A REVIEW ON CLEANER AND SAFER PROPELLANT

MATERIALS FOR SPACE VEHICLES AND THEIR

CHARACTERISATION

1
Ashutosh Dev*, 1Yogesh Dumbre, 1Alice Rana ,2Shreela Sapkota, 1Prasiddha Raut
1
Department of Mechanical Engineering, Kathmandu University, Dhulikhel, Nepal
2
Department of Computer Science and Engineering, Kathmandu University,Dhulikhel, Nepal

*Corresponding address: ad07101319@student.ku.edu.np

ABSTRACT
Chemical fuels are used as rocket propellant in the majority of today's rockets. A material used by a rocket as, or to
develop in a synthetic reaction, the response mass (propulsive mass) that is fired out of a rocket engine to offer push,
and therefore give shuttle thrust, is known as rocket propellant. Satellites and space stations that stay in orbit for an
extended period of time use hypergolic, highly energetic fuels that ignite instantly when exposed to an oxidizer. The
current generation of hypergolic fuels is based on hydrazine, a highly poisonous and extremely unstable chemical
molecule made up of nitrogen and hydrogen atoms. This paper focuses on fuels of different types of rocket
propulsion systems and frameworks catering to the need of cleaner and safer propellant materials. Developments
and breakthroughs in fields of (Metal Organic Frameworks) MOFs, Hybrid Rocket Technology, Hydrogen
Propellants, Ammonia Borane are reviewed and characterized in this paper.

INTRODUCTION

The characteristics of a rocket are heavily reliant on the proper selection of propellant, as it accounts for the majority
of its weight, power, and performance parameters. The heat to be converted to work in liquid rocket propellants is
frequently obtained as a byproduct of the chemical reaction of combustion, i.e., a turbulent reaction resulting from
the oxidation of one substance by another. The oxidizing substance is referred to as an oxidizer, while the oxidized
substance is referred to as fuel. When burned with oxygen, methane (CH4) is a soft cryogenic hydrocarbon
propellant with a lower density and generally better performance [1]. As a result, Methane offers a unique potential
to combine the benefits of Hydrogen and Kerosene in a single fuel. A typical propellant for rockets is kerosene,
which is a blend of various hydrocarbons. Since the dawn of liquid propulsion, it has been widely utilized in the
United States and Russia [3]. Because of its lower inherent danger of handling and higher energy density,
hydroxylammonium nitrate (HAN) monopropellant is being studied as a substitute for hydration. The most well-
known fuel in modern hybrid rockets is HTPB (hydroxyl terminated polybutadiene). It has a firm rubber consistency
and may be customized with strength, burn rate, and burn temperature modifiers. For a long time, HTPB has been a
popular binder and fuel for solid rockets [1]. Hybrid rocket motors based on paraffin wax have the potential to
replace present solid rocket motors as booster components of launch vehicles. Wax-based hybrid rockets have a
number of benefits over solid rocket motors currently in use. The fuel hydrazine is a monopropellant, whose
molecule includes just one type of flammable atom, Hydrogen, while nitrogen during combustion contains only one
type of combustible atom, Nitrogen Intensifies gas production and evolves in a free form in combustion products.
Because the flammable portion of the Hydrazine is composed entirely of Hydrazine and has a high calorific value.

Hybrid rocket fuels

Hybrid rocket fuel is a type of fuel which contains solid fuel and liquid oxidizer. Comparatively it is safer, cleaner

and cheaper to conventional solid and liquid rocket fuel.

Advantage of hybrid rocket fuel over solid rocket fuel[1]

1. A hybrid rocket motor can provide thrust throttling ability which makes hybrid rockets able to switch
between wider range or larger thrust and to shut down and restart.
2. Hybrid rockets are less sensitive to cracks and debonds in fuel grain unlike solid rocket fuel.
3. Hybrid fuel can produce higher value of specific impulse
4. Oxidizers like N2O are less toxic and have self-pressurizing properties which eliminate the use of
additional gasses for maintaining the pressure.

Advantage of hybrid rocket fuel over liquid rocket fuel

1. Commonly used hybrid fuels are environmentally friendly, less toxic, non-hazardous to transport and store
compared to many volatile liquid fuels.
2. Hybrid fuel generally produces a higher density of specific impulse than liquid bi-propellent.
3. Engine using hybrid rocket fuel requires half of feed system hardware relative to a liquid fuel engine.

