FirePhysChem 2 (2022) 1–3

Contents lists available at ScienceDirect

FirePhysChem
journal homepage: http://www.keaipublishing.com/cn/journals/firephyschem/

Editorial from the guest editors

Weiqiang Pang a,1,2,∗, Luigi T. DeLuca b,3,4
a
Xi’an Modern Chemistry Research Institute, Xi’an, Shaanxi 710065, China
b
SPLab, Department of Aerospace Science and Technology, Politecnico di Milano, Milan 20156, Italy

a r t i c l e i n f o

Keywords:
Solid rocket propulsion
Solid propellants
Solid fuels
Composite energetic materials
Metals
Graphite
Burning rate catalysts
Characterization
Combustion
Performance
Applications
Molecular dynamic simulation

Editorial from the guest editors impulse (Is ) at most around 80 s (under standard operating conditions).
Development sensibly accelerated in the 19th century thanks to the dis-
In recent years, the frequency of rocket launches has considerably in- covery of liquid nitroglycerin (NG) by the Italian Sobrero in 1846, which
creased due to advances in space technology, space exploration, space led to the manufacture in Europe of homogeneous double base (DB) pro-
tourism, and the need to conduct space-based zero-gravity experiments pellants increasing the delivered Is , say to 150 s. Finally, in 1942, the
on space stations. Most space launchers use solid propellant for the American Jack Parson manufactured the first castable composite propel-
booster stage, and sometimes even for the main stages, because of the lant based on potassium perchlorate and further raised the delivered Is
prominent solid propellant capability to produce large thrust promptly to near 180 s. At Atlantic Research Corporation (ARC) in 1955 and Aero-
and with a relatively simple technology. Solid rocket propellants are jet in 1956, both in USA, a further increase of performance was made
composite energetic materials meant to generate large amounts of hot possible by using aluminum (Al) as energetic fuel in conjunction with
gases by combustion, which produce thrust by feeding the supersonic ammonium perchlorate (AP) and the support of synthetic polymers, rais-
gas dynamic nozzles of rocket and missile motors. The propellant na- ing Is to about 230 s. The successive step of nano-sized Al (nAl) powder
ture and behavior directly affect the space launcher performance as was realized at the Institute of Chemical Physics (ICP) in Moscow, Rus-
well as the combat effectiveness and survivability of missile weapons. sia, in 1970, but the acceptance for industrial applications is still under
Thus, solid propellants play a crucial role in the progress of missile and discussion.
aerospace technology. Since then, progress has been much slower and only the introduc-
The development of solid energetic materials started more than 2000 tion of energetic plasticizers made it possible for delivered Is to go past
years ago in China with black powder, or something very close to it. For 250 s. Regarding nano-sized particles, they have a great potential for
centuries slow but continuous refinements made possible for the origi- aerospace propulsion applications, because of rapid ignition and short
nal fireworks to give birth in India to primordial rocket motors, based combustion times. Nano-sized particles can be included in solid fuels,
on black powder and iron case, with a delivered gravimetric specific solid propellants, or even as energetic gellant in liquid systems. How-
ever, while productive for nanothermites and other applications, in the

∗
Corresponding author.
E-mail address: nwpu_pwq@163.com (W. Pang).
1
Website: https://www.researchgate.net/profile/Weiqiang_Pang2
2
Interests: Composite Energetic Materials, Nano-Structured Materials, Solid Rocket Propellants, Ignition, Combustion, Simulation
3
Website: https://www.researchgate.net/profile/Luigi_DeLuca
4
Interests: Aerospace Propulsion, Solid Propellant, Hybrid Propellant, Energetic Materials, Combustion, Transient Burning

https://doi.org/10.1016/j.fpc.2022.03.002

Available online 29 March 2022

2667-1344/© 2019 Xi’an Modern Chemistry Research Institute. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/)
W. Pang and L.T. DeLuca FirePhysChem 2 (2022) 1–3

