Key Engineering Materials Submitted: 2020-05-12

ISSN: 1662-9795, Vol. 877, pp 108-113 Revised: 2020-05-13

© 2021 Trans Tech Publications Ltd, Switzerland Accepted: 2020-05-14
Online: 2021-02-25

Effect of Antimony Trioxide and Carbon Black on the Mechanical

Properties and Ablation Properties of Liner Insulation in Rocket Motors
Thirapat Kitinirunkul1,2,a, Prakob Kitchaiya1,b, Chesda Kiriratnikom2,c,
Paisarn Boonyarat2,d and Suchuchchai Nuanklai2,e
1
Department of Chemical Engineering, Faculty of Engineering, King Mongkut’s Institute
of Technology Ladkrabang, Thailand
2
Defence Technology Institute, Ministry of Defence, Thailand
a
[email protected], [email protected], [email protected], [email protected],
e
[email protected]

Keywords: liner insulation, rocket motor, carbon black, antimony trioxide, ablation

Abstract. This study focused on the mechanical properties and ablation properties of liner insulation
in rocket motors for improving rocket performance by means of tensile strength, elongation, ablation
rate and density. The following parameters were varied: amount of zinc oxide, antimony trioxide and
carbon black (N550). It was found that the insulation of the rocket motors with antimony trioxide and
carbon black provided higher the elongation and ablation rate. Thus, it was able to endure more heat
from hot gas in combustion chamber. The result suggests that use of antimony trioxide and carbon
black as filler in liner insulation can improve the thermal insulators and case-bonded in rocket motor
between the solid propellant and the rocket motor tube.

Introduction
The rocket has 3 main components which are Warhead, rocket motor and nozzle. And the rocket
motor has main components which are rocket motor tube (case), liner insulation and solid propellant,
as in Figure 1.

Figure 1. The rocket components

The rocket motor case material will be made with light metals or composite materials. But the
temperature of hot gas in combustion chamber is 2,000-3,500 K [1-2]. It higher than the melting point
of metals or composite materials. Thus, the rocket motor must have liner insulation to prevent the
rocket motor case from the damage.
A solid propellant (Fuel /Binder/Oxidizer) is a solid-fuel that use to be the propulsion system of
rockets.
The liner insulation in tube is a case-bonded and Thermal insulators, used as heat-barrier materials,
between the solid propellant and the rocket motor tube [3]. Because the composite propellant burns at
very high temperatures. Therefore, it is necessary to coat the liner insulation inside the rocket tube.
When burned, it will protect the heat from the flame of the propellant.

All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of Trans
Tech Publications Ltd, www.scientific.net. (#549422560-30/12/20,00:59:58)
 Key Engineering Materials Vol. 877 109

For rocket at the same caliber. The improving rocket performance with a longer firing range must
increase more solid propellant in rocket motor for fire the rocket to go farther. Increasing the
performance of liner insulation to have more thermal resistant, it will be reduced the thickness of liner
insulation, which will be able to add the solid propellant more. However, if the liner is reduced too
much until it is unable to prevent heat from inside the combustion chamber, it will affect the rocket
motor tube, which will cause the tube to become deformed or leak before the rocket reaches its target.
This problem may cause the rocket explosion or changing the direction of the rocket [4]. The good
ablative martial must have a low ablation rate, low density and good mechanical strength.
The density of the liner insulation, depending upon the density of the individual filler. The lower
values are preferable to reduce the inert mass of the rocket motor.
The ablation rate is the key attributes of liner insulation in rocket motor [5]. The ablation rate
estimated through the following equation;
Ablation rate = d / t (1)
where d = original thickness of the specimen (mm), t = burn-through time (s).
The ablation process is an erosive phenomenon with a removal of material by a combination of
thermo-mechanical, thermo-chemical, and thermo-physical factors such as, surface melting,
sublimation, charring, evaporation, decomposition in depth and film cooling, [6] from high
temperature, pressure, and velocity of combustion flame in the solid rocket motor, as in Figure 2. That
is, physical and chemical changes that absorb heat. During the rocket motors working, under these
extreme conditions, the insulation materials would be degraded and then carbonized to form a char
layer. A temperature gradient would be formed in the char layer, which decreases the penetration of
the heat in the insulator and provides thermal protection for the motor chamber.When heat from the
surface conduct through the char layer reaches the virgin material, it starts to change state. The
insulation starts to decompose and pyrolysis reactions start, generating gaseous by-products and a
porous char residue. In fact, the pyrolysis gases produced by the charring matrix through the char
layer and absorb heat providing cooling. And the char layer also reduces the oxygen diffusion from
the boundary layer to the virgin bulk, thus playing a hindering action against the exothermic
degradation reactions of the neat polymeric matrix. The carbonaceous residue of polymer is a
relatively weak medium that can be removed by the friction action due to the interaction with
high-pressure and temperature combustion products of rocket propellants. For this reason, some
reinforcements must be added to the virgin polymer since the polymer alone cannot efficiently work
as an ablative material. For this purpose, fibrous reinforcements made of alumina, silica, carbon,
glass, and mineral asbestos, were successfully combined with the polymer.[7-9]

