FirePhysChem 2 (2022) 56–66

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FirePhysChem
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Hydrogen peroxide – A promising oxidizer for rocket propulsion and its

application in solid rocket propellants
Wioleta Kopacz a, Adam Okninski a,∗, Anna Kasztankiewicz a, Paweł Nowakowski a,
Grzegorz Rarata a,b, Pawel Maksimowski c
a
Lukasiewicz Research Network - Institute of Aviation, Center of Space Technologies, Al. Krakowska 110/114, 02-256 Warsaw, Poland
b
European Commission, Joint Research Centre, Retieseweg 111, 2440 Geel, Belgium
c Warsaw University of Technology, Faculty of Chemistry, Department of High-Energetic Materials, Noakowskiego 3, 00-664 Warsaw, Poland

a r t i c l e i n f o a b s t r a c t

Keywords: This paper discusses the potential use of hydrogen peroxide as oxidizer for solid rocket propulsion. While hy-
Hydrogen Peroxide drogen peroxide is a liquid in normal conditions, it may be used in solid rocket motor grains. Use of hydrogen
High Test Peroxide peroxide of HTP class (High Test Peroxide) is proposed. It has been known for many decades but its utilization has
Solid Rocket Propellant
been historically limited to liquid propellants. Until recently is application even in liquid state in rocket propul-
Solid Rocket Motor
sion for space and defence has been limited due to storability and safety issues. With the availability of new
Storable Propellant
Green Propellants grades of HTP with higher purity and concentrations, enhanced performance, safety and storability are possible.
This results in HTP being considered for a wide range of rocket propulsion systems: as oxidizer in bipropellant
and hybrid propulsion systems, as well a monopropellant. To ensure proper analysis of the potential of using
HTP in next-generation solid rocket propellants, this paper reviews existing rocket propulsion applications of
HTP. Modern use requires high performance and common current composite propellant compositions utilize am-
monium perchlorate (AP) as oxidizer, what has several disadvantages, which are discussed. Alternative oxidizing
compounds include ammonium dinitiramide (ADN), ammonium nitrate (AN), hydrazinium nitroformate (HNF),
hexanitrohexaazaisowurtzitane (HNIW) and several other secondary explosives. Key properties of solid propel-
lant oxidizers are listed and discussed. The need for further alternatives, despite numerous recent advances in
solid rocket oxidizer technology is justified. The global push forward high performance green propulsion is one
of the main motivations behind considering HTP for solid rocket propulsion. Theoretical performance of solid
rocket motors using solid grains containing a high mass fraction of HTP is presented. This includes performance
considering several fuels and additives and different oxidizer loadings. Up to date concepts of using hydrogen per-
oxide in solid propellants are reviewed. Solid cryogenic propellants using hydrogen peroxide are mentioned, but
focus is given to solid propellants which could ensure flexible operations, thus use in state-of-the-art solid rocket
motors. Challenges of HTP application as an oxidizer for solid propulsion are listed. This includes a discussion
concerning its reactivity, thus limited compatibility with organic materials. Recommendations for further exper-
imental work are proposed. Potential technology applications are listed with explanations why these particular
niches may benefit from utilization of the new solid propellant technology.

Abbreviations GTO Geostationary Transfer Orbit

ADN Ammonium Dinitramide HAN Hydroxylammonium Nitrate
AFM-315E Air Force Monopropellant 315E HNF Hydrazinium Nitroformate
AN Ammonium Nitrate HMX High Melting Explosive
AP Ammonium Perchlorate HNIW Hexanitrohexaazaisowurtzitane
BAMO 3,3′-bis(azidomethyl)oxetane HTP High Test Peroxide
CSP Cryogenic Solid Propellants HTPB Hydroxyl-Terminated Polybutadiene
EAR Export Administration Regulations ICBM Intercontinental Ballistic Missile
ESA European Space Agency ITAR International Traffic in Arms
GEO Geostationary Orbit KP Potassium Perchlorate

∗
Corresponding author.
E-mail address: adam.okninski@ilot.lukasiewicz.gov.pl (A. Okninski).

https://doi.org/10.1016/j.fpc.2022.03.009
Received 10 January 2022; Received in revised form 25 February 2022; Accepted 28 February 2022
Available online 29 March 2022
2667-1344/© 2022 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. Kopacz, A. Okninski, A. Kasztankiewicz et al. FirePhysChem 2 (2022) 56–66

