Article

Polymers and Polymer Composites

Using potential of filament-wound carbon/

2021, Vol. 29(9S) S1541–S1554
© The Author(s) 2021
Article reuse guidelines:
glass polymeric composites as rocket motor sagepub.com/journals-permissions
DOI: 10.1177/09673911211056787
journals.sagepub.com/home/ppc
thermal insulation

Jelena Rusmirović1 , Jela Galović1, Marija Kluz1, Srdja Perković1, Saša Brzić1,2,
Marica Bogosavljević1, Aleksandar Milojković1, and Tihomir Kovačević1

Abstract
The study aim is to develop hybrid filament-wound polymeric composites based on flame retardant polyester resin (UPe) and
multi-layer structured glass or combined carbon and glass fibers for use as ablative thermal insulation of rocket motor by wet
filament winding technique. The composites have a multi-layered structure consisting of two layers of carbon (CF) or glass
woven fabric (GF) and one layer of carbon or glass direct roving (CR or GR, respectively), repeated in three cycles. Structural
analysis, performed using FTIR spectroscopy and dynamical-mechanical analysis, confirm highly polymerized network. Lower
values of the tanδ peak height indicate improved interfacial adhesion between carbon/glass fibers and UPe. The improvements
of thermal insulation index of 37% and erosion rate of 38.6% at 180°C are achieved for combined carbon/glass fiber–based
composite compared to the neat UPe. Tensile and interlaminar shear properties are investigated according to the fiber
orientation and the highest values of tensile and interlaminar shear strengths are obtained for composites with longitudinal
orientation, 417.48 MPa and 22.30 MPa, respectively. Compared to the neat UPe, which degrades after 50 s at 3000°C, the
composites are stable up to 192 s.

Keywords
Thermosetting composites, fiberglass, carbon fiber, filament winding, insulation

Introduction
Glass and carbon fiber–based composites have been designed by the wet filament winding (wFW) technique used in
production of flat laminates, elbows or curved-surface, adjustable for use as construction piping systems, marine and
aerospace construction elements, thermal insulators and in ballistic application.1–9 Characteristics of fiber-based composites
obtained via wFW are mainly affected by their composition, geometry/shape, and process conditions, such as fiber and resin
type, filler addition, winding angle, speed and tension force and finishing reinforcing layer.10,11 In general, wFW technique
places the resin impregnated fibers under the defined angle and applied tension force in form of circumference of a steel tool of
the desired shape.2,11 The wFW provides high production rate, quality of the products and repeatability of the composite
performances compared to other fabrication techniques.12 Moreover, this technique allows obtaining desired mechanical
properties of final product with different fiber orientation.2 In the presented work, the wFW technique is employed to produce
an ablative high temperature protection material (TPM) based on flame retardant polyester resin and multi-layer structured
glass or combined carbon and glass fibers which can be used as thermal insulation of the rocket motor.
Thermal insulating materials which contain an ablator are one of the most reliable TPMs used in designing construction
elements for rocket motors.13 A low-density and light-weight fiber-reinforced thermal protection composites, which exhibit
excellent mechanical and energy-absorbing performances, gain increasing attention for achieving the higher requirements in
the rocket aspects.13 The most promising polymers for impregnation of carbon and glass fibers/fabrics and for production of
light-weight TPM composites are phenolic, epoxy, and polyester resin.14–21 Among them, the unsaturated polyester resins
(UPe) are widely used to impregnate glass and carbon fibers or fabrics due to good compatibility, high protection potential
related to the corrosion, extreme temperature and internal pressure.2 UPe-based composites, reinforced with glass/carbon
fibers, represent typical engineering construction materials of high standards with regards to mechanical and thermal
properties.15,22 Moreover, such composites possess an appropriate temperature range according to the application conditions
(thermal insulation of rocket motor or nozzle, inhibition of solid rocket propellant grain, etc.)2,23 and steel retain low weight to

1
Military Technical Institute, Belgrade, Serbia,
2
Military Academy, University of Defense, Belgrade, Serbia

Corresponding author:
Correspondence: Dr Jelena Rusmirović, Department for Materials and Protection, Military Technical Institute, Ratka Resanovića 1, Belgrade 11030, Serbia,
jrusmirovic@tmf.bg.ac.rs
S1542 Polymers and Polymer Composites 29(9S)