Figure 2. The ablation process [7-8]

Liner Insulation consists of Binder, Curing Agent, Plasticizer, Accelerator and Filler. The groups
of chemicals used as substances Polyol (OH) and Isocyanate (NCO) mixed according to the ratio. To
compatibility and bonding with the propellant and liner. The compositions should be based on the
110 Material and Manufacturing Technology XI

same binder. A liner formulation based on Hydroxyl Terminated Polybutadiene (HTPB) as a basic
resin with different fillers and crosslinking agent [10]. Giants coated the liner insulation consists of
HTPB and dimeryl diisocyanate (DDI) [11]. Haska, et al. have coated the liner insulation consists of
HTPB-IPDI with composite propellant and rocket motor tube [12]. Kakade, et al. have coated the
liner insulation consists of HTPB and Toluene diisocyanate (TDI with various of filler such as, silica,
antimony trioxide and carbon black, melamine, lithopone, asbestos, titanium oxide, kaolin, mica, talc,
alumina trihydrate. The result of this research shows, the carbon black (N-550), silica and antimony
trioxide have the highest mechanical properties, low density and low ablation rate. [13]
In this studied coated the liner insulation by HTPB and Toluene diisocyanate (TDI) because the
solid propellant in this case used HTPB-TDI-based. And use silicon dioxide, zinc oxide, carbon black
(N-550) and antimony trioxide as a filler.

Methodology
Material. The Hydroxyl Terminated Polybutadiene (HTPB) from Zibo Qilong Chemical Industry
Co., Ltd. Toluene diisocyanate (TDI) from Sigma Aldrich co., Ltd. Carbon Black N550 from Thai
Carbon Black PCL. Antimony Trioxide from Chemical Innovation Co., Ltd.
Measurements. The mechanical properties were measured by using a universal testing machine
(Instron 5966).
The density was measured by using a density analyzer (Mettler toledo xp 105).
The ablation properties were measured by using oxygen and acetylene ablation testing equipment
is illustrated in Figure 3 according to ASTM E285. Hot combustion gases are directed along the
normal to the specimen until burn-through is achieved and calculate the ablation rate of the material is
determined by dividing the original thickness by the time to burn-through. [14]

Figure 3. Schematic Diagram of Gas System [14]

Preparation of Liner Insulation for Rocket Motors. Preparation of liner insulation by bringing
HTPB to remove moisture by vacuum mixer at 80°C for 2 hours. Remove moisture of zinc oxide,
silicon dioxide, antimony trioxide and carbon black by dry oven at 120°C for 48 hours. Then mixing
the composition in table 1 except TDI by vacuum mixer at room temperature for 2 hours. Then added
TDI in mixer and. After that filled liner insulation in mold and curing by oven at 50°C for 6 hours in
Figure 4.
 Key Engineering Materials Vol. 877 111

Table 1. The composition of liner insulation for rocket motors

Liner amount Sample Sample Sample Sample Sample Sample Sample
(%Wt.) 1 2 3 4 5 6 7
HTPB 60.20 60.20 60.20 60.20 60.20 60.20 60.20
Silicon Dioxide 3.50 3.50 3.50 3.50 3.50 3.50 3.50
Zinc Oxide 19.50 14.50 9.50 4.50 14.50 9.50 4.50
Antimony Trioxide 0.00 5.00 10.00 15.00 0.00 0.00 0.00
Carbon Black 0.00 0.00 0.00 0.00 5.00 10.00 15.00
TDI 10.40 10.40 10.40 10.40 10.40 10.40 10.40
Other 6.40 6.40 6.40 6.40 6.40 6.40 6.40

Figure 4. Mold curing liner insulation

Results and Discussion

The properties of liner insulation for rocket motors have been recorded as table 2. The sample 1
shown currently used liner insulation. And the test condition of liner insulation see table 3.
Table 2. The properties of liner insulation for rocket motors
Sample Sample Sample Sample Sample Sample Sample
Unit
1 2 3 4 5 6 7
Tensile strength MPa 7.09 5.54 5.54 5.81 4.87 4.93 5.08
Elongation % 258.87 269.82 270.46 289.69 195.96 203.44 208.32
Density g/cm3 1.167 1.151 1.161 1.164 1.135 1.112 1.095
Ablation rate mm/s 1.73 1.558 1.499 1.405 1.472 1.392 1.433
Table 3. The test condition of liner insulation
Item Unit Design value Test conditions
Tensile strength MPa ≥1.2 20°C, 100mm/min
Elongation rate % ≥150 20°C, 100mm/min
Density g/cm3 ≤1.2 20 °C
Ablation rate mm/s ≤1.8 Oxygen-acetylene
112 Material and Manufacturing Technology XI

