High Performance Polymers

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Nitrile butadiene rubber-based heat-shielding insulations for solid rocket motors: Effect of polyimide
fibrous reinforcement on the morphology and properties
Yuan Zhao, Shihao Hu, Wei Liu, Guangliang An, Zhanpeng Wu, Dezhen Wu and Riguang Jin
High Performance Polymers published online 31 July 2014
DOI: 10.1177/0954008314541819

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Original Article

High Performance Polymers

1–8
Nitrile butadiene rubber-based ª The Author(s) 2014
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heat-shielding insulations for solid sagepub.co.uk/journalsPermissions.nav

DOI: 10.1177/0954008314541819
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rocket motors: Effect of polyimide
fibrous reinforcement on the
morphology and properties

Yuan Zhao1, Shihao Hu2, Wei Liu1, Guangliang An1,

Zhanpeng Wu1, Dezhen Wu1 and Riguang Jin1

Abstract
Chopped polyimide (PI) fiber-filled nitrile butadiene rubber (NBR) insulations for solid rocket motors were fabricated by
surface modification of chopped PI fibers treated under oxygen plasma and subsequently by mixing formulation of NBR
insulations on a two-roll mill. The effects of chopped PI fibers’ surface modification on the mechanical and ablative prop-
erties were investigated. Results showed that excellent mechanical and ablative properties of the NBR insulations were
attributable to the high thermal stability and unique interfacial interactions between fiber and the matrix because of the
rougher surface character of modified chopped PI fibers. The microstructures of insulation and ablated charred layers
were also characterized by scanning electron microscopy and atomic force microscopy.

Keywords
Polyimide fiber, nitrile butadiene rubber, insulation, solid rocket motors, surface modification

Introduction Kevlar fiber is one of the most successful replacements

It is a common practice to implement various elastomeric
insulations to protect the combustion chamber of solid
rocket motors (SRMs) from the extreme temperatures gen-
erated during the firing of solid propellants. Most heat-
shielding elastomeric insulations utilized today are made
of ethylenepropylenediene monomer (EPDM), nitrile buta-
diene rubber (NBR), or silicone rubber.1–3 In addition, elas-
tomeric insulations are often filled with fibrous materials to
achieve higher mechanical strength, better thermal stabi-
lity, and improved insulation. Chopped fibers are added
into the insulations of rocket motors to enhance both the
charring process and the ablation-insulating performance.
Asbestos-filled NBR (AS-NBR) has been widely used in
several SRMs over the past decades. However, in recent
years, AS-free (AF) insulations have attracted more atten-
tion because of the carcinogenic effects of AS.4–9
Flexible organic fibers, such as short aramid fibers, are
often employed in elastomeric insulations on the basis of
their flexibility to withstand shear stress during mixing.
In contrast, carbon and glass fibers subject to an easy dete-
rioration into smaller particles or shred during processing.
of AS fiber because of its excellent properties, referring
to References [10–12]. On the other hand, compared with
aramid fibers, polyimide (PI) fibers that contain aromatic
imide groups in their molecular chains offer better disper-
sion, thermal and erosion resistance properties.13–16 For
example, the maximum thermal decomposition tempera-
ture of pyromellitic dianhydride-4,40 -diamino diphenyl
ether (PMDA-ODA)-type PI is 616.0 C and its char residue
at 800 C is 53.4%, while those values for Kevlar fibers are
599.5 C and 37.6%, respectively (Figure 1). Whereas the
1
Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of
Education, Beijing University of Chemical Technology, Beijing, People’s
Republic of China
2
Department of Mechanical and Aerospace Engineering, University of
Florida, Gainesville, FL, USA
Corresponding author:
Zhanpeng Wu, Key Laboratory of Carbon Fiber and Functional Polymers,
Ministry of Education, Beijing University of Chemical Technology, 15 Bei
San Huan East Road, Beijing 100029, People’s Republic of China.
Email: wuzp@mail.buct.edu.cn