Different fuel and oxidizer used in hybrid rocket system and their theoretical performance

The list of different hybrid propellant with their air fuel ratio and specific impulse are listed below [1]. Hybrid fuel
could be less dense and lighter than a solid solution. The higher I sp value gives more advantage over solid

formulation and also over monomethyl hydrazine (MMH)/Nitrogen Tetroxide (NTO)[2].

fuel oxidizer Oxygen fuel ratio Specific impulse

O/F ratio Isp
HTPB LOx 1.9 280
PMM LOx 1.5 259
 HTPB N2O 7.1 247
HTPB N2O4 3.5 258
HTPB RFNA 4.3 247
HTPB FLOx(OF2) 3.3 314
PE LOx 2.5 279
PE N2O 8 247
Paraffin LOx 2.5 281
Paraffin N2O 8 248
Paraffin N2O 4 248
HTPB/AL (40%) LOx 1.1 274
HTPB/AL (40%) N2O 3.5 252
HTPB/AL (40%) N2O4 1.7 261
HTPB/AL (40%) FLOx(OF2) 2.5 312
Cellulose (C6H10O5) GOx 1 247
Carbon Air 11.3 184
Carbon LOx 1.9 249
carbon N2O 6.3 236
Table.1 O/F Ratio Comparsion[2]

Limitation of hybrid propulsion

Hybrid fuel has lots of potential as a primary rocket fuel but it has lots of drawbacks due to which it cannot be used
in a large thruster. Compared to liquid propulsion, the specific impulse of classical hybrids is not good. The
development of a new propulsion family is expensive in terms of financial and human investment. The regression
rate is really low, it results in a complex design of the solid part with a multiport grain, and difficulties in
combustion control. It produces a large number of residuals that result in damage to the propulsion system. The
objective is to obtain the same level as that of LOx/methane or to be better in terms of Isv

Cryogenic Propellent and Performance associated.

Cryogenic propellant are the types of propellants that require extremely low temperatures to store in their solid form.

This below table shows the list of some cryogenic propellant with their theoretical performance [1] [2].
fuel Oxidizer O/F ratio Isp
CH4(s) LOx 3 291
CH4(s)/Be (36%) LOx 1.3 306
NH3(s)/Be (36%) LOx 0.47 307
Pentane(s) LOx 2.7 279
Table.2 O/F Ratio of Different Fuels.[4]

Comparison between the most common solid, liquid, bipropellant and hybrid fuel

propellant Type Mixture ratio Equivalent Isv

density (Pc=7 Mpa,
Kg/m3 ∑=40)

AP/HTPB/AI Solid 68/18/14 1750 315

LOX/HTPB Hybrid 72/28 1060 354
NOT/MMH Liquid 2.37 1200 341
H2O2/RP1 7 1320 314
LOX/CH4 Bipropellants 2.77 1030 358
LOX/CH4 3.45 830 369
LOX/LH2 4.8 320 455
Table.3 Comparisions of Isv

Hydroxyl-terminated polybutadiene (HTPB) and nitrous oxide (N2O)

HTPB is one of the most commonly used polymeric binders as a rocket propellant due to its high compatibility, low
viscosity and the superior mechanical property [1]. Di-nitrogen monoxide N 2O also known as laughing gas has a
point of -89.50C at 1 atm pressure and is normally maintained as a liquid at a pressure about 58 bar [2]. Its molecular
weight is 44 gm and density is 1226kg/m 3 at 20oC. The critical temperature and pressure of N 2O is 7.27 MPa and
36.6oC [2].
Advantages of using N2O as an oxidizer:

1. If the operating pressure is below 45 bar, it does not require a pressurization system because of its
self-pressurization characteristics.
2. N2O is safer, and cheaper than other liquid oxidizers like LOx.
3. It can provide vapor pressure at ambient temperature that allows two phase storage and efficient
oxidizer delivery through a self-pressuring process.
4. The ullage volume increases sufficiently which allows the residual ullage gasses to combust with
fuel even after all the fuel has been discharged from the chamber.
5. At an ambient temperature the N2O has relatively high pressure so that the motor can operate at a
chamber pressure which is enough to achieve required thrust.
6. Inert gasses like helium can be used in pressurizing N 2O tanks to ensure necessary flow rate if the
operation pressure is above 45 bar.