The results of the analysis are as follows:

1) The increasing of the %wt. of Antimony Trioxide and Carbon Black affected tensile strength
increased.
2) The increasing of the %wt. of Antimony Trioxide and Carbon Black affected elongation
increased.
3) The increasing of the %wt. of Antimony Trioxide affected density increased.
4) The increasing of the %wt. of Carbon Black affected density declined.
5) The increasing of the %wt. of Antimony Trioxide and Carbon Black affected ablation rate
declined.
Mechanical Properties. The result in Figure 5-6, shown that the tensile strength and elongation of
samples 2-7 are more than the design value. The result in Figure 7, shown that the density of samples
2-7 are less than 1.2 g/cm3.
Ablation Properties. The result in Figure 8, shown that ablation rate of sample 2-7 are less than
1.8 mm/s. And see in Figure 5-8 the main effects analysis to determine sample 4 that were the best
condition.

Figure 5. Tensile strength of liner insulation Figure 6. Elongation of liner insulation

Figure 7. Density of liner insulation Figure 8. Ablation rate of liner insulation

Conclusions
This research was carried out to study the influence of Antimony Trioxide and Carbon Black on
the mechanical properties and ablation properties of Liner insulation for rocket motors. Sample 4 give
the tensile strength was 5.81 MPa, elongation was 289.69%, density was 1.164 g/cm3 and the
ablation rate was 1.405 mm/s. The Insulation formulation using zinc oxide 4.5%wt. as a filler with a
combination of Antimony Trioxide 15%wt. as a flame retardant give the highest mechanical
properties, thermal stability, low density, and low ablation rates. So, the best condition
 Key Engineering Materials Vol. 877 113

Acknowledgements
This work was supported in part by Research and Development Workshop Department, Defence
Technology Institute, Ministry of Defence, Thailand

References
[1] W.H. Beck: Pyrolysis studies of polymeric materials used as binders in composite propellants:
a review. Combust and Flame Vol. 70, Issue 2 (1987), p. 171–190.
[2] National aeronautics and space administration: Solid rocket motor nozzles. NASA space vehicle
design criteria (Chemical propulsion), United States. (1975)
[3] X. Jia, Z. Zeng, G. Li, D. Hui, X. Yang and S. Wangd: Enhancement of ablative and interfacial
bonding properties of EPDM composites by incorporating epoxy phenolic resin. Composites
Part B: Engineering Vol. 54 (2013), p. 234-240.
[4] R. Vesna: Case Bonded System for Composite Solid Propellants. Scientific Technical Review,
Vol.57. (2007)
[5] N.K. Nath and K.B. Dinesh: Performance evaluation of flex nozzle ablative liners by conducting
solid rocket motor ground firing test. Journal of Manufacturing Engineering Vol. 12, Issue 4
(2017), p. 191-195.
[6] N.K. Nath and P. Mallesham: Development of Composite Ablative Liners For Solid Rocket
Motor Flex Nozzles. Journal of Aerospace Sciences & Technologies Vol. 65 (2013), p. 254-261.
[7] L. Jiang, X. Kun, L. Xiang, L. Qiang, and W. Shu-xian: Characteristics and formation mechanism
of compact/porous structures in char layers of EPDM insulation materials. Carbon
Vol. 127 (2018), p. 498-509.
[8] R. Marco, N. Maurizio and T. Luigi: An Introduction to Ablative Materials and
High-Temperature Testing Protocols. Nanomaterials in Rocket Propulsion Systems. (2019),
p. 529-549.
[9] S.V. Balaji, C.C. Gary, P.K. Roy and A. Anahita: Computational Tools for Re-entry
Aerothermodynamics: Part II. Surface Ablation, Aerospace Sciences Meeting and Exhibit,
United States. (2008)
[10] G.P. Sutton: Rocket Propulsion Elements, 6th Edition, John Wiley & Sons. (1992)
[11] T.W Giants: Case-bond liner systems for solid rocket motors. Aerospace Corporation Report
No.TR 0090 (5935-02), The Aerospace Corporation, California, USA. (1991)
[12] C.B. Haska, E. Bayramali, F. Pekel and O. Saim: Mechanical properties of HTPB-IPDI-based
elastomers. Journal of Applied Polymer Science Vol. 64, Issue 12, (1997), p. 2347-2354.
[13] S.D. Kakade, S.B. Navale, U.B. Kadarn and M. Gupta: Effect of Fillers and Fire Retardant
Compounds on Hydroxy-Terminated Polybutadiene-Based Insulators. Defence Science Journal
Vol. 51, No.2 (2000)
[14] ASTM Designation E285-08: Standard Test Method for Oxyacetylene Ablation Testing of
Thermal Insulation Materials. (2015)