LAE Liquid Apogee Engine itary and civilian developments. Nevertheless, for several applications
LEO Low Earth Orbit high performance remains a key requirement. This includes upper-stage
LMP-103s Liquid Monopropellant 103s propulsion and vehicles with strict envelope limits and very demand-
LOX Liquid Oxygen ing missions. Since lack of major performance improvements for com-
LRE Liquid Rocket Engine monly known and investigated propellants, can be historicaly observed,
MON Mixed Oxides of Nitrogen therefore focus on propellants yet somehow unexplored should be con-
MMH Monomethylhydrazine sidered. This does not necessary mean that only new compounds may
NF Nitroform enable major innovations. While numerous new energetic binder devel-
NIS Sodium-iodide symporter opments [19] and propellant formulations [20] are investigated world-
PAA Sodium polyacrylate wide, many novel compounds will need many years for industrial imple-
PB Polybutadiene mentation. As in the case of HNIW (often referred to as CL-20 – China
PE Polyethylene Lake-20), large-scale production of new compounds can be limited for
RCS Reaction Control System many years and very high costs inhibit their wide utilization despite
REACH Registration, Evaluation, Authorisation and Restriction of good properties for use in rocket propellants and explosives [21,22].
Chemicals Therfeore, looking into well known compounds in an innovative way
RDX Research Department Explosive may be an option for seeking advances which would be possible for
SDM Space Debris Mitigation faster and wider industrial implementation – an example approach of
SRM Solid Rocket Motor this type has been proposed within this paper and is discussed in the
TRL Technology Readiness Level following paragraphs. It assumes using a well established green rocket
oxidizer: hydrogen peroxide.
1. Introduction
2. The constant search for green high performance solid rocket
Solid propellants have been the main effort of research and devel- propellants
opment activities within the area of rocket propulsion technology since
the dawn of rocket artillery and missile technology [1]. Their exten- Apart from performance and cost minimisation requirements, the
sive use stretches across a constantly expanding range of military sys- aerospace and defence sectors, as nearly all other technical domains,
tems and since the very beginning of interest in spaceflight, they have are under the constant pressure to push for green solutions. In particular
been also considered for civilian space technology application – firstly the area of chemical propellants is considered critical. Anastas proposed
during initial low atitude flights [2] and since 1958 as stages in nu- twelve principles regarding green chemical engineering [23]. This con-
merous orbital launch vehicles [3]. The wide use of solid rocket mo- sidered obtaining greener chemicals, processes and final products, what
tors is due to their long duration storability, relative ease of transporta- is more than relevant after nearly 25 years after the establishment of
tion and launch preparations, high reliability and robustness. Very wide this approach. Chemical processes shall be safe for humans and the sur-
ranges of obtainable solid propellant burn rates (from sub-mm/s burn rounding environment. The fundamental concept assumes that efforts
rates up to over 50 mm/s) [4] allow for design of systems for various should be given to preventing generating pollution and hazards, unlike
applications. New propellants shall allow, apart from ground storage, concentrating on post factum nautralisation of harm. Apart from green
long duration missions in space conditions [5,6]. Solid propellants with combustion products, the overall life cycle assessment may also be con-
minimum signature for military use [7,8] and minimum solid and con- sidered, what has been of direct interest regarding rocket propellants for
densable combustion products, due to space debris mitigation require- space transportation and in-space propulsion [24,25]. New propellants
ments [3], are available. New grain manufacturing processes, includ- in Europe are not to use chemicals expected to be banned by the REACH
ing additive manufacturing are also considered to meet requirements of regulation of the European Union. A definition of green propellants for
the most demanding applications [9] and advancements in SRM design, space applications cane be found in [26]. Moreover, to ease commercial
modelling and optimization are observed worldwide [10]. Therefore, as applications and technology utilization, propellants with a limited num-
of the third decade of the 21st century solid rocket propulsion remains ber of compounds subject to ITAR, EAR and other export regulations are
a major area of development worldwide, despite the emergence of var- anticipated. Other trends and requirements for new energetic material
ious new rocket propulsion technologies, including: green high perfor- developments can be found in Refs. [27,28]. Green propellant composi-
mance storable monopropellants [11], new hypergolic conventional fu- tions should also demonstrate long duration ground and in-space stora-
els [12], hypergolic ionic liquid fuels [13], modern hybrid rocket propul- bilty, which improves system operational envelopes and increases the
sion [14], detonative propulsion [15], gelled propulsion [16] and air- range of potential applications.
breathing high speed combustion propulsion systems including ramjets
3. Hydrogen peroxide: Its properties and applications in chemical
and scramjets [17]. Since solid rocket propulsion remains one of the key
rocket propulsion
investment areas regarding missile and space vehicle technology, it is ex-
pected to be an important potential technology candidate to be used in
An example of an inherently green chemical for propulsion and
newly developed vehicles and stages requiring high thrust-to-weight ra-
power is hydrogen peroxide [29]. Hydrogen peroxide is a high perfor-
tios or simplicity and reliability. One must look for further niches where
mance liquid rocket oxidizer, second only to liquid oxygen [30]. Its high
innovation and advancements can still be made within the area of solid
grades are called HTP (high Test Peroxide). Catalytic decomposition of
rocket propellants, since performance of operational rocket propulsion
anhydrous HTP allows the release of 2.887 MJ of energy per 1 kg of
systems during the last 70 years, shown in Ref. [18], makes it clear that
hydrogen peroxide [31]. The reaction presented in Eq. (1) takes place:
no groundbreaking improvements in terms of delivered specific impulse
have been made in the last 50 years, despite numerous advancements
H2 O2 → H2 O + 1∕2O2 (1)
in enhancing the understanding of chemical rocket propulsion systems.
This is due to nearly meeting chemical equilibrium performance for the This exothermic reaction leads to generation of hot (adiabatic de-
solid propellants commonly used. Some system-level performance ad- composition temperature of 1267 K) water steam and superheated oxy-
vances are being made by enhancing operation pressures, improving uti- gen. Thus, HTP decomposition leads to green products. Mass-wise 47%
lized construction materials, design features and motor propellant mass of the reaction products of anhydrous hydrogen peroxide is oxygen,
fractions. New manufacturing processes and lean organisation allow for what makes its high concentrations efficient for use as oxidizer with var-
cost-effectiveness, which has become a major driver in terms of both mil- ious fuels. While hydregon peroxide has been known since 1818 [32],

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Table 1
Key properties of 98% hydrogen peroxide, based on data from Ref. [39]

Oxygen content Usable oxygen content Vapour pressure

Oxidizer Formula mass-wise/ [-] mass-wise/ [-] at 30°C / mmHg

98% hydrogen peroxide 98% H2 O2 (aq.) 94% 46% 3

(concentration defined
mass-wise)