thickness ratio due to low density.13 There are various methods of production of polymer-based carbon/glass fiber composites,
such as hand lay-up method,14 vacuum infusion and microwave-assisted compression molding24 but wFW provides potential
to adjust certain properties, so it is commonly used for the designing of rocket motors.2,25
Properties of wFW obtained composites depend on the filament structure and applied reinforcing agent as well.26 There are
several phenomena associated with glass fiber melting and reacting with the charring UPe polymer matrix, which are followed
with formatting of mechanically stable silicon carbide structure and heat adsorption during the phase transformation.16 In
contrast, carbon fibers are good heat conductors and possess high specific strength and modulus. Thermal properties of such
structures can be improved by introducing powdered fillers such as micro- or nano-silicon dioxide,27,28 alumina tri-
hydrate,29–31 and graphene-nanoplatelets14 in a polymer matrix prior to fiber impregnation.16 These fillers exhibit a synergistic
effect with the fibers in terms of improving thermal characteristics as demonstrated in the following literature.14 Hence,
alumina tri-hydrate as low-cost, thermally stable upon 800°C with a total weight loss of 7.4% 32 can be effectively used to
increase the heat resistance of fiber-reinforced polymer composites.29 The effect of alumina tri-hydrate on fire resistance of
polymers can be summarized by the following effects: cooling down the polymer burning surface (heat sink material);
releasing water vapor during the thermal decomposition causing the dilution of the combustible gases; forming insulating
protective barrier of aluminum (III) oxide; and reducing smoke emission.33
The aim of this study was to develop multi-layer structured composites where matrix was self-extinguished halogen-free
UPe resin containing alumina tri-hydrate, while reinforcements were carbon or glass woven roving in first layer and carbon or
glass direct roving in following layers. The carbon/glass multi-layered composite structures were manufactured by the wFW
technique and the effects of interlayers on mechanical, rheological and thermal properties of the resulting composites were
examined. These tests took into consideration the following aspects: (a) development of standard glass fiber-based composite;
(b) development of hybrid carbon/glass fiber-based composite; (c) effect of fiber orientation on mechanical properties; (d)
effect of force load transmission (through carbon or glass layer) on interlaminar shear properties; and (e) effect of material
composition on thermal and mechanical characteristics. The materials developed in this study could be used as fire-resistant
ablative thermal insulation of rocket motor.

Experimental
Materials
Carbon fiber GG206P (G. Angeloni. S.r.l., Italy, characteristics: 200 g/m2, plane, width 30 mm, and thickness 0.19 mm) and
medium-heavy fiberglass woven roving (R&D Faserverbundwerkstoffe, GmbH, Germany, characteristics: 200 g/m2, plane,
width 30 mm, and thickness 0.22 mm); carbon fiber Tenax HTS40 F13, 800 tex (R&D Faserverbundwerkstoffe GmbH,
Germany) and fiberglass direct roving, 300 tex (Kelteks Ltd, Croatia), were used for the production of the flat composite
laminates. Pre-filled, unsaturated halogen-free UPe resin, Dion® FR 7721-00, (Reichhold, USA), which contained alumina tri-
hydrate as fire-retardant was used as polymer matrix for composite preparation. The 50% solution of the methyl ethyl ketone
peroxide in toluene (MEKP, Sigma Aldrich, Germany) was used as UPe resin initiator/hardener.

Samples Preparation
Composite laminates were prepared using wFW machine (Forplex Plasterex, France), equipped with GE Fanuc series O-T
software (Figure 1). The carbon/glass woven and direct roving were first impregnated with pre-initiated UPe resin in a resin

Figure 1. Forplex plasterex filament winding machine.

Rusmirović et al. S1543

bath and further wound on steel plate-shaped tool, 250 × 270 mm, with pins on both sides. The wFW tension force was 15 N
per band of glass/carbon roving (two rovings in a band). The composites had a multi-layered structure consisting of two layers
of carbon (CF) or glass woven fabric (GF) and one layer of carbon or glass direct roving (CR or GR, respectively), repeated in
three cycles. Top layer contained glass fibers. The velocity of the filament winding was 21 m/min, while winding was only in
one direction without fiber interlacing in cycles. Afterward, the composites were cured at 70°C for 3 h and post-cured at 80°C
for 5 h. The desired and predicted overall thickness of the composite laminates was 4.0 mm. Besides, cured flat sheets were
subjected to mechanical processing using a universal lathe to targeted thickness. The samples for tensile and interlaminar shear
tests, dynamic-mechanical, and thermal analysis were made from sheets of 250 × 270 mm dimension according to the
Supplementary Scheme 1 in Online Supplement File.
The cured carbon/glass multi-layered composite samples were designated as UPe_GF (only glass-based reinforcement)
and UPe_CGF (combined glass- and carbon-based reinforcement) and shown in Figure 2.