With a pyro grain to serve as an ignition heat source and some catalytic effects for the nitrous oxide, a diffusion
flame is established upon the injection of nitrous oxide into a combustion chamber with a single port HTPB grain
[3]. The generated heat from the diffusion flame continues to decompose the nitrous oxide and HTPB through
convective and radiative heat transfer. Then, the decomposed gas species are mixed and combusted in the diffusion
flame to produce mainly water vapor and carbon dioxide.

Paraffin based rocket fuel

Paraffin are straight chain or branched hydrocarbons having chemical formula C nH2n+2 and the name of each member
ends with -ane. Examples of paraffin are propane, isopentane, normal heptane, etc[4]. The rapid regression rate of
paraffin-based rocket fuel has attracted a lot of interest compared to traditional polymeric fuels like HTPB
(Hydroxyl-terminated polybutadiene), which have a slow regression rate and create insufficient thrust. Because of
the growth in the mass flowing rate of the fuel, paraffin energizes at 3-4 times the rate of HTPB in terms of
regression rate, implying much larger thrust motors. Various HTPB-based fuel mixes were investigated, but after
preliminary testing and assembly, the main focus shifted to combining HTPB with Paraffin. When compared to a
variety of other compounds, the combination of Paraffin and HTPB creates "clean" gasses. They are also simple to
get and work with because they are non-hazardous. In the rocketry industry, HTPB molding and detailing is
extremely well recognized. Paraffin is also easy to cast and pour because it can simply be warmed past its melting
point and poured into a shape. It was expected that mixing Paraffin with HTPB will improve the Isp of HTPB
because Paraffin regression rate was significantly higher than that of unadulterated HTPB[6].
Because there was no knowing of what the concoction structure of the real Mer-chains would come from the
polymerization procedure, blending the two energizes homogeneously did not appear to be the greatest
methodology.
In its stead, a non-homogeneous methodology was adopted, which included integrating powdered Paraffin bits into
the HTPB while the casting and relieving processes were still in progress. During casting, these lumps would remain
solid inside the HTPB fuel center. During the engine's combustion, the fuel would regress down to these pockets of
Paraffin and discharge little globules of Paraffin into the burning fire, similar to how typical Paraffin engines
entrain. HTPB is constantly combined with tiny Paraffin circles and cast into fuel centers.

Apart from little thin areas around the surface of the circles, the two fuels are not thought to be molecularly
reinforced in any significant way. The biggest drawback of producing the wax centers was the wax's tendency to
decrease in volume as it transitioned from liquid to solid, which occasionally caused splitting inside the fuel center.
To avoid this problem, Paraffin Wax was allowed to cool and resolidify gradually at ambient temperature. In terms
of regression rate, the combined fuel allegedly outperformed simple HTPB. Surprisingly, the higher Paraffin fuel
concentration regressed faster than the lower fixation blend.
The regression rate of Paraffin was substantially higher than that of alternate energizers. The high regression rate is
offered by Paraffin Wax due to its nature of forming droplets which readily escape from a liquid layer on the surface
of the fuel into the flame zone. This flame zone is comparatively separated from the fuel surface [3]. The use of
hydrogen peroxide and a catalyst bed as the oxidizer adds to the simplicity because it eliminates the need for a
complicated and expensive igniter system. Hydrogen peroxide is also advantageous because it has a high specific
gravity and a high oxygen-to-steam ratio. Because the wax was still in a liquid form after the first test, collecting the
leftover wax was a challenge. Due to the soft fuel, some deformation was also detected after the fire.