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2 High Performance Polymers
Figure 1. The TG curves of pristine (a) Kevlar fiber and (b) PI
fiber. TG: thermogravimetric; PI: polyimide.
surface of PI fiber is too smooth and too inert to form a
good bonding interface with the elastomeric matrix, which
is a major challenge that impairs the ablation resistance and
mechanical integrity of PI fiber-filled NBR insulations.17
Recently, our group has reported that the adhesion
between PI fiber and inorganic material can be improved
by surface modification.18 After the chopped PI fibers were
modified in an alkaline aqueous solution, the PI fiber-filled
EPDM insulations showed excellent mechanical and
ablation-resistant properties. Meanwhile, it has been proved
that plasma treatment could also feasibly modify the surface
properties of PI films via imide-ring cleavage reaction,19–23
where the active particles in the plasma atmosphere can react
with PI molecules to form carboxylic acid groups, hydroxyl
groups, and other polar groups.
Herein, surfaces of PI fibers were modified by plasma
treatment, and they were first used to prepare NBR-based
insulations for an SRM. We expect that this approach could
demonstrate many advantages, including but not limited to
good mechanical properties, excellent ablation, and ideal
charred layers during firing of the SRM. This technique
could be feasibly extend to the fabrication of elastomeric
insulations or other functional organic composite materials
filled with PI fibers to protect chambers of SRMs and/or
some other potential applications.
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Experimental
Materials
PMDA-ODA-type PI fibers were prepared by a two-step
processing method as in our previous, study, with a dia-
meter of 10–20 mm; density of 1.45 g/cm3; strength of
560 MPa and modulus of 6–10 GPa.24 NBR (NBR 40; acry-
lonitrile content 35–41 wt%) was provided by courtesy of
Hongxia Chemical Plant (China). Kevlar fiber (length 3–
5 mm) was supplied by Jiangmen Six Part Fiber Co. Ltd
(China) and dried in a vacuum-drying oven for 5 h at
120 C before use. Fumed silica (diameter 12 nm) was pur-
chased from Shenyang Chemical Co. Ltd (China). A boron-
containing phenol-formaldehyde resin was purchased from
Shanxi Taihang Impede fire Polymer Co. Ltd (China). All
other additives such as sulfur or zinc oxide were commer-
cially available materials and were used as received.
Surface modification of PI fibers
The oxygen plasma treatment was conducted in a 40-kHz
radio frequency plasma generator (Prep2, Gala instru-
mente, Germany). The system includes a vacuum chamber,
three mass flow controllers, a pressure gauge, a pumping
system, and a radio source. Oxygen was fed into the
vacuum chamber. The operation pressure was set at
0.075–0.15 torr. PI fibers were treated by oxygen plasma
for 10 min with a fix power of 200 W. Finally, the modified
PI fibers were cut into 3–5 mm in length and then dried in a
vacuum-drying oven for 5 h at 120 C.
Preparation of chopped fiber-filled NBR thermal
insulations
In the formulation of chopped fiber-filled NBR thermal
insulations, the contents of surface-modified chopped PI
fibers were varied as 0, 2, 4, 6, and 8 parts per hundred
of rubber (phr), while the contents of other ingredients were
kept constant. For comparison, NBR insulations filled with
6 phr pristine-chopped PI fibers and 6 phr pristine-chopped
Kevlar fibers were also prepared. Fabrication of the thermal
insulations was described as follows. First, NBR was plas-
ticized for 3–5 min on a two-roll open mill at a friction ratio
of 1:1.1 using conventional processing technologies of
elastomeric products and then kept in an oven for 24 h at
60 C. Subsequently, fumed silica, organic chopped fibers,
and all other additives were added. After addition of dicu-
myl peroxide, sulfur, and accelerator, the materials were
extruded 10 times to ensure better dispersion with the nip
gaps of the two rollers <1 mm. Finally, the resulting mate-
rials were stripped-off the mill and vulcanized in an iron
box on a flat vulcanizing machine (QLB-25T, Jiangdu Xiz-
henwei Testing Machinery Co. Ltd, China) for 50 min at
150 C.
Zhao et al.
Table 1. Effects of plasma treatment on surface chemical compo-
sitions of PI fibers.
Surface relative mass fraction (%)
Chemical element Pristine PI Modified PI
N1s 2.32 4.50
C1s 75.14 69.53
O1s 18.52 22.25
O/C 24.65 32.00
N/C 3.09 6.47
PI: polyimide.
Characterization
The ablation properties were measured on an oxyacetylene
ablation tester (YS-22, Xi’an Huian Chemical Co., China).
The flow rate and pressure of oxygen were set to 1512 L/h
and 0.4 MPa, respectively, while the flow rate and pressure
of acetylene were set to 1116 L/h and 0.095 MPa, respec-