Characterization Methods
The density of cured carbon/glass multi-layered composite samples was determined according to the ISO 1183-1:2012
standard, Plastics—Methods for determining the density of noncellular plastics.34
Fourier transforms infrared spectroscopy (FTIR) spectra of the cured composite were recorded in absorbance mode using a
NicoletÔ iSÔ 10 FTIR Spectrometer (Thermo Fisher Scientific, USA) with Smart iTRÔ FTIR sampling accessories, within a
range of 400–4000 cm–1, at a resolution of 4 cm
1 and in 20 scan mode.
Dynamic-mechanical analysis (DMA) study of the cured composite samples was performed in torsion deformation mode
using the Modular Compact Rheometer MCR-302 (Anton Paar GmbH, Austria) equipped with standard fixtures (SRF12) for
rectangular bars, temperature chamber (CTD-620) having high temperature stability (±0.1). The standard sample of a
rectangular bar shape (44 × 10 × 4 mm) was tested by using “temperature ramp test”’ at temperature range from 40°C to
180°C, the heating rate was 5°Cmin
1, the single angular frequency of 1 Hz, and strain amplitude was 0.01%.
Thermal properties of the cured DION® FR 7721-00 resin and composite inhibitor were studied by a modified oxy-
acetylene ablation testing of thermal insulation materials35 using an high-temperature infrared thermometer (Extech, Boston,
Massachusett, USA) and an oxyacetylene flame (Supplementary Figure 1(a) in Online Supplement Material). Samples of
standard dimension (100 × 100 × 6 mm) were used. The following parameters were obtained as test results: insulation index
(IT), erosion rate (E), temperature (Tb) and time (tb) of combustion.
Bond strength between composites and aluminized composite rocket propellant was determined using standard adhesion
tests by Instron 1122 Universal Testing Instrument (Instron, Norwood, Massachusett, USA), at 20°C with force loading rate of
10 mmmin
1 (Supplementary Figure 1 in Online Supplement Material).

Figure 2. Structure of the a) GG206P carbon and b) R&D Faserverbundwerkstoffe glass fabric; and of the cured c) UPe_CGF and d)
UPe_GF multi-layered composite structure.
S1544 Polymers and Polymer Composites 29(9S)

Figure 3. Schematic diagram for the a) tensile and b) interlaminar shear strength testing.

Interlaminar shear strength was determined using standard ASTM D2344 test,36 while uniaxial tensile test was determined
using standard ASTM D303937 using Schenck Trebel RM 100 (RoTec GmbH, Darmstadt, Germany). Two load directions
were applied during the interlaminar shear strength evaluation: over carbon and glass layer for UPe_CGF composite.
Longitudinal and transverse tensile strengths were determined for both composite laminates. Schematic diagrams for the
tensile and interlaminar shear strength tests are shown in Figure 3.
Failure analysis of the cured composites and samples after mechanical characterization was performed using SMTV Visor
Inspection System (Michael Bruch, Germany).

Results and Discussion

Density of Composite Material
An optimal material porosity and low thermal conductivity can be achieved by tailoring the density of the composite,
which make the composite suitable for use as a passive thermal insulation as well as an ablative system.38 The density of
polymer composite ablatives can be maintained to a minimum by limiting the degree of mechanical compaction of the
fibers/fillers by achieving the minimum required mechanical strength.38 Table 1 shows the average density values of
composite samples of standard dimension (10 × 10 mm). The density of the UPe_CGF composite is 1.699 g/cm3 and lower
than density of the UPe_GF composite indicating that this low-weight material can be used as thermal insulation of the
rocket motor.
Rusmirović et al. S1545

Table 1. Experimental conditions and density determination results.

Temperature 30°C Sample ρ avg, g/cm3

Air humidity 38.3% UPe_GF 1.749±0.012

ρ H2O (30°C) 0.996 g/cm3 UPe_CGF 1.699±0.028

FTIR Analysis
FTIR spectra of uncured neat DION® FR 7721-00 resin, cured UPe_CGF composite and CF and GF are presented in Figure 4.
The peaks observed in the FTIR spectra of UPe and UPe_CGF around values of 3618, 3524, 3444, and 3375 cm
1 and the low
intensity peak at 697 cm
1 originate from hydroxyl (OH) groups stretching vibrations of resin and alumina tri-hydrate, which
is used as a flame retardant in the polymer matrix. The alumina tri-hydrate filler exhibits peaks at lower wavenumber (around
500 and 1150 cm
1) corresponding to Al-O bonds,39 but these peaks are overlapping with the ones originating from the
valence vibration of polyester backbone.
Symmetric and asymmetric vibrations of methyl (CH3) and methylene (CH2) groups are observed around values of 3050,
2825, and 2840 cm
1, while their bending vibrations are remarked at about 1454 cm
1. 15,40 The intensity of these peaks is
significantly reduced in FTIR spectrum of cured UPe_CGF composite. The band at 1728 cm
1 in the FTIR spectrum of the
corresponding composite originates from carbonyl C=O (ester) group present in the polyester resin.15 This peak is shifted to a
higher wavenumber compared to the neat UPe (1720 cm
1) indicating interactions between resin and CF, CR and glass fibers.
Moreover, ester C-O stretching vibration is observed at about 1372 cm
1.15 The peak at 1490 cm
1 in UPe originates from the
stretching vibration of the C=C and disappears after curing. Si-O-Si vibrations are observed as a broad peak at 915 cm
1.
Similar FTIR results are obtained for the UPe_GF sample.