its consideration for rocket propulsion had to wait for the birth of liquid well as costs are drivers often more important than high specific impulse.
rocket propulsion concepts. Its utilization has been historically firstly With constantly decreasing costs of orbital launches, robust low-cost
limited to liquid propellants [33] and later advances led to its parallel satellite propulsion systems are often favoured over higher performing
use in hybrid rocket motors [34]. Propulsion applications utilize hy- propellants, despite their potentially higher total mass. HTP monopro-
drogen peroxide concentrations above 70% and rocket propulsion typ- pellant thrusters can use catalytic decomposition [46,47] or thermal de-
icaly uses concentrations exceeding 85%. However, close to 100% can composition [48]. HTP costs are lower than those of most liquid mono-
be achieved and values above 99.99% have been demonstrated [35]. propellants and while hydrazine application costs constantly increase
All concentrations discussed and referenced in this paper consider con- due to operations and safety requirements, HTP becomes a wider choice
centration values given mass-wise. Key data of 98% HTP, which is one for spacecraft and rocket RCS systems. The modern ADN-based green
of the grades gaining increased popularity, is provided in Table 1. Hy- monopropellant LMP-103s is, due to its costs, considered nearly only for
drogen peroxide’s high density is one of its advantages, which allows high performance spacecraft applications and new developments show
high volumetric performance of propulsion and power systems utilizing that it is not the first choice for next generation low-cost missions. The
it. Due to HTP’s low-toxicity, low-irritation, low-corrosivity and low- HAN-based AFM-315E is another option, but its high flame temperature
volatility it can be handled and safely used by engineers after training and high preheating requirements also make it not a widely considered
and maintaining necessary focus and procedures [36]. However, some option for low-cost missions and small platforms. Moreover, by vapor-
widely used Refs. [37,38] present hydrogen peroxide as a very danger- ization of LMP-103s and AFM-315E of solvements, explosive materials
ous propellant, what may have led, apart from the advances regard- are revcovered [49], what poses potential hazards. More on the compar-
ing hydrazine, to HTP’s limited use during the last 50 years. Indeed, ison of HTP and other modern monopropellants can be found in Refs.
larger amounts of impurities in contact with HTP, such as grease or [11,50].
dirt, or contact with chemicaly non-compatible materials can lead to HTP can be used as an oxidizer with liquid rocket fuels: either in
its spontaneous decomposition [39] and several accidents have histor- bipropellant engine configurations with catalytic HTP decomposition,
ically taken place with various grades of hydrogen peroxide in several what ensures quasi-hypergolic fuel ignition [51,52] or with fuels be-
industries [40]. Ref. [33] gives a summary of early HTP incidents in ing hypergolic with HTP (either promoted by catalytic fuel additives or
Nazi Germany but provides positive feedback concerning HTP use for being directly reactive with HTP) [12] or simply with a conventional
rocket propulsion. Ref. [41] provides a more modern analysis of safety igniter, what has been also demonstrated feasible, despite its limited
of HTP utilization for rocket propulsion and examples of risks and their application. HTP-based bipropellant thrusters are considered for reac-
mitigation regarding use of rocket grade hydrogen peroxide are listed tion control and the technology can be used in Liquid Apogee Engines,
in Ref. [42]. Historically, the American MIL-P-16005 specification was since performance of several green HTP-base bipropellant combinations
used [39,43]. Oxidizer concentration, its purity, stabilizers used strongly nearly matches modern MON/MMH storable propellant engines, while
influence the necessary handling approach and associated risks. How- allowing for higher density performance [53]. Moreover, HTP-based en-
ever, most state-of-the-art propulsion test stands’ procedures require di- gines are also considered for launch vehicle applications [54] and the
luting any HTP spills with water and water sprinklers are key infras- historical British Black Arrow launch vehicle proved that this approach
tructural elements. Decreasing the concentration allows for further safe is feasible and can allow development of robust vehicles with relatively
operations. Of course incidents, as in case of other rocket oxidizers, al- small envelopes.
ways remain a threat, thus carefulness and educated actions must always Another way of utilizing hydrogen peroxide is within hybrid rocket
remain a priority, despite recent improved assessments regarding HTP motors, where HTP is used with solid fuel. A review of HTP-based hy-
safety. brid rocket motors can be found in Ref. [35]. Ignition using catalyst beds
Even early grades of HTP allowed its storabilty during ground stor- [49] or ignition with hypergolic solid fuel is possible [55]. Different HTP
age and early orbital missions (in Syncom II, Syncom III and Early Bird grades can be considered [56]. In 2017 the ILR-33 AMBER suborbital
spacecraft), what is discussed in Ref. [44]. However, apart from suc- rocket developed by the Lukasiewicz Research Network – Institute of
cessful early applications [45], until recently hydrogen peroxide utiliza- Aviation from Poland demonstrated in-flight use of HTP of concentra-
tion in rocket propulsion for space and defence was limited due to ex- tion exceeding 98% in its hybrid main stage [57]. Advantages of using
pected storability and safety issues. With the availability of new grades HTP as oxidizer in small suborbital rockets are discussed in Ref. [58].
of HTP with higher purity and concentrations, enhanced performance, Developments of larger hybrid vehicles using HTP as oxidizer include
safety and storability are possible. Several examples of modern stora- Nammo’s Nucleus suborbital rocket [59] and the Eris small lauch vehi-
bility assessments are described in Refs. [35,44]. Enhanced storability cle of Gilmour Aerospace [60]. More on space transportation vehicles
is key in terms of use in military systems or for orbital applications. and their HTP-based hybrid propulsion systems can be found in Ref.
While historical HTP in-flight applications were limited to HTP concen- [14].
trations up to 90%, in 2017 use of concentration exceeding 98% has HTP can also be utilized in gelled form – either as gelled oxidizer
been demonstrated during the ILR-AMBER suborbital flight, which has (which can be injected or pressed into a combustion chamber and used
been followed by consecutive missions [35]. with liquid, gelled or solid fuel [61,62]) or as part of a slurry contain-
HTP can be utilized as a green high density monopropellant. Provid- ing both HTP oxidizer and fuel. A review of gels for rocket and ramjet
ing up to 180 seconds of specific impulse in vacuum conditions in case propulsion is presented in Ref. [16].
of 98% HTP it has performance below hydrazine. However, it delivers While hydrogen peroxide is a liquid in normal conditions, it may
higher density specific impulse than hydrazine systems and is an effi- be also used in solid rocket motor grains. Such use of hydrogen
cient low-cost solution, especially of interest for relatively small space- peroxide of HTP class is proposed and discussed in the following
craft platforms, where mechanical configuration and envelope limits, as paragraphs.

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Table 2
Characteristics of the most popular inorganic oxidizers based on data from Refs. [65,66,64]

Density/ g ∙ Available Heat of formation

Oxidizer Molecular formula cm−3 [65] oxygen / % [65] / kJ ∙ mol−1 Melting point or transition temperature/°C

Ammonium nitrate (AN) NH4 NO3 1.73 19.5 -65.2 169 (phase transitions)
Ammonium perchlorate (AP) NH4 ClO4 1.95 34.0 -290.3 > 200 (solid-solid transition, dec)
Potassium perchlorate (KP) KClO4 2.52 46.2 -433.4 > 400 (dec)