case of rocket propellants the implementation of nano-scale energetic In the recent years, the emergence of high-energy density com-
materials (nEMs) is still limited to laboratory scale and scientific inves- pounds (such as CL-20, DNTF, ADN, TKX-50, etc.) and high-energy fu-
tigations, except for special ingredients present in little amounts such as els (AlH3 , boron, metal alloys, etc.), allowed formulating new propel-
catalysts and ballistic modifiers. lants with an increased energy density. In addition, reactive compos-
Overall, solid rocket propulsion is considered by many experts a ma- ite energetic materials were investigated, such as metal organic frame-
ture technology today. DB propellants, as homogeneous mixtures of NC work compounds (MOFs), metastable intermixed composites (MICs),
(nitrocellulose) with NG (nitroglycerin), have been widely applied to Al/polytetrafluoroethylene (PTFE) core-shell shaped composites, etc.
solid rocket propulsion. They are smokeless, can count on adjustable MOFs have a variable composition and structural characteristics with
energy level and abundant raw material sources, and are suitable for great application potential; they can be used in solid propellants as com-
free standing motor grain configurations thanks to their high strength bustion catalysts and energetic additives. MICs are among the most pop-
and elastic modulus. On the other hand, limitations are faced because of ular research topics in the field of EMs and nAl-based MICs are an ex-
the low-temperature embrittlement caused by the semi-rigid NC macro- cellent alternative to nAl. MICs that contain nAl as the main component
molecule. Composite propellants are a multi-phase mixture of oxidizing can provide the benefits of reduced size reactants and increased reac-
particles (such as AP) and metal fuel particles (such as Al) with high tivity by using nanoscale fuels and oxidizers. Using nAl/fluoropolymers
polymers as matrix. For example, hydroxyl terminated polybutadiene MICs, the volatile aluminum fluoride is formed instead of aluminum ox-
(HTPB) is a polymer widely used in propulsion both for composite solid ide at relatively low temperatures; thus, enhanced combustion without
propellants and hybrid fuels. This is due to HTPB ease of manufacturing, sintering and exothermic reactions between the Al2 O3 shell and fluorine
slow aging, and capacity of providing good mechanical properties also are expected.
to highly loaded grains. The composite modified double base (CMDB) This Special Issue of FirePhysChem collects contributions covering
propellant, often used in military missiles and space vehicles, properly recent progress and novel applications in solid rocket propulsion. Atten-
combines specific features of the two previous kinds of propellant. tion is focused on design, characterization, properties, and especially the
New requests are invoked for solid rocket propellants to be still at- state-of-the-art of this class of thermochemical propulsion devices. A to-
tractive for large-scale operations. On top of the energetic performance, tal of 20 papers was selected for publication after a standard peer review
density, low-cost, low-sensitivity to multiple stimuli, low-characteristic process: the first 10 papers - 5 from Chinese authors and 5 from inter-
signature, slow aging, safety, green features before and after burning, national authors – are included in this Spring 2022 special issue, while
easy disposal, and reuse technology are also of great interest to re- the remaining 10 papers will be published in this Fall 2022 special is-
searchers and users of solid propellants. Materials such as desensitizers, sue. Participation of young authors with novel/innovative concepts was
plasticizers, catalysts and so on are often incorporated into propellant especially encouraged. Young PhD. candidates or laureates were looked
composition and require attention. Thus, high-energy, low vulnerabil- for since they are more prone to new ideas or visions. Of course, with
ity, and green solid propellants, laser-driven combustion, etc. are now the assistance of their advisors.
hot topics world-wide. LingZe Kong used molecular simulation to evaluate the protection
Today, an important challenge concerns the solid oxidizer. AP is the capability of different antioxidants in the HTPB-based propellants by
most widely used ingredient in modern rocketry and AP-based solid pro- quantum chemistry, molecular dynamics, and Monte Carlo methods.
pellants are known for high performance, good combustion characteris- Zhao Qin et al. prepared a novel reactive powder, Al/PTFE (polyte-
tics, easy availability, and low cost. The reasons for the AP success are trafluoroethylene) 70/30 in mass, by mechanical activation and care-
high burning rate, simple burning rate tailoring, non-hygroscopic crys- fully analyzed its properties. The effects on burning rate, flame struc-
tals, and easy compatibility with fuel binders. On the other hand, AP- ture, and quenched surface of CL-20 - based CMDB propellants were
based propellants are extremely toxic, promote carcinogenic effects on analyzed.
the human health, are hazardous for the environment, and require safe Fluoropolymers (FP) can improve the ignition and combustion of
operational handling and storage. As an example, the European Space Al particles through pre-ignition reactions with the alumina passivation
Launcher Ariane-5 contains 476 tons of AP-based composite propellant, layer, but the mechanism is still unclear. Thus, Shixi Wu et al. prepared
which converts into 270 tons of concentrated HCl upon combustion. two kinds of energetic microspheres, Al/AP@FP and Al/RDX@FP, with
Hence, regular use of AP can lead to detrimental effects on earth at- FP as the supporting framework. High-speed camera, acoustic emission,
mosphere and on the upper ozone layer. Thus, an urgent need exists to and laser particle size analyzer were used to characterize the Al particle
replace AP. For example, ammonium dinitramide (ADN) [NH4 N(NO2 )2 ] combustion and the propellant ballistic properties.
is one of the candidates to replace AP fully or partially in nearly all kinds Fuel-rich formulations can utilize sea water or air as oxidant with
of solid rocket propellants. ADN mainly consists of nitrogen (N), oxygen ramjet. Under the same conditions of volume or weight, compared with
(O), and hydrogen (H), making its combustion products harmless to the the conventional propellant, fuel-rich solid propellants allow a stronger
environment. Further, the presence of dinitramide anion [N(NO2 )2 − ] mobility of missiles/torpedoes. Since the AP content in fuel-rich propel-
imparts high density, high heat of formation, and high oxygen content. lants is much less than that in conventional propellants, it is difficult
Another important challenge regards Al, which is commonly used as to increase the burning rate by relying on the superfine AP or AP de-
a fuel in solid rocket propellants because of its ability to boost the overall composition catalysts. Thus, RongJie Yang et al. investigate the com-
performance of a rocket motor. Adding Al increases the specific impulse, bustion behaviors of Al/Mg-based fuel-rich HTPB propellants with 40
density, and the total energy density of the propellant, while minimizing mass% metal content with and without the addition of a fast-burning
combustion instabilities by generating condensed combustion products, compound or burning rate catalyst.
which attenuate the acoustic oscillations in the motor cavity. However, Azido polyether-based propellants, such as GAP, BAMO, AMMO,
aluminized particles are prone to agglomeration, resulting in incomplete have attracted much attention due to their high energy and low me-
chemical energy conversion of the propellant as well as increased ero- chanical sensitivity. To investigate the effects of plasticizers on the
sion of the nozzle walls through increased slag deposition. Furthermore, pBAMO-b-GAP copolymer (the copolymer of 3,3’-bis(azidomethy) ox-
large particles require more energy to accelerate than small particles, etane and glycidyl azide polymer), JiangFeng Pei et al. evaluated the
hence reducing the delivered specific impulse. Over the past decades, binding energy, solubility parameter, and mechanical properties of
different ways to tailor the propellant formulation were tested, such as copolymer/plasticizer mixed systems by molecular dynamics simula-
increasing the AP concentration, reducing the metal content, resorting tions. The mechanical properties of the tested formulations were also
to burning rate catalysts, decreasing the Al particle size, and introduc- studied experimentally.
ing new ingredients such as nAl, metallic alloys, fluoropolymer coatings, Djalal Trache et al. study the effect of micro- and nanoparticles of
and more. copper oxide (μCuO and nCuO) on the thermal decomposition of com-