tively. The total ablation time was 20 s. The distance
between the face of specimens and the torch tip was kept
as 10 mm, and the angle of the torch with respect to the sur-
face of specimens was 90 . The specimen was cylindrical
in shape with a thickness of 10 mm and a diameter of
30 mm. The linear ablation rate is adopted to evaluate how
fast the material is damaged or burned by the flame. The
ablative thickness is tested as a product of the thickness
change before and after ablation tests of each specimen,
and the linear ablation rate is calculated by dividing the
ablative thickness by the total ablative time (20 s). That
is, a lower linear ablation rate represents a higher abla-
tion–resistance.
The mechanical properties of NBR thermal insulations
were tested using an electronic universal testing machine
(Sans, MTS system Co. Ltd, China). The specimens were
cut from a thermally molded sheet into the standard cross
section of tensile samples, having two shoulders and with
a gauge length of 25.0 mm, a width of 6.0 mm, and a thick-
ness of 2–3 mm (measured before the test). The standard
specimens were first lined up probably by adjusting the
grips of the testing machine, and a loading rate of 500
mm/min was applied. Both the tensile strength and elonga-
tion at break were determined by averaging out the values
for five specimens of the same formulation.
Surface chemistry of PI fibers was analyzed by X-ray
photoelectron spectroscopy (XPS; Escalab 250, Thermo
Electron Corporation, USA). XPS spectra were obtained
using aluminum K (h ¼ 1486.6 eV) X-ray source with a
power of 150 W. The XPS measurements were performed
at a vacuum condition lower than 108 torr. Spectra were
acquired at a takeoff angle of 90 relative to the sample surface.
Surface roughness of PI fibers were characterized by
atomic force microscopy (AFM; Multimode 8, Veeco,
Plainview, New York, USA). A piece of PI fiber was
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3
attached to a steel sample stage. Tapping mode was used
to scan the surface of PI fibers. AFM images of PI fiber
were obtained for a scanning area of 3  3 mm2 under tap-
ping mode. Surface roughness values were calculated from
the instrument software.
Surface morphology and cross sections of PI fibers, frac-
ture surfaces of the tensile specimens and charred layers
of the insulations were characterized using a scanning elec-
tron microscope (JSM-7600F, JEOL, Japan) at an acceler-
ating voltage of 15 kV after samples were coated with
approximately 5 nm of a palladium/gold alloy. Chemical
composition of the exposed fiber was examined using an
energy-dispersive spectrometer (Oxford X-Max, Oxford
Instruments, Abingdon, England, UK).
Results and discussion
Surface modification of PI fibers
It is a good way to enhance the interfacial interactions
between fibers and NBR matrixes via enhancing the
roughness and surface area of chopped PI fibers. Oxy-
gen plasma treatment is selected to improve the surface
affinity of PI fibers as it has many oxygen-containing
active particles including O2, Oþ 2 , O, and so on, which
can react with PI molecules to form free radicals by
reactive sputter etching effect.25,26 These free radicals
reacting with oxygen could form carboxyl, hydroxyl,
and amino groups. XPS results (Table 1 and Figure 2)
showed that the percentage of oxygen and nitrogen on
the surfaces increased, with a decreasing trend of the
carbon concentration after plasma treatment. The values
of O/C and N/C increase from 24.65% and 3.09% to
32.00% and 6.47%, respectively, which suggests the for-
mation of new functional groups. The concentration of
corresponding functional groups can be calculated from
the XPS C1s peak areas (Figure 3), as summarized in
Table 2. It was found that a new group at 289.0 eV,
which may be attributable to –COO–, appeared on the
surface of modified PI fibers. In addition, the –C–C–
and –N(CO)2 concentrations decreased, while the –C–
N–, –C–O–, and –C¼O concentrations increased after
plasma treatment.
On the other hand, SEM images in Figure 4 and AFM
images in Figure 5 showed that surfaces of PI fibers treated
by plasma were much rougher than those of pristine PI fibers.
The surface of untreated PI fiber was smooth yet streaked
because of the wet spinning process, whereas modified PI
fiber appeared to considerably roughen in all directions. AFM
measurements showed that the surface roughness had
increased from 24.0 nm to 54.0 nm. The increase of surface
roughness was caused by the different etch rates of crystalline
and noncrystalline regions of original PI fibers, and it is suf-
ficient to enhance the interfacial interactions between PI
fibers and NBR matrix as demonstrated later.
4 High Performance Polymers