4. Existing solid rocket propellant formualtions – properties, that of the required iodine [74], therefore it significantly inhibits its up-
advantages and disadvantages of different oxidizers take. It gets into the human body by eating products and drinking water
containing perchlorate anion. AP is easily soluble in water, and the per-
Heterogeneous solid rocket propellants also known as composite pro- chlorate ion is stable, it remains for a long time in soil and in surface-
pellants, consist of solid, crystalline particles of an inorganic or less com- and groundwater [74]. Research on samples confirms that after more
monly an organic oxidant, dispersed with powdered fuel and additives than 600 days their concentration drops by only 5% [76].
in a polymer matrix. As other solid propellants, they have found a wide Due to the problematic nature of these oxidants, alternative solutions
range in both military and civilian applications. Their most common use are still being sought. One of the most popular substances is ammonium
is in rocket motors of missiles, military air-targets, sounding rockets and dinitramide (ADN). ADN is considered as one of the most promising ox-
launch vehicles [2]. Currently developed applications also include deor- idizing components of modern and future solid propellant formulations,
bitation rocket motors for satellites [63]. Modern space transportation because it is eco-friendly and more energetic and has no plume signature
and in-space propulsion applications are actually nearly limited to het- (especially important for military applications) because there is no chlo-
erogeneous solid propellants, unlike in the case of military utilization. rine in its molecular structure. In comparison with perchlorates it has
The oxidizer is the main ingredient of the composite propellant and significantly higher heat of formation (Table 3), which results in better
constitutes over 60% of the mass of the total composition. The oxidizer performance. Its biggest disadvantage is high hygroscopicity. There are
possesses high oxidation potential and a highly electronegative atom or assumptions that the special hydrogen bonds among ADN and stronger
group. The periodic classification of elements can be used to distinguish hydrogen bonds between ADN and water molecules could possibly be
the oxidizer (high electronegativity) and the fuel (high electropositiv- the main reason of the severe hygroscopicity of the compound [77].
ity). The oxidation potential of the oxidizing group varies in the follow- Other drawbacks are fairly high sensitivity crystals, costly synthesis, and
ing order: F− > OF− > NF2 − > ClF4 − > O− > NO3 − > ClO4 − > NO2 − > sensitivity towards light [78]. There are many routes of ADN synthesis
ClO3 − [64]. This shows that perchlorates and nitrates are better oxidiz- [79] however the most promising route to scaling-up is carried out at -
ers than nitrites and chlorates. Table 2 present three historically popular 40°C using fuming HNO3 (> 98%) and concentrated H2 SO4 (98%) which
solid rocket motor oxidizers. is problematic from an economic and environmental point of view.
Comparing the properties of the presented oxidants, it is not difficult An alternative oxidizer is hydrazinium nitroformate (HNF). Like
to see why AP is the most popular one. AN, despite its high availability, is ADN it allows to obtain halogen-free propellant formulations. The main
thermally sensitive and undergoes several (five stable) phase transitions compound to obtain HNF is nitroform (NF). There are various ways to
in the temperature range of -200°C to 125°C and at a certain temperature obtain NF via the nitration of acetylene gas/acetic anhydride/acetone
value it undergoes significant volume change [67], which greatly limits [83,84] but these methods were found hazardous due to highly exother-
the possibility of its use without additives affecting phase changes. In mic nature of reaction. The synthesis of NF by the nitration of iso-
comparison KP has much lower heat of formation than AN or AP and propanol has been found to be safe but it has an unsatisfactory low
shows hygroscopic properties (as does also AN), which are undesirable yield of 25% [85], what affects the profitability of the entire process of
in the case of propellant components. In some research KP is proposed HNF synthesis. Another drawback of HNF is that it has a high sensitiv-
as a burning rate modifier that allows increase burn rate without com- ity to friction due to sharp needle-shaped crystals [86]. Preparation of
promising the performance [68]. AP is considered as the best oxidizer HNF-based propellants requires desensitization of HNF during crystal-
of the presented three due to its good performance but it also has many lization process to modify its morphological characteristics. HNF has a
shortcomings, including instability, high negative enthalpy of formation relatively high density and significantly better heat of formation than
(-290.3 kJ/mol [64]), and claimed health and environmental issues re- perchlorates (Table 3) but due to safety issues it is not considered as a
sulting from its production and combustion products [66,69,70]. AP is possible replacement for AP in the nearest future.
moreover considered a new micro-pollutant of the environment. The in- Due to the constant search for better oxidizers (with higher per-
crease in the areas of its occurrence in the natural environment is mainly formance and being more eco-friendly) also Secondary Explosives (Cy-
due to human activity. The production and wide use of solid propellants clotrimethylenetrinitramine - RDX, cyclotetramethylene tetranitramine
and pyrotechnic articles are to blame for this state of affairs [71]. The - HMX) found application in solid rocket propellants as combustion mod-
military industry determines the scale of the production of AP, which ifiers [4]. Another of the promising representatives is hexaazaisowurtz-
is estimated to account for 90% of the production of all perchlorates itane (HNIW). RDX, HMX and HNIW are often referred to as oxidizers
[72,73]. but it is notable that they in fact have negative amounts of free oxy-
The perchlorate ion is not significantly metabolized by humans and gen, thus not allowing for full oxidation of any propellant species if
it is responsible for thyroid disorders. Because of its similarity to iodide being the only oxidizer in a SRM grain. HNIW is a relatively new mate-
in ionic size and charge, it competes with iodide for uptake into the thy- rial obtained in the late 1980s [87], identified as a potential candidate
roid gland. At therapeutic dosage levels (100–1000 mg/day) [66], this to replace HMX [88]. HNIW has a cage structure and it exists in five
competitive inhibition results in reduced production of the thyroid hor- polymorphic forms: 𝛼, 𝛽, 𝛾, 𝛿 and 𝜀 with the highest crystal density. In
mones T3 and T4 and a consequent increase in TSH (thyroid stimulation comparison with RDX and HMX (Table 4), or other presented oxidizers
hormone) via a negative feedback loop involving the thyroid, pituitary (Tables 2 and 3), HNIW has significantly better heat of formation and
and hypothalamus [74,75]. It is of particular importance for the neu- the highest density (in its 𝜀 form). It has also a slightly negative oxygen
rological development of the fetus (its absence results in impaired de- balance which is desirable for explosive materials because it prevents
velopment and reduced intelligence quotient). The perchlorate ion has the formation of nitrogen oxides and excessive amounts of soot during
a high affinity for NIS (sodium-iodide symporter), several dozen times combustion. Its biggest drawbacks are sensitivity to impact and friction.