Figure 4. FTIR spectrum of the cured composite UPe_CGF, uncured UPe, carbon fabric (CF) and glass fabric (GF).
S1546 Polymers and Polymer Composites 29(9S)

Dynamic-Mechanical Analysis
DMA is a standard technique used to investigate viscoelastic properties of polymers in a wide temperature range. The
temperature dependences of storage modulus (G0), loss modulus (G00) and damping factor (tanδ) of cured UPe resin, UPe_GF
and UPe_CGF composites are shown in Figures 5 and 6. G0 reflects elastic, while G00 reflects viscous behavior of polymer
matrix. In addition, Table 2 shows rheological characteristics of analyzed samples: storage modulus in glassy state and rubbery
plateau (G0GS and G0RP, respectively), glass transition temperature (Tg) and tanδ peak height.
It can be noticed that composites display higher values of the G0 in glassy state compared to the neat UPe resin. Such a
phenomenon is associated to the strength of fiber/matrix interactions and the way the polymer chains are packaged.41 An
increase in temperature causes a decrease in G0 for all samples which is the consequence of greater movement of the polymer
segments. Composites display a smaller drop in G0 as temperature increases, which is manifested in one relaxation process,
implying that reinforced resin possesses homogeneity in structure, that is, wetting of fibers is quite satisfied. In general,
composites exhibit a significantly higher G0 in a rubbery plateau than neat resin, whereby the one containing only GF shows a
slightly greater value compared to one with the combined carbon and glass fibers. Although carbon fibers possesses a higher
rigidity than GF and therefore less mobility under the influence of increased temperature, there is probably poor CF wetting
with UPe resin which results in a lower G0 for corresponding composite compared to the material containing only glass fibers.
Obtained increase of G0 values for composites samples indicates that carbon and/or glass fibers increase the UPe capacity to
support mechanical constraints with recoverable deformation, while composites stiffness is substantially increased.42
Figure 5(b) shows that G00 slightly rises to the transition region and then significantly decreases as the temperature continues to
increase for all samples. That increase in value of loss modulus in the transition region is attributed to internal friction which promotes
energy dissipation caused by the presence of reinforcements.43,44 Internal friction is the result of polymer bridges sliding along other
parts of the molecular network and carbon or glass fibers. In addition, such an increase in G00 also occurs due to the movement of free
domains of the UPe segment present between linked network.45 The slight broadening of the G00 peak for composites compared to
UPe resin indicates the effect of fibers incorporation, which inhibits the relaxation process in reinforced materials.46 A significant
drop in G00 for all samples is a result of favorable free motion of the macromolecule segments within the polymer structure.
The tanδ height values are similar for UPe_CGF and UPe_GF composites; however, the tanδ height value for cured UPe at
the Tg is ≈30% higher than for composites. Decrease in tanδ height values for composite is usually caused by the restriction of
the free movement of the polyester resin chain segments.44 Also, lowering of tanδ peak value for composites indicates good
interfacial adhesion between carbon/glass fibers and UPe matrix.
The glass transition temperature (Tg) is determined from tanδ peak position (Figure 6) and it reaches a value of 110.1°C for
neat UPe resin, 107.1 and 113.7°C for UPe_CGF and UPe_GF composites, respectively. The increase in Tg for UPe_GF
occurs due to the immobilization of the UPe macromolecular chains near the surface of the glass fibers.47 The slightly decrease
in Tg for hybrid UPe_CGF composite occurs due to higher rigidity of the woven carbon fibers, which causes lowering the
temperature of relaxation.42 Similar results are obtained in DMA studies done on pine apple/glass hybrid composites, natural/
glass fibers composites and carbon/glass hybrid composites.42

Thermal Properties
The thermal properties play an important role in using composite materials as thermal protection of rocket motors. Due to that,
the modified ablation test is performed and results are presented in Table 3 and Figure 7. The values of insulation index and
erosion rate are shown in Table 4.

Figure 5. Temperature dependence of storage modulus (G0) and loss modulus (G00) of cured UPe resin and corresponding composites.
Rusmirović et al. S1547

Figure 6. Temperature dependence of tanδ of cured UPe resin and corresponding composites.

Table 2. DMA results of UPe and corresponding composites.

<Sample G0GS, MPa G0RP, MPa Tg (tanδ peak,°C) tanδ peak height

UPe 1,698.0 28.2 110.1 0.43

UPe_CGF 2,660.0 102.2 107.1 0.33
UPe_GF 3,396.0 128.5 113.7 0.33

Table 3. Physical characteristics (mass before (m1) and after (m2) ablation test, and mass loss (Δm)) of the sample before and after
flammability test.

Sample m1, g m2 , g Δm, g tba, s Tbb, °C

UPe 74.42 57.89 16.53 50 320.0

UPe_GF 88.32 65.04 23.28 171 Stablec
UPe_CGF 97.57 65.58 31.99 192 Stablec
a
tb represents the time of degradation.
b
Tb represents the temperature of degradation.
c
oxyacetylene flame temperature ≈3000°C.