2
W. Pang and L.T. DeLuca FirePhysChem 2 (2022) 1–3

posite solid propellants based on AP, HTPB and binary fuel mixture of Al It is our great pleasure to thank the following international review-
and Li tetrahydridoaluminate (AP/HTPB/Al+LiAlH4 ). The kinetic mod- ers for their substantial help in raising the quality of this Special Is-
eling of the thermal decomposition process is discussed. The decompo- sue. Without their efforts, its publication would not have been possible:
sition mechanisms of the investigated propellant samples have changed Adriano Annovazzi, Luciano Galfetti, Alon Gany, Nagendra Kumar, Daniele
through the incorporation of nano- and micro-CuO. Pavarin, Evgeny Shafirovich, Djalal Trache, Alexander Vorozhtsov, Yinon
In large motors with solid composite propellants, a multi-batch pro- Yavor, XuHui Chi, XueHai Ju, LinLin Liu, GaoChun Li, Jie Liu, QiLong Yan,
cess is common, whereby each batch is prepared consecutively without Xing Zhou, ZheJun Wang, and YingChun Wu. We would also like to thank
adding the curing agent. Only once all batches are ready, the casting pro- all the authors for their contribution and collaboration in following the
cess starts with the addition of the curing agent. Thus, for each batch recommendations received by the reviewers, editors, and publishers.
there is some storage time between the end of preparation and the effec-
Prof. Weiqiang Pang
tive casting. Bruno Cesar Christo da Cunha et al. evaluated the influence
Xi’an Modern Chemistry Research Institute
of this storage time on the rheological properties of the slurry and the
final mechanical properties of the grain by monitoring the viscosity in
time.
Adam Okninski et al. discuss the potential use of hydrogen peroxide
HTP (High Test Peroxide) class as oxidizer for solid rocket propulsion.
While hydrogen peroxide is a liquid in normal conditions and its uti-
lization has been historically limited to liquid propulsion, it can also be
used in solid rocket motor grains. In this respect, updated concepts are
reviewed.
Since expandable graphite (EG) is a form of intercalated graphite, Prof. Luigi T. DeLuca
Alon Gany et al. investigate a novel method for manipulating and SPLab, Politecnico di Milano
enhancing the burning of solid fuels and propellants by expandable
graphite additive. At elevated temperature EG undergoes an increase
in volume, forming elongated strings/fibers many folds longer than the
original particles/flakes.
Yinon Yavor et al. formulated and tested a novel green solid propel-
lant consisting of ∼20% boron + ∼60% AN + ∼20% water with a small
amount of gelling agent. Mechanical and ballistic properties of propel-
lant strands were investigated and revealed promising for applications.