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Table 3
Comparison of selected properties of ADN and HNF based on data from Refs. [80–82]

Oxidizer Molecular formula Density/ g ∙ cm−3 Oxygen balance / % Heat of formation / kJ ∙ mol−1 Melting point /°C

Ammonium dinitramide (ADN) NH4 N(NO2 )2 1.82 26 -148 93.5

Hydrazinium nitroformate (HNF) N2 H5 C(NO2 )3 1.86-1.93 13 -71 – -72 110-124

Table 4
Comparison of selected properties of Secondary Explosives used in novel rocket propellants based on data from Refs. [86,89]

Density/ g ∙c Oxygen balance Heat of formation Sensitivity to

Name Molecular formula m −3 /% / kJ ∙ mol−1 impact / h50%, cm Friction/ kg

Hexaazaisowurtzitane (HNIW) C6 N12 H6 O12 2.04 -11.0 +454 24 8

Cyclotrimethylenetrinitramine (RDX) C3 H 6 N 6 O 6 1.81 -21.6 +63 46 16
Cyclotetramethylene tetranitramine (HMX) C4 H 8 N 8 O 8 1.91 -21.6 +76 38 14

Fig. 1. Typical liquid and solid rocket oxidizers and their available oxygen and
characteristic processing temperatures, based on compounds’ properties taken
from Refs. [21,91,93–96]

The cost of CL-20 synthesis is an additional problem. Many synthetic

methods have been described in the literature but they involve several
steps using very expensive catalysts [65].
Despite the real need to replace AP in newly developed rocket propel-
lant compositions, it is necessary to look at the issue more broadly. To- Fig. 2. Heats of formation as function of molecular weight for various typical
day, attempts to increase the performance of solid propellants by “just” a oxidizer products, taken from Ref. [7]
few percent, while reducing their toxicity, are made at enormous costs.
These studies involve the development of expensive energetic compo-
nents as ADN, HNF or Cl-20 mainly with inferior safety parameters (sen- AP limits the maximum effective amount of aluminum (or other high
sitivity to friction, impact, lower decomposition temperature) in com- performance fuel additive). HTP offers an advantage regarding this is-
parison to AP. More on the search of green rocket oxidizers for solid sue and allows for performance increase due to its high capability to
propellants may be found in Ref. [90]. Despite its specific properties, provide oxygen to burn high performance fuel compounds. In-line with
hydrogen peroxide can be an interesting alternative to today’s state-of- the oxidizing group oxidizing potential gradation, described in para-
the-art oxidizers, as presented in this article. graph 4 and in detail in Ref. [64], the oxidizing capabilites of O− are
better than that of perchlorates and nitrates (and are only preceded by
5. HTP-based solid propellants – why could they be of interest? several fluorine-rich compounds, which have proven not to be robust
solutions for low-cost propulsion). Fig. 2 presents a wide set of heats of
While the paragraph on properties of high grades of hydrogen perox- formation for major oxidizer species that can be found in rocket propul-
ide provides basic information on the compound, its use in solid rocket sion systems as a function of their molecular weight [7]. While ozone,
propellants is not intuitive. Moreover, a review of heats of formations, fluorine, fluorine oxides and chlorium oxides are visible as promising,
expressed in units of energy per mass of compound, of state-of-the-art they are not robust and easily handled propellants. Several more com-
solid and liquid rocket oxidizers shows that hydrogen peroxide has the mon oxidizing agents present in chlorates, perchlorates and nitrates are
lowest one among typical liquid oxidizers and lower than ADN, AP and connected by lines. Fig. 2 shows that the ratio of heat of formation to
even AN. It has also low density when compared to AP. On the other oxidizer group molar weight is not advantageous for hydrogen perox-
hand, its very high oxygen content allows for favourable propellant ide. However, unlike HTP, the non-oxidizing molecules included in AP’s
composition optimization. The amount of available oxygen in typical formula, apart from hydrogen, have low heats of combustion. HTP’s low
oxidizers is presented in Fig. 1. This value is critical in fine-tuning pro- toxicity, “green” properties and heritage in various industries makes it
pellant compositions. For AP/HTPB propellants aluminum content is up a candidate for ultimately low-cost solutions, as already acknowledged
to circa 20% mass-wise, since further metal powder addition does not by part of the liquid propulsion community. As shall be discussed in
enhance performance despite the very high heat of formation of the alu- paragraphs 6.1-6.3 samples of HTP-based solid propellants have been
minum oxide combustion product. This is since the available oxygen in successfully manufactured in laboratory conditions and test-fired. This

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However, the results obtained may be illustrious regarding the potential

of HTP-based grains. It is noticable that for some of the proposed solid
propellants use of hydrogen peroxide as oxidizer in the grain leads to
higher performance than using oxygen embedded in the grain. This is
interpreted as being due to the fact that the H2 O from HTP decompo-
sition recombines with the metal from the fuel, instead of exiting the
nozzle as water steam. Thus, metal oxides occur in the nozzle outflow
and part of the hydrogen remains unoxidized and being a light gas it
enhances performance.