Figure 3. XPS C1s spectra of (a) pristine and (b) plasma-treated

Figure 2. XPS survey spectra of (a) pristine and (b) plasma- PI fibers. PI: polyimide; XPS: X-ray photoelectron spectroscopy.
treated PI fibers. PI: polyimide; XPS: X-ray photoelectron
spectroscopy.
Table 2. Effects of plasma treatment on the concentration of func-
Effects of the contents of PI fibers on the ablative tional groups of PI fiber surface.
properties of NBR insulations The concentration of
The linear ablation rates of NBR insulations are listed in functional groups (%)
Table 3. It clearly shows that the linear ablation rate
Samples –C–C– –C–N– –C–O– –C¼O –N(CO)2 –COO–
declines substantially and levels off with the increase of
PI fibers in content, which pinpoints the optimum enhance- Untreated 63.89 31.39 1.12 1.02 2.58 0
ment of the ablative properties after certain amount of Treated 56.56 33.40 1.75 3.47 1.85 2.97
addition of plasma-treated chopped PI fibers. PI: polyimide.
To further inspect the surface microstructures of charred
layers of the insulations, SEM was applied for selected
samples in Table 3. Many voids and cracks were formed fibrous structure (marked with an arrow in Figure 6(c)),
in the charred layers when the decomposed gases were gen- while the fibrous structure of Kevlar fibers had been signif-
erated under thermal stress for all samples. There were still icantly deteriorated after ablation. To further confirm the
several clear differences between the microstructures of PI elemental components of charred PI fibers, energy-
fiber-filled and the control samples. As shown in Figure dispersive spectrometry (EDS) was employed for measur-
6(c), many fibers still remained intact in the charred layers ing the chemical element content (Figure 7(b)). The results
for the insulations filled with 6 phr modified chopped PI of the EDS show a content of 95.59% C, 3.05% O, and
fibers, while few fibers were identified in Kevlar-filled 1.36% Si, which captured the intrinsic characteristics of
insulations after ablation. The insulations filled with PI graphitized PI fibers subjected to burning gases. Therefore,
fibers also seemed to have more intact charred layers due it is suggested that surface modified PI fibers improve the
to the effects of fiber reinforcements. In other words, the ablation performance of NBR insulations via integrated
carbonaceous residue of PI fibers still kept their intrinsic carbonaceous residue of PI fibers, which may effectively

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Zhao et al. 5

Figure 5. 3D AFM images of (a) pristine and (b) plasma-treated PI

fibers. PI: polyimide; 3D: three dimensional; AFM: atomic force
microscopy.

Table 3. Mechanical and ablative properties of NBR thermal

insulations.