HYDRAZINE BASED PROPULSION FUELS

The formation of Hydrazine molecules from Nitrogen and Hydrogen atoms under heat absorption makes it an
endothermic substance, which is the second reason for the substance's high calorific value. Its high density (1.04
kg/liter) and high boiling point are further advantages as a rocket fuel (113oC). Hydrazine, on the other hand, has a
number of drawbacks. It is a clear liquid that freezes at 1°C in typical conditions. Hydrazine is problematic to use
because of its high freezing point, especially in the winter [4]. It must be warmed if it is stored or filled into the
rocket during the cold season. An even more serious disadvantage is its proclivity for explosive breakdown when
heated or subjected to impacts. Other drawbacks include oxidation caused by the reaction with air, as well as the
hygroscopic characteristic of oxygen. Other atoms or atom groups can be substituted for hydrogen atoms in the
Hydrazine molecule. Alkalis of Hydrazine are compounds in which hydrogen atoms are substituted by hydrocarbon
radicals (methyl CH3, ethyl C2H5, and others). They differ from Hydrazine in terms of their physio-chemical
properties (density, viscosity, and so on) as well as their calorific value. Among these, methylhydrazine CHmHN-
NH2 and unsymmetrical dimethylhydrazine, (OH) N-NH2, are the most attractive as rocket fuels [3].
These compounds are less potent than Hydrazine because their molecules contain a significant proportion of Carbon,
which has a lower calorific value than Hydrogen. Their advantage is that they are liquid at a wide range of
temperatures, making their use easier. Unsymmetrical dimethylhydrazine is the most well-known. It's a liquid that
freezes at -57.20°C and boils at 63.10°C [4]. The strong reactivity of dimethylhydrazine is one of its distinguishing
features. It reacts with oxygen in the air more than Hydrazine, producing dimethylamine and water. It interacts with
CO2 in the air to produce (CH3)2 N-NH2-CO2 salts, which are insoluble in dimethylhydrazine and hence form a
solid deposit. When stored, dimethylhydrazine must not come in contact with the air because of its high reactivity. It
is best stored under a slight pressure from a neutral gas, e.g., Nitrogen. Pure dimethylhydrazine does not attack
construction materials. It promotes corrosion of aluminum and its alloys. It has a fairly high heat resistance and
begins to decompose only at about 700 to 800 oC. Unlike Hydrazine, neither liquid, nor gaseous, dimethylhydrazine
explodes from impacts but easily. Ignites in air (ignition temperature 10 oC, self-ignition at 250oC), hence it must be
regarded as inflammable.

Dimethyl Hydrazine should be stored in special containers far away from other buildings. The containers should be
placed underground since the smallest spark from static electricity may cause a fire. It can be extinguished with
water, being miscible with it at all ratios as it dilutes dimethylhydrazine and cools it at the same time. Diluted with
two or three parts water, it no longer burns in the open air. Carbon dioxide is another excellent extinguisher,
although chemical foams often employed as fire extinguishers are ineffective in this situation. Dimethyl-hydrazine is
a valuable propellant component due to its high chemical reactivity. It produces a propellant with forced ignition
when using liquid oxygen, and hypergolic propellants when using nitric-acid oxidizers. When compared to other
self-igniting components, dimethylhydrazine has a very low ignition delay (of the order of 0.005 sec) with nitric-
acid oxidizers, which varies significantly depending on the temperature of the components [7].

It is well soluble not only in water, but also in Hydrocarbon fuels; it is therefore possible to obtain hypergolic fuels
based on dimethylhydrazine with the aid of commonly available and inexpensive petroleum products such as
Kerosene. Self-igniting fuels with an acceptable Ignition delay time (not exceeding 0.03sec) are obtainable by
mixing it with Kerosene. The content of the latter says attain 40%[5]. Dimethylhydrazine-Kerosene mixtures
change their ignition delay time on contact with nitric-acid oxidizers more abruptly with increasing temperatures
than pure dimethylhydrazine[4]. Because it is such a hazardous material, it must be handled with extreme caution.
All Hydrazine fuels have the same qualities as alkalis, however they do not irritate the skin like alkalis do. They
must, however, be kept away from humans because they penetrate the body and are extremely toxic. The odor of
dimethyl hydrazine is distinctive. It can be noticed in very small concentrations in the air. Hydrazine and
dimethylhydrazine have twice the toxicity of nitric acid. Smaller amounts should be handled with safety eyewear
and gloves, whereas greater amounts should be handled with protective suits. Gas masks must be used as soon as the
odor of dimethyl Hydrazine is detected in the air. Splashes of the chemical can be removed off clothing using a lot
of water. The garments must be completely washed before being reused. Because dimethylhydrazine is a potent
poison, it should never be dumped down the drain. When a monopropellant Hydrazine engine is fired in a vacuum,
the principal exhaust components are Nitrogen, Hydrogen, and Ammonia[4].
Hydrogen Based Propellants

Hydrogen has long been recognized as a superior thermodynamic rocket fuel. With all oxidizers, it has a high heat of
reaction, and the gaseous reaction has a low average molecular weight. Chemical systems that use any other
currently available fuel generate less specific impulses than hydrogen-based systems. The high diffusivity and
chemical reactivity of hydrogen, as well as its large cooling capacity, make designing injectors and thrust chambers
considerably easier. However, the element has a number of drawbacks, including a low boiling point and density,
necessitating investigation into the payload capacities of actual vehicles employing this fuel to discover its true
value.