6. Three approaches to development of solid propellants using

HTP as oxidizer

6.1. Cryogenic solid rocket propellants

The first notion of the potential of using hydrogen peroxide in solid

propellants is via utilizing it in solid state by decreasing its tempera-
ture. This has been discussed as early as in 1965 in Ref. [103] and such
propellants were named cold solid propellants. The concept of the man-
Fig. 3. Results of thermochemical calculations of vacuum performance of solid
propellants using HTP and comparison with reference storable propellants, ob- ufacturing process assumed mixing hydrogen peroxide with metal pow-
tained by the authors using NASA CEA [97] der or metal hydrate fuel and freezing the mixture, thus obtaining a
solid propellant grain. Both hydrogen peroxide, as well as oxygen and
nitrous tetroxide were considered for use as solid oxidizers and even
concerns also propellants which are to be ultimately storable in ambi- liquid fuels were considered for freezing (including RP-1). Later work
ent conditions. For manufacturing and handling safety, the maximum on so-called cryogenic (CSP) or refrigerated solid propellants was de-
allowable oxidizer temperature is an important parameter. In case of scribed by Lo in 1967 Ref. [104] and further laboratory work followed,
solid oxidizers temperature of decomposition or melting is often cited including use of HTP [105–107]. Work on CSP using hydrogen peroxide
[91]. In case of liquid propellants an important parameter is their boil- usually considered 87.5% HTP [108]. Ref. [106] mentions that the pro-
ing temperature and this value has been included for liquid oxidizers in pellant was sub-cooled by 5-10 K below the melting point of 87.5% HTP
Fig. 1. However, in case of HTP of concentrations above 74%, explosive to allow easier operations. Its storage was to take place at 260 K. Ref.
vapours can be generated at temperatures lower than the boiling point [107] mentions the HydroxalaneTM propellant using hydrogen peroxide,
[92]. Moreover, for 98% HTP rapid vapour decomposition occurs above a polymer and metal fuel or metal hydrates as additives. It was expected
395 K and decomposition begins at approximately 348 K [92]. There- to be storable in the range between 253 and 273 K. The expected spe-
fore, an additional point representing this fact concerning HTP has been cific impulse was in the range of 355-375 s, while 315 s were quoted for
added to the plot in Fig. 1. Deeper investigation is required to specify the same conditions for the baseline aluminized AP/HTPB composition.
safe procedures. Naturally, all controlled laboratory work on sample The HydroxalaneTM propellants had densities in the range of 1377-1462
preparation does not exceed temperatures above the ones encountered kg/m3 , thus below 1800 kg/m3 of the state-of-the-art composite solid
during mixing, casting and propellant conditioning processes. propellant taken as the reference point. However, hot firings included
Theoretical performance of solid rocket motors using grains contain- mainly refrigirated grains using frozen water, unlike HTP as oxidizer
ing a high mass fraction of HTP is presented. This includes performance (mostly water was used and a low concentrated 30% hydrogen peroxide
considering several fuels and additives and different oxidizer loadings. was selected for partial testing) and issues wth amounts of residue oc-
Fig. 3. provides performance calculation results with MON/MHH and curred (13% of the grain mass remained in the SRM after its firing in case
AP/HTPB propellants given for reference. Calculations have been car- of of 30% aluminium loading of the grain). CSP grain mechanical prop-
ried out using NASA CEA software [97]. 92% of equilibrium perfor- erties and interfacial bonding are among key technology disadvantages.
mance is plotted as recommended in Ref. [37]. All SRM compositions The low temperature of solidification of 30% hydrogen peroxide reduces
assume a chamber pressure of 70 bar, while 10 bar is assumed for its applicability in CSP [107]. Adequate mechanical properties of grains
MON/MMH due to the typical parameters of feeding systems used for using this grade of oxidizer is obtained via their conditioning at 238-
LAE. Nozzle area ratios of 100 were set. PE was used as a potential 243 K. Therefore the propellant, which undergoes heat treatment dur-
binder, although other binders may be better in terms of manufactura- ing the manufactuing process is susceptible to structural defects occur-
bility, since it is the only fuel tested in a rocket propulsion vehicle using ring during solidification. During this process a porous structure is cre-
98% HTP during an in-flight mission (within a hybrid rocket motor). ated and tension discontinuities occur due to the differences in thermal
HTPB binder system properties were taken Ref. [8]. In case of advanced expansion of particular components. The developers of HydroxalaneTM
solid propellants, higher performance energeric binders including GAP verified the effect of thermal expansion for a neutral propellant grain
[98] or BAMO [99] can also be considered for HTP-based propulsion, by substituting aluminum powder by silicon oxide. Although no grain
but they were not included in this paper. Fuel additives classically used deformations, thermal insulation defects nor issues with insulation ad-
in solid propellants as aluminum powder [100] or aluminim hydrate hesion were noted at low temperatures, significant structural changes
[101] were taken into account. Notably, aluminium demonstrates good occurred due to component interactions. CSP are therefore problem-
chemical compatinility with HTP. Use of various metal nanopowders atic in terms of limited readiness for operations at normal conditions
may be an other perspective solution [102] and boosting performance and long-duration launch preparations and processes are an issue due
by including metal hydrates, as shown in the very first concept of solid to propellant melting. An innovative concept regarding CSP is utilization
HTP propellants [103], is a promising trend in rocket propulsion [101]. of modular dissected grains, where stacks of seperate fuel and oxidizer
For comparison, Ref. [103] presents theoretical calcualtions for pure grains are used [109,110]. This way numerous oxidizers and fuels can
HTP. It assumed a frozen oxidizer, which would be simultaneously the be combined without issues due to chemical compatibility. PE and HTPB
binder in which the fuel would be embedded. Therefore no addtional are materials which can be used both as efficient fuel modules, as well as
absorbent or binder is concerned. This may be an issue in terms of me- baffles between oxidizer and more energetic fuel grains. Grain manufac-
chanical properties of the grain, despite appealing performance figures. turing via freezing in liquid nitrogen is possible [111]. Since the overall