Table 3 shows that time to ignition for the neat UPe resin is 50 s, while the composites have significantly greater thermal
stability, 242% and 264% higher than the resin. When the polymeric material is exposed to a hyperthermal environment,
temperature at the surface starts increasing and thermally induced reactions take place, resulting in the formation of gaseous
products and charred residue.16 However, this char does not have enough mechanical integrity, cracks easily and allows the
S1548 Polymers and Polymer Composites 29(9S)

Figure 7. Sample of cured UPe and UPe_GF and UPe_CGF composites before (a) to (c) and after ablation test (d) to (i).

Table 4. Values of isolation indexes at 80 and 180°C and erosion rate.

Sample I80, s/m I180, s/m E, m/s

UPe 3,000 6,250 8.00 × 10
5

UPe_GF 3,285 7,482 3.20 × 10
5
UPe_CGF 3,704 8,586 3.09 × 10
5

Table 5. Maximal shear force (Fmax) and interlaminar shear strength (τ) for UPe_GF and UPe_CGF composites.

Longitudinal shear test Transverse shear test

Sample (Fmax)avg, N τavg, MPa Sample (Fmax)avg, N τavg, MPa

UPe_GF 1,461.33±222.44 19.275±2.15 UPe_GF 767.67±88.08 10.197±1.120

UPe_CGFa 1,860.33±222.44 22.297±1.675 UPe_CGFa 1,045.33±66.89 11.955±0.725
UPe_CGFb 1,626.0±225.33 19.875±3.11 UPe_CGFb 655.67±69.11 7.853±0.669
a
Force load through carbon layer.
b
Force load through glass layer.
Rusmirović et al. S1549

Figure 8. (a) Samples subjected to interlaminar shear strength test; (b) load–displacement curves.
S1550 Polymers and Polymer Composites 29(9S)

Figure 9. (a) Load–displacement curves; (b) samples subjected to tensile tests.

Table 6. Maximum tensile force (Fmax) and longitudinal and transverse tensile strength (Xt and Yt) for UPe_GF and UPe_CGF composites.

(Fmax)avg, N (Xt)avg, MPa (Fmax)avg, N (Yt)avg, MPa

Sample— longitudinal tensile test transverse tensile test

UPe_GF 30,335.0±2,145.0 233.44±18.94 5,865.5±740.5 56.01±7.42

UPe_CGF 53,470.0±2,495.0 417.48±18.72 4,997.0±300 46.94±2.17

transfer of heat flux to the virgin material, causing its further degradation. The introduction of reinforcements within the
polymer structure, such as CF, CR, or glass fibers, is beneficial in several ways: fibers endothermically absorb heat and give
mechanical strength to the charred/carbonaceous material.16 This is particularly significant for combustion of thermally
inhibited propellant, when mechanically weak protection layer (char) can be mechanically eroded/removed by the friction
action exercised by the high pressure and combustion products.16,48 The highest insulation capacity is achieved for UPe_CGF
at both investigated temperatures. Erosion rate decreases significantly for UPe_CGF and UPe_GF composites compared to the
neat UPe resin (Table 4). The introduction of fibers reduces delamination between these polymer phases (Figure 7).16,48
Moreover, glass and carbon fibers in composite undergo many endothermic processes, such as melting and evaporation, thus
working as an additional heat sink.16,48 From the point of view of rocket motor design, both composites meet requirements of
thermal stability.

Mechanical Properties
The results of verification of mechanical properties obtained by testing the interlaminar shear strength are summarized in
Table 5. The shear force dependence of displacement is presented in Figure 8. The mechanism of failure of the composite
structure is very similar and takes place through two phases (i) elastic and (ii) damage at a certain stress (intra- and interlaminar
failure) 3 (Figure 8). During the elastic failure, shear force increases and reaches the maximum values and then decreases
stepwise (Figure 8). This stepwise decrease in shear force is caused by intralaminar damages, which include fiber fracture and
Rusmirović et al. S1551

Figure 10. Curve of dependence of load force and length of peel.

