1.54
tensile strength was investigated. The samples exposed to
UV and visible light for 6 days were chosen to check whether
there is a significant difference. The results of tensile strength exceptions.
loss after 6 days of exposure are presented graphically in The strength ratio of the braid and yarn sheathed with
Figure 7. With the exception of the results of the braid unloaded PE showed the highest ratios which means there
protected by PE White CC®, the yarn tensile strength loss was significant difference between braid strength per yarn
showed higher values compared to the braid tensile strength and individual yarn strength raveled from braid. Also, the
loss. strength ratios of the braid and yarn unsheathed and
The braid with no protection showed 72 % of strength loss sheathed with PE 10 % TiO2 and PE 5 % TiO2 showed value
while the corresponding yarn showed 77 % of strength loss. from 1.05 to 1.54 which is also significantly larger than one.
The braid protected by unloaded PE sheath showed 59 % of This can be explained by weak link effect and structure
strength loss while the yarn showed 73 % of strength loss. assistant. Since a yarn or braid breaks at its weakest point,
The braids protected by PE loaded with 5 % and 10 % TiO2 the variability of the structure determines its strength. Braid
showed 43 % and 29 % strength loss and the yarns showed which is a group of yarns exhibits lower variability than a
59 % and 50 % of strength loss, respectively. single yarn since a yarn breaks at its weakest point while
To sum up, the entire PBO braid lost less amount of tensile braid breaks at its weakest cross-sections that contained
strength than individual yarns except the braid sheathed with many constituents. Although in the braid each yarn has
PE White CC®. Also, the samples that were given more weakest point at random locations, the weak point effect is
protection have larger difference between the result of braid dramatically reduced since they are supported or compensated
test and the result of yarn test. by other constituents of the braid structure. Therefore, yarns
Table 2 shows the results of the strength ratio defined as exhibit more variability than braids and are weaker than
the ratio of yarn strength in the braid (or the braid strength braids.
divided by number of yarns in the braid) to individual yarn Also the inter-yarn friction caused by the braid interlacing
strength load as determined from raveled yarn test. Most of (2×2 interlacing) causes fiber binding, which in turn yarn
values are larger than unity (1.0) which means the yarns in reduces the effective gauge length, and hence the weak link
the braid had higher strength than individual yarns with few effect is reduced. Additionally, yarn and fiber binding in the
braid structure hinders individual yarn or fiber from individual
break a matter that allows load sharing of yarns and fibers.
Figure 6 shows more strength loss in individual yarn
compared to braids, in all samples except in White PE CC®.
In the case of White PE CC®, no significant difference was
seen in strength loss of braid and the individual yarns. This
phenomenon can be explained by varying degree of brittleness
of the sheath in samples. It was observed sheaths containing
TiO2 nanoparticles were more brittle after exposure to UV-
VIS radiations. It seems likely that brittleness in the sheath
caused development of small cracks which resulted in
formation of new weak spots or further weakening of existing
weak points on the braid. All these factors would increase
the structural variation in the individual yarns, thus increasing
Figure 7. Tensile strength loss of the PBO braid and yarn after the strength loss in individual yarns. The braid however
6 days of exposure. could still largely compensate for the weakening of individual
652 Fibers and Polymers 2013, Vol.14, No.4 Jessica Won et al.

yarns due to the structural assistance. No significant brittleness braid tensile strength showed braids sheathed with LDPE
was seen in sheaths containing White PE CC®. Varying loaded with White PE CC® and 10 % TiO2 lost the least
diffusive ability of different UV blockers is also like to amount of their tensile strength; 36.8 % and 29.4 %
contribute to the above phenomenon. In Table 2, the PE respectively. However, the braid with no protection lost
unloaded sample has the highest ratio after 6 days of 72.4 % of its tensile strength.
exposure because of the lack protection resulting from the
absence of UV blockers in sheath. While the sheath provide Acknowledgement
some protection against the radiations, localized weakening
of the individual yarns thus reduction of overall strength of This work is funded by NASA Balloon Program Office
the yarns, however the braid is able to compensate for many (Grant Number NNXlOAE26G) and the State of North
of these localized weakening in the individual yarns. Lower Carolina. The authors extend their appreciation to Dr. Rahul
ratio in case of samples with no protective sheath suggests Vallabh of NC State University College of Textiles for his
that direct exposure resulted in significant weakening at the valuable discussion.
cross-over points relative to the weakening of the individual
yarns. The synergistic interaction of these factors is being References
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