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grain configuration is different than in case of classic SRM, state-of-the- validate it. However, it should be clearly noted that gel-like and sta-
art methods of burn rate and combustion process characterization are ble, solid-like new formulations made of concentrated hydrogen perox-
not adequate to reflect the complexity of the modular dissected grain ide have already been reported in literature [16]. Therefore HTP-based
approach. More information on CSP combustion can be found in Refs. grains may be either casted and transported after the full manufacturing
[105,106,109,110,112]. process is completed or the HTP can be loaded into the solid fuel matrix
just prior to SRM use. The first scenario is more appealing if safe grain
6.2. Solid propellants cured at room temperature transportation is possible, however their ground storability and shelf life
are unknown at this point in time. In the second case separate HTP and
Further notable advancements concerning use of HTP in solid propel- separate fuel matrix storage is possible with no need to transport poten-
lant considered the concept allowing using HTP in standard conditions, tially hazardous solid grains. However, this leads to significant decrease
thus without the need of propellant cooling. The major milestone was of operations’ flexibility as in the case of liquid propellant vehicles. Such
achieved in China and first work on this subject was reported in 2013 an approach is expected to limit the solutions applicability regarding
[113,108]. The solid propellant containing H2 O2 cured at room temper- quick-response systems.
ature was given an acronym of SPHP. The technology uses sodium poly-
acrylate as an efficient absorbent of HTP. The 98% HTP grade utilized
6.3. Solid propellant using HTP encapsulation
stabilizers to ensure the propellant stability at room temperature. This
allowed obtaining particles containing hydrogen peroxide. In the second
In principle direct contact of oxidizer and combustible matrial leads
step these particles, along aluminum powder, polypropylene powder,
to the oxidizer’s (and often fuel’s) limited chemical stability and acceler-
curing agent and other additives, were added into a specially obtained
ated degradation – this occurs in a more significant manner than in case
hydrocarbon polymer binder LZY [108]. The obtained slurry was casted
of oxidizer and fuel separation and storage in contained tanks. There-
as classic composite propellants. It was reported that the novel propel-
fore the natural challenge is how to combine a very reactive liquid ox-
lant was insensitive to friction, and that the impact and electrostatic
idizer with fuel in order to form a safe and storable propellant despite
sensitivity were similar to the conventional metalizated AP/HTPB pro-
their direct contact. Several patents have been obtained in the relevant
pellants [108]. However, the scattered particles of HTP could be easily
field. The 1959 invention described in Ref. [114] is the first notion of
deformed and had relatively low tensie strength. The project led to burn
the possibility of using liquid propellants in solid rocket motor grains.
rate characterization and laboratory SRM test firings with burn times
Liquid compounds were to be enclosed in spherical capsules, compat-
below 1 s. The motors contained up to 0.3 kg of the new propellant.
ible with the liquids, as well as the propellant matrix. The invention
This approach has been also of preliminary investigation in Poland
considered that both liquid oxidizers of fuels can be encapsulated. The
at Institute of Aviation. Preliminary calculations of HTP-based SRMs
idea assumed the possibility to include addtional, more efficient, com-
were carried out in 2016 by Okninski and Nowakowski and initial lab-
pounds in the baseline solid propellant. In 2008 Gany [115] proposed
oratory research using the absorbent technology (also based on sodium
a novel solution, where potential for full elimination of solid oxidizers
polyacrylate) was conducted by Rarata using 98% HTP. It allowed for
is mentioned and an increase of specific impulse in the range of 5-15%
manufacturing samples up to 20 g of mass. The prepared samples were
is possile. Liquid or gelled oxidizer is to be ecapsulated in a chemically
aluminized with aluminium content up to 20%, as in the case of classic
compatible material with aluminium, PTFE and PE being mentioned as
SRMs, but no showstoppers for increasing this value above 20% have
potential material candidates. This solution mentions 90% HTP as a po-
been identified. After acquiring several HTP-related R&D projects in
tential oxidizer candidate for use in oxidizer capsules. The aluminum
other fields, this work has been paused until 2020, when it was reini-
capsules could serve as an efficient fuel and a propellant mass compo-
tiated by Kopacz with work pushed into the direction described in the
sion of 15% HTPB, 55% HTP (90%) and 30% aluminium is presented. It
following paragraph – HTP encapsulation.
is to provide a specific impulse 6% higher than that of a highly alu-
In the described approach, concentrated hydrogen peroxide is ab-
minium loaded AP/HTPB propellant. Another patent considers using
sorbed (embedded) within the whole solid matrix polymer material
porous structures, similar to foams, which could be saturated with HTP
(characterised by strong absorptive properties toward liquids) at am-
[116]. Such foams could be made from i.e. isobutylene-isoprene rubber
bient temperature. This concept should allow reaching relatively high
and the final grain could contain up to 75% of oxidizer mass-wise. The
energy efficiency provided that the highest concentration of hydrogen
foams could be also, during their manufacturing process, enriched with
peroxide (e.g. 98% HTP) is being used together with strong absorptive
metallic fuel to increase performance and their mechanical properties
media (some of which are characterised by relatively high liquid load-
could be improved by aluminum fibers. Several other solutions across
ing efficiency – greater than 90% of the total mass may be the mass of
patents granted worldwide include other forms of potential HTP encap-
absorbed liquid). Some of the absorptive solid materials (fuel phases)
sulation, even if HTP is not mentioned explicite in the invention. This
considered are rather well resistant mechanically, easily processed and
includes also larger-scale encapsulation approaches in forms of small
already being in use as various kind of advanced absorbers (e.g. super-
tubes or other thin layers of combustible materials between which rela-
absorbent polymers, SAPs). These are materials that have the ability to
tively small volumes of oxidizers could be trapped. Oxidation resistant,
absorb and retain relatively large volumes of water (or aqueous solu-
preferably non-organic compatible solid construction materials would
tions). Similar approaches already proved that even liquid nitrogen can
be needed for safe designs. However, no verification of the feasibility of
be firmly trapped in a solid matrix material and rendered safe for long
operations of such rocket motors could be found in open literature.
distant transportation. If highly concentrated hydrogen peroxide could
be trapped inside the volume of a solid polymer fuel matrix, then the
material would be e.g. additionally bounded and formed in a grain by 7. Expected further development challenges
the addition of a binder-like component. The candidate solid fuel ma-
trix should be made from fully compatible towards hydrogen peroxide Naturally, as in the case of relatively unexplored concepts, there still
polymers (that show no any signs of adverse reaction with HTP dur- remains a lot of unknowns and potential technology development chal-
ing various compatibility tests), which are hydrophilic and have a high lenges. HTP’s reactivity causes its limited compatibility with organic
affinity for water (e.g. some cross-linked synthetic polymers). Materi- materials and leads to threat of decomposition during storage while em-
als that are likely to form high explosive mixtures with HTP should be bedded within a solid propellant grain. HTP diffusion and exudation
avoided – but it should be noted that also LOX and NTO may create high from the grain are issues which must be studied. This may be phenom-
explosives with some organic solids or powders. Therefore, the concept ena much more significant than migration and evaporation of liquid
requires a significant amount of literature and experimental work to nitroglicerine in double base propellants. With potential very high HTP