buckling as well as cracking of the polymer matrix, giving the residual strength of the composite laminate. Moreover, the force
load induces the formation of micro-failures at the UPe/fiber phase boundary. Composites exhibit high anisotropy since
maximum values of shear force ((Fmax)avg) and interlaminar shear strength (τ) are obtained for samples with longitudinally
orientated reinforcements (Table 5). Higher values of Fmax and τ are obtained for UPe_CGF composite in both load directions,
Fmax = 1,860.33 N, τ = 22.297 MPa, and Fmax = 1,626.0 N, τ = 19.875 MPa, over carbon and glass layer, respectively.
Improved interaction of the UPe matrix with carbon fibers causes higher values of shear force and strength. The obtained
results indicate that composite materials have sufficient strength for application in thermal insulation of solid rocket
propellants.
Based on the mean results of six specimens, it is demonstrated that the longitudinal fiber orientation shows dominated
impact to the tensile strength and maximal forces of UPe/GF and UPe/CGF composites.49 It is clearly remarked that
longitudinal tensile strength is more than five times higher than transverse tensile strength for UPe/GF and more than 10 times
higher for the UPe/CGF, suggesting the high anisotropy of analyzed composites. However, the lowest value for transverse
tensile strength shows UPe/CGF composite. Moreover, the decreasing in transverse tensile strength also lies in smaller or
bigger disruption within the material structure that occurs during mechanical processing of samples (cutting the standard
specimens) from unidirectional flat sheets.26 It is demonstrated that cutting laminates containing fibers transversely in the
carbon and glass fiber direction can cause damages within the laminate structure and reduce the mechanical properties as
well.26
Furthermore, uniformity of the mean values of longitudinal tensile strength (Xt) for both UPe/GF and UPe/CGF laminates
is observed.26 Standard deviation of Xt was 4.5% and 8.1% for UPe/CGF and UPe/GF, respectively. Lower uniformity of the
transverse tensile strength (Yt) values, up to 13.4% for UPe_GF, is obtained (Table 6). Corresponding load-displacement
curves are shown in Figure 9. Composites exhibit elastic failure, which is reflected by the linear growth of force with
displacement up to maximum determined values. After that, the intra- and interlaminar failures of the composites are remarked
S1552 Polymers and Polymer Composites 29(9S)

(Figure 9), which are followed by fall and re-growth of force values (serrated force-elongation plot). Samples subjected to the
longitudinal tensile tests show delamination of the CF and GF. Opposite is observed for the composites subjected to the
transverse tensile test. Schematic diagram of comparation of the tensile and interlaminar shear strength is shown in
Supplementary Figure 3 in the Online Supplemental Material.

Bond Strength between Composites and Aluminized Composite Rocket Propellant

The dependence of the length of peel on the force load is obtained a result of the adhesion test (Figure 10). It can be remarked
that the force increases linearly up to 2.5 N, after which the composite rocket propellant breaks. The bonding strength between
UPe_GF and composite propellant shows a slightly lower value of the force plateau, around 1.57 N, after which a rupture
occurs. This indicates a slightly weaker adhesion of propellant and UPe_GF material. The smoothness of the F-l curve
indicates that a uniform bond is achieved between UPe_CGF and composite rocket propellant over the entire contact surface.
This phenomenon is associated with adequate sample preparation and good adhesion between these two materials. In addition,
the break of the propellant implies that the adhesion forces are greater than cohesion forces within the propellant structures.
High adhesion is a prerequisite for the application of composite materials such as TPM in rocket propellant grains design. De-
bonding between composite and propellant is undesirable due to increasing the burning surface, which causes spreading
flames, reducing efficiency and finally motor failure. This indicates a slightly weaker adhesion of propellant and UPe_GF
material reinforced with only glass fibers.

Conclusion
The presented paper confirmed the usability potential of ablative multi-layered polymeric composites, based on self-
extinguished UPe and carbon/glass fibers, as TPM in rocket propellant grain design. Composites prepared by the wFW using
plane carbon or fiberglass woven roving, 200 g/m2, carbon and fiberglass direct roving and halogen-free unsaturated polyester
resin showed good dimensional, mechanical and thermal stability. Thermal properties of the prepared composite inhibitors
were studied by ablation test, while mechanical properties were determined using dynamic-mechanical, tensile and inter-
laminar shear strength analysis. Improved mechanical properties, e.g. higher values of tensile and interlaminar shear strength
are obtained for hybrid carbon/glass fiber-based composite compared to the neat UPe and UPe_GF as well. Accordingly,
longitudinal fiber orientation in hybrid UPe_CGF sample provides the highest shear and tensile strengths of 22.30 MPa and
417.48 MPa, respectively. Moreover, hybrid UPe_CGF shows excellent thermal stability up to 192 s at 3000°C and significant
improvements of isolation index at 180°C for 37% and erosion rate for 38.6%. Ablation and mechanical tests indicated that
hybrid UPe_CGF composite could be applied as TPM in designing of rocket motors.

Acknowledgments
The authors are grateful to the Ministry of Education, Science and Technological Development of the Republic of Serbia for the support
provided, as part of the project: Contract No. 451-03-9/2021-14/200325.

Declaration of conflicting interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Funding
The author(s) received no financial support for the research, authorship, and/or publication of this article.

Data availability statement

The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

ORCID iDs
Jelena Rusmirović  https://orcid.org/0000-0002-7151-2666

Supplemental material
Supplemental material for this article is available online.