Contents Tensile Elongation Ablation

of fibers strength at break rate
Fibers (phr) (MPa) (%) (mm/s)

Modified PI 0 21.6 666.7 0.122

Modified PI 2 20.4 726.1 0.064
Modified PI 4 17.7 706.8 0.054
Modified PI 6 18.7 699.3 0.050
Figure 4. SEM images of (a) pristine and (b) plasma-treated PI Modified PI 8 18.2 768.7 0.050
fibers. PI: polyimide; SEM: scanning electron microscopy. Pristine PI 6 13.2 492.9 0.132
Pristine Kevlar 6 15.4 666.6 0.137
fix the charred layer and protect the elastomeric matrix.
NBR: nitrile butadiene rubber; PI: polyimide.
The linear ablation rate of PI fiber-filled insulations
decreased to 0.05 mm/s compared with 0.137 mm/s of
Kevlar-filled insulations. PI fibers were 18.7 MPa and 699.3%, while those filled
with 6 phr Kevlar fibers were 15.4 MPa and 666.6%,
respectively. The insulation filled with 6 phr unmodified
Effects of the contents of PI fibers on mechanical
PI fibers showed the worst mechanical properties, only
properties of NBR insulations 13.7 MPa and 473.3%, presumably because of the low
The mechanical properties of NBR insulations filled with interfacial strength between the PI fibers and matrix. SEM
two kinds of organic fibers are shown in Table 3. Because was also applied to characterize the morphology of tensile
of improvement of the surface roughness of PI fibers and fracture surfaces (Figure 8). As shown in Figure 8, the frac-
addition of many polar groups on its surfaces, the modified tured surfaces of pristine PI fiber-filled insulation under-
PI fiber-filled NBR insulations showed better mechanical went a fiber bridging and pullout event (Figure 8(b)) due
properties than those filled with the same content of pristine to the relatively weak interfaces, while those filled with
PI and Kevlar fibers. For example, tensile strength and modified PI fibers show virtually no pullout effect (Figure
elongation of NBR insulations filled with 6 phr modified 8(c)). Since the plasma treatment improved the interfacial

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6 High Performance Polymers
Figure 6. SEM images of charred layers after ablation test for
NBR insulation filled with various contents of organic fibers: (a) 0
phr fiber; (b) 6 phr chopped Kevlar fibers; and (c) 6 phr surface
modified chopped PI fibers. PI: polyimide; NBR: nitrile butadiene
rubber; SEM: scanning electron microscopy.
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Figure 7. (a) Magnified image of the carbonaceous residue on a PI
fiber that was marked with an box in Figure 6(c) and (b) its cor-
responding EDS data. PI: polyimide.
interactions between PI fibers and NBR matrix, the PI
fibers broke near the fracturing surfaces of the specimens.
Thus, surface modification (i.e., physical and chemical)
of PI fibers could enhance the adhesion properties between
fibers and NBR matrix and in turn result in the excellent
mechanical properties of fiber-filled NBR insulations com-
paring to others.
Conclusions
In conclusion, NBR insulations with excellent mechanical
and ablative properties were fabricated using surface-
modified (oxygen plasma treatment) chopped PI fibers and
with a two-roll mill. Plasma treatment can effectively
improve the roughness of PI fibers and at the same time
form many polar functional groups on its surfaces. This
effect leads to a significant enhancement of interfacial
interactions between PI fibers and NBR matrix. Compared
with Kevlar fiber-filled NBR insulations, chopped PI fiber-
Zhao et al. 7

filled NBR insulations show better mechanical and erosion

resistance properties. To enhance the fiber–elastomer adhe-
sive property, surface treatment of the PI fibers is necessary
to improve its surface roughness. It is expected that the cur-
rent approach based on surface modification of chopped PI
fibers provide better charring and ablative performances of
insulations for solid rockets and may feasibly extend to the
design of many other polymeric composites for of various
potential applications as well.

Funding
This research was financially supported by the National Key
Basic Research Program of China (2014CB643600) and National
Natural Science Foundation of China (51273018 and 50973006).

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