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W. Kopacz, A. Okninski, A. Kasztankiewicz et al. FirePhysChem 2 (2022) 56–66

content in SRM grains, liquid displacements may accelerate fuel ma- no solid or condensable combustion products could be achieved. This
trix aging and internal stresses may occure leading to gas release and would be a significantly higher performance propellant than in case of
structural discontinuities. Thus would affect grain mechanical proper- AN-based solutions typical for gas generators. As for in-space applica-
ties, stability and combustion. Ways of improving the compatibility be- tions, application in exploration missions, thus: kick stages, retrorockets
tween HTP and the fuel components within the grain matrix must be for entering lunar or planetary orbits are possible uses of new SRMs if
a priority. Oxygen precipitation and HTP’s concentration decrease and their storabiltiy is not an issue. Such missions require high performance.
corresponding effects must be analysed in detail. For the purpose of a Similary, propulsive de-orbit and especially controlled-deorbit is a area
preliminary assessment literature data from compatiblity investigations of increasing potential for high performance solid rocket motors [3].
of HTP with construction materials can be used. Such data from tests
concerning compatibility of various alloys, and polymers for use within
fluidic components of HTP liquid propulsion systems is often in-house 9. Conclusions
know-how of entities working with HTP propulsion technology. Fur-
therly, without an initial assessment of storability, aging as well as safety In summary, a relatively new application of hydrogen peroxide that
and handling properties (impact, friction, electrostatic discharge) larger- has potentially perspective capabilities has been discussed. The unique-
scale tests should not be performed. Transportation of HTP-based grains ness of the solution is to use HTP as oxidizer in solid rocket propellant
is another issue to consider. The ultimate propellant manufaturing tech- grains. One of the potential benefits is performance beyond both: exist-
nology must enable the possibility to produce complex grain geometries ing solid rocket propellants, as well as commonly utilized storable liquid
in-line with internal and external ballistic requirements of today’s mis- propellants. The following key conclusions can be made:
siles and space systems. Grain deformation in various temperatures (and
integrity, especially facing large pressure gradients within the combus- 1 The low density of HTP (high in comparison to liquid oxidizers, but
tion chamber, acceleration and other flight loads) should be examined low in comparison to state-of-the-art solid rocket oxidizers) is not
to understand what can be expected during prototype SRM ignition and such a disadvantage as it could be considered, since in solid propel-
firing. Ignition dynamics and propellant response to different heat fluxes lant formulations using metal and metal hydrate additives, the op-
must be studied. Similarly, combustion efficiency and stability should be timal oxidizer-to-fuel ratio drops significantly in comparison to the
investigated. Extensive eperimental work will have to involve character- one commonly expected in bipropellant and hybrid rocket motors us-
isation of the burn rate of HTP-based solid propellants used in ambient ing typical hydrocarbon or polymer fuels. Thus the high content of
conditions. Different mechnisms than in classic solid heterogenous pro- metal increases the average propellant density. Current solid propel-
pellants or HTP-based refrigerated propellants may be expected. Ease lant rocket technology suffers from technical limitations concerning
of tailoring ballistic performance of the new propellant via additives solid particle loading due to binder system and manufacturing con-
is necessary. In case of HTP encapsulation, the possibility of obtaining straints and grain mechanical property requirements. The proposed
different capsule sizes is essential in case of the need to have high oxi- technology allows for adding high amounts of energetic additives -
dizer loadings (vide bimodal and trimodal packing of oxidizer particles such high oxidizer loading in order to maximize performance, as in
in classic composite propellants – although in this case it is not required case of AP, will not be needed. The preliminary theoretical perfor-
for grain density enhancement). mance assessment shows that specific impulse of over 350 seconds is
possible, what makes it competitive to classic storable liquid rocket
8. Novel solid propellant application propellants and narrows the performance gap between solid propel-
lants and liquid rocket propellants using LOX with hydrocarbons. In
Potential industrial applications of the technology include SRM of some cases, performance of HTP-based solid systems shall be beyond
rocket stages (either for missiles or suborbital and orbital vehicles for systems using LOX. The proposed propellant family has no HCl in its
space applications), where high performance is required and no strict combustion products and offers a green solution for next-generation
volumetric constraints are present. thus envelope requirements are not systems.
the system-level driver [107]. This leads to larger motor cases and po- 2 The significance of this paper is due to the fact that most previous
tentially increase of dry mass fractions, however SRMs are known for works considering solid propellants using oxidizers, which are liq-
their high propellant mass fractions even for small vehicles. Despite low uid in normal conditions, assumed that such oxidizers would require
density, potentially unprecedented in the last decades gain of perfor- keeping the grain in low temperatures. Thus, SRM constant condi-
mance could be achieved with HTP-based solid propellants using high tioning would be needed, making the concept less attractive for op-
concents of metal powders, metal hydrates and potentially other ener- erations, especially regarding defence applications. Moreover, CSP
getic additives as i.e. silanes (although compatibility issues would be exhibit mechanical property issues. Laboratory work on HTP-based
decisive in the last case). State-of-the-art solid rocket propellant tech- propellant grains, which are storable in ambient conditions has been
nology is based on composite formulations typically using AP as oxi- initiated approximately 10 years ago in China and is presently also
dizer, aluminum powder as fuel and thus solid particles may comprise on-going in Poland. Despite low TRLs of such solutions (either con-
up to approximately 90% of the uninhibited grain mass. The attainable cerning use of absorbants or encapsulation), preliminary results are
specific impulse is at the level of 305 s in vacuum in case of advanced promising. Moreover, some new technologies, as additive manufac-
aluminized AP/HTPB propellants. However, most motors do not exceed turing, may allow manufacturing of advanced porous foams and
290 s with no hydrates added, what is below the performance of mod- other structures (as can be seen in the case of i.e. filters and cat-
ern storable bipropellant rocket engines. Thus the discussed potential alysts) which can also embed HTP.
performance increase could be decisive in terms of wider application 3 High grades of HTP in terms of both: concentration and purity are
of SRM, in particular using HTP as oxidizer. Other typical solid pro- preferred to maximise performance and storability. Extensive work
pellant applications including stage-seperation, ullage, spin-control, de- on the detailed propellant composition is needed to assess compati-
scent, deceleration and launch abort system rocket motors are consid- bility issues and thermal stability. Unlike in case of liquid HTP uti-
ered not attractive for the new technology since high performance is not lization, issues due to spillage and need of oxidizer tank venting are
a critical requirement for them and in the first stages of the new techol- not of concern during vehicle launch and propulsion system oper-
ogy potential application, it may not be yet enough cost-effecticve. As ations. Moreover, while liquid HTP requires using catalyst beds in
for gas generators, they usually do not have strict propellant perfor- most applications and therefore the amount and types of stabilizers
mance maximization requirements. However, non-metalized HTP-based are contrained (due to the threat of catalyst poisoning), the proposed
solid propellants could be applied in gas generators with turbines, since concept does not have this drawback. The freedom in using stabiliz-

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W. Kopacz, A. Okninski, A. Kasztankiewicz et al. FirePhysChem 2 (2022) 56–66

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