References
1. Eggers F, Almeida JHS, Azevedo CB, et al. Mechanical response of filament wound composite rings under tension and compression.
Polym Test 2019; 78: 105951.
2. Bassler J. Colorado state university rocket team builds newly designed rocket fuselage with filament winding equipment provided by
prodigm, lattice composites resins, and composites one carbon fibers. Reinf Plast 2020; 64: 92–96.
Rusmirović et al. S1553

3. Rafiee R. On the mechanical performance of glass-fibre-reinforced thermosetting-resin pipes: A review. Compos Structures 2016; 143:
151–164.
4. Khan R. Fiber bridging in composite laminates: A literature review. Compos Structures 2019; 229: 111418.
5. Papa I, Boccarusso L., Langella A., et al. Carbon/glass hybrid composite laminates in vinylester resin: Bending and low velocity impact
tests. Compos Structures 2020; 232: 111571.
6. Chen W, Li P, Yu Y, et al. Curing kinetics study of an epoxy resin system for T800 carbon fiber filament wound composites by dynamic
and isothermal DSC. J Appl Polym Sci 2008; 107: 1493–1499.
7. Almeida JHS, Souza SDB, Botelho EC, et al. Carbon fiber-reinforced epoxy filament-wound composite laminates exposed to hy-
grothermal conditioning. J Mater Sci 2016; 51: 4697–4708.
8. Taheri-Behrooz F, Esmkhani M and Yaghoobi-Chatroodi A. Effect of testing procedure on the in-plane shear properties of CNF/glass/
epoxy composites. Polym Polym Composites 2020; 28: 159–169.
9. Bhat A, Naveen J, Jawaid M, et al. Advancement in fiber reinforced polymer, metal alloys and multi-layered armour systems for
ballistic applications: A review. J Mater Res Technol 2021; 15: 1300–1317.
10. Jia X, Chen G, Yu Y, et al. Effect of geometric factor, winding angle and pre-crack angle on quasi-static crushing behavior of filament
wound CFRP cylinder. Composites B: Eng 2013; 45: 1336–1343.
11. Castro SGP, Almeida JHS Jr, St-Pierre L, et al. Measuring geometric imperfections of variable-angle filament-wound cylinders with a
simple digital image correlation setup. Compos Structures 2021; 276: 114497.
12. Quanjin M, M Sahat I, Mat Rejab MR, et al. The energy-absorbing characteristics of filament wound hybrid carbon fiber-reinforced
plastic/polylactic acid tubes with different infill pattern structures. J Reinf Plast Compos 2019; 38: 1067–1088.
13. Kubota Y, Miyamoto O, Aoki T, et al. New thermal protection system using high-temperature carbon fibre-reinforced plastic sandwich
panel. Acta Astronautica 2019; 160: 519–526.
14. Fathi A, Liaghat G, Sabouri H, et al. Experimental investigation of quasi-static behavior of composite and fiber metal laminate panels
modified by graphene nanoplatelets. J Reinf PlastCompos 2021; 40: 518–532.
15. Rusmirović J, Lukić V, Kovačević T, et al. Fireproof phosphorylated kraft lignin/polyester based composites: Green material for rocket
propellant thermal protection systems. Sci Tech Rev 2019; 69: 16–22.
16. Natali M, Kenny JM and Torre L. Science and technology of polymeric ablative materials for thermal protection systems and
propulsion devices: A review. Prog Mater Sci 2016; 84: 192–275.
17. Almeida JHS, Ribeiro ML, Tita V, et al. Damage modeling for carbon fiber/epoxy filament wound composite tubes under radial
compression. Compos Structures 2017; 160: 204–210.
18. Rojas-Sanchez J, Schmack T, Boesl B, et al. Strain rate-dependent characterization of carbon fibre-reinforced composite laminates
using four-point bending tests. J Reinf Plast Composs 2020; 39: 165–174.
19. Solomon B, George D, Shunmugesh K, et al. The effect of fibers loading on the mechanical properties of carbon epoxy composite.
Polym Polym Compos 2017; 25: 237–240.
20. Irfan MS, Saeed F, Gill YQ, et al. Effects of hybridization and fiber orientation on flexural properties of hybrid short glass fiber- and
short carbon fiber-reinforced vinyl ester composites. Polym Polym Compos 2018; 26: 371–379.
21. O’Donnell J and Chalivendra V. Multi-functional glass/carbon fibers hybrid inter/intra laminated composites. Compos C Open Access
2021; 4: 100121.
22. Reuter J, Greiner L, Kukla P, et al. Efficient flame retardant interplay of unsaturated polyester resin formulations based on ammonium
polyphosphate. Polym Degrad Stab 2020; 178: 109134.
23. Boussetta H, Beyaoui M, Laksimi A, et al. Study of the filament wound glass/polyester composite damage behavior by acoustic
emission data unsupervised learning. Appl Acoust 2017; 127: 175–183.
24. Guleria T, Verma N, Zafar S, et al. Fabrication of Kevlar-reinforced ultra-high molecular weight polyethylene composite through
microwave-assisted compression molding for body armor applications. J Reinf Plast Compos 2021; 40: 307–320.
25. Radulović J and Karkalić R. Filament wound filter housing: Key for rational purification process of highly corrosive solutions. Sci Tech
Rev 2019; 69: 45–52.
26. Radulovic J. Characterization of filamentwound polymeric composite materials. Sci Tech Rev 2008: 66–75.
27. Rusmirović J, Radoman T, Džunuzović ES, et al. Effect of the modified silica nanofiller on the mechanical properties of unsaturated
polyester resins based on recycled polyethylene terephthalate. Polym Compos 2017; 38: 538–554.
28. Rusmirovic JD, Trifkovic KT, Bugarski B, et al. High performances unsaturated polyester based nanocomposites: Effect of vinyl
modified nanosilica on mechanical properties. Express Polym Lett 2016; 10: 139–159.
29. Petersen MR, Chen A, Roll M, et al. Mechanical properties of fire-retardant glass fiber-reinforced polymer materials with alumina tri-
hydrate filler. Compos B: Eng 2015; 78: 109–121.
30. Kovačević T, Drah A, Božić A, et al. The surface modification of alumina particles for its application in unsaturated polyester resins. In:
26th International Conference Ecological Truth & Environmental Research, Bor, Serbia, 12-15 Jun 2018, pp. 338–342. Bor: Serbia.
31. Mohanty A, Srivastava VK and Sastry PU. Investigation of mechanical properties of alumina nanoparticle-loaded hybrid glass/carbon-
fiber-reinforced epoxy composites. J Appl Polym Sci 2014; 131: 1–7.
32. Drah A, Kovačević T, Rusmirović J, et al. Effect of surface activation of alumina particles on the performances of thermosetting-based
composite materials. J Compos Mater 2019; 53(19): 2727-2742.
33. Elbasuney S. Novel multi-component flame retardant system based on nanoscopic aluminium-trihydroxide (ATH). Powder Technol
2017; 305: 538–545.
34. ISO 1183-1:2012. Second Edition. In: Plastics — Methods for determining the density of non-cellular plastics: ISO, 2012
S1554 Polymers and Polymer Composites 29(9S)

35. Oxyacetylene ablation testing of thermal insulation materials. In: ASTM E 285: ASTM, 2008.
36. Standard test method for short-beam strength of polymer matrix composite materials and their laminates. In: ASTM D 2344: ASTM,
2016: 3.
37. Standard test method for tensile properties of polymer matrix composite materials. In: ASTM D 3039: ASTM, 2008.
38. John B, Mathew D, Deependran B, et al. Medium-density ablative composites: processing, characterisation and thermal response under
moderate atmospheric re-entry heating conditions. J Mater Sci 2011; 46: 5017–5028.
39. González-Gómez MA, Belderbos S, Yañez-Vilar S, et al. Development of superparamagnetic nanoparticles coated with polyacrylic
acid and aluminum hydroxide as an efficient contrast agent for multimodal imaging. Nanomaterials 2019; 9: 1626.
40. Kovačević T, Rusmirović J, Tomić N, et al. New composites based on waste PET and non-metallic fraction from waste printed circuit
boards: Mechanical and thermal properties. Compos B Eng 2017; 127: 1–14.
41. Goertzen WK and Kessler MR. Dynamic mechanical analysis of carbon/epoxy composites for structural pipeline repair. Compos B:
Eng 2007; 38: 1–9.
42. Jawaid M, Abdul Khalil HPS and Alattas OS. Woven hybrid biocomposites: Dynamic mechanical and thermal properties. Compos A:
Appl Sci Manufacturing 2012; 43: 288–293.
43. Romanzini D, Lavoratti A, Ornaghi HL, et al. Influence of fiber content on the mechanical and dynamic mechanical properties of glass/
ramie polymer composites. Mater Des 2013; 47: 9–15.
44. Lavoratti A, Scienza LC and Zattera AJ. Dynamic-mechanical and thermomechanical properties of cellulose nanofiber/polyester resin
composites. Carbohydr Polym 2016; 136: 955–963.
45. Mezger TG. The Rheology Handbook, 2010. Epub ahead of print 2010. DOI: 10.1108/ijppm.2010.07959dab.003.
46. Goertzen WK and Kessler MR. Dynamic mechanical analysis of carbon/epoxy composites for structural pipeline repair. Composites B:
Eng 2007; 38: 1–9.
47. Murugan R., Ramesh R. and Padmanabhan K. Investigation on static and dynamic mechanical properties of epoxy based woven fabric
glass/carbon hybrid composite laminates. Proced Eng 2014; 97: 459–468.
48. Natali M. and Torre L. Composite Materials: Ablative. In: Wiley Encyclopedia of Composites. Hoboken, NJ, USA: John Wiley & Sons;
2012. Epub ahead of print 20 July 2012. DOI: 10.1002/9781118097298.weoc045.
49. Zheng X. and Park C. W. Thermal and mechanical properties of carbon fiber-reinforced resin composites with copper/boron nitride
coating. Compos Struct 2019; 220: 494–501.