The percentage breakdown of the Ammonia, which is controlled by the required specific impulse, determines the
concentration of these gasses. When paired with an oxidizer like liquid oxygen, it's light and extremely strong,
blazing at nearly 3,000 degrees Celsius (5,500 degrees Fahrenheit)[5]. However, when liquid hydrogen was first
developed in the 1960s, it posed significant challenges and hazards. Liquid hydrogen and liquid oxygen are
cryogenic gasses that only change phase to liquid at extremely low temperatures. Liquid hydrogen must be kept at -
252 degrees Celsius (-423 degrees Fahrenheit) and properly insulated from all sources of heat to avoid boiling off
and expanding and bursting the propellant tank[4]. Because liquid hydrogen may seep through minute breaches
between tank welds, a rocket that can safely employ this form of fuel will necessitate very specialized engineering.
When paired with an oxidizer such as liquid oxygen, liquid hydrogen delivers the highest specific impulse, or
efficiency in relation to the quantity of propellant burnt, of any known rocket propellant.The use of liquid hydrogen
in the upper stages of current rockets to boost space payload capacity is the most urgent use. When a third stage is
added to a normal two-stage spacecraft, utilizing hydrogen instead of conventional propellants in the third stage
boosts the payload carried to a 300-mile earth orbit by 10%[4]. When higher velocity requirements are present, such
as in a 24-hour orbit, the hydrogen third stage may deliver double the payload of a conventional third stage. A
single-stage spacecraft's payload can also be enhanced by adding a hydrogen stage.

Hydrogen possesses physical qualities that make it a suitable working fluid in a nuclear rocket, in addition to being
attractive as a rocket fuel due to its chemical features. Hydrogen stands out yet again, with a specific impulse more
than double that of any other expellant. Nuclear rockets employing hydrogen as the only working fluid are projected
to have a specific impulse twice that of the best chemical systems at average reactor operating temperatures.
Thermodynamic performance of liquid hydrogen is largely determined by the exhaust chamber pressure and its

relation to the exhaust pressure utilized. When used as the fuel in a propellant combination, liquid hydrogen is
theoretically compatible with a wide range of oxidizers. However, liquid oxygen and liquid fluorine are the two
most important of these oxidizers; the former combination because it has a current application and plays an
important role; the latter combination because it or its chemical derivatives offer a significant improvement in
performance over LOX (Liquid Oxygen) systems[4]. As a result, the performance metrics addressed in relation to
hydrogen are confined to the two oxidizers mentioned above. As an energetic oxidizer for liquid hydrogen, liquid
oxygen is second only to liquid fluorine. Again, greatest performance occurs 'on the fuel-rich side of stoichiometric
combustion. Water is, without a doubt, the primary source of energy in this system. As the system gets more
oxidizer rich, dissociation and the accompanying spread between shifting and frozen particular impulses increases.
The main distinction between the H2-02 and the R2 -F2 systems is the former's lower combustion temperature[5].
Although oxidizing hydrogen to hydrogen-fluoride rather than water results in somewhat better performance, a
much hotter flame must be endured[8]. The biggest disadvantage of liquid Hydrogen is that it has a low boiling
point of -2540C, which is 7100 degrees lower than liquid Oxygen[6]. This makes storing and transporting huge
volumes of liquid hydrogen challenging. Another significant drawback is the low density (0.07 ka/liter). Hydrogen
produces propellants with far higher specific impulses than Hydrazine and petroleum compounds. Hydrocarbons and
liquid oxygen have a long history as rocket fuel, and they continue to play an important role in the military and
space programs.
Until now, the debate over the relative merits of employing liquid hydrogen as a high-energy propellant has focused
solely on its theoretical performance. Although this performance is appealing, there are advantages, downsides, and
trouble areas connected with the usage of hydrogen, just as there are with other rocket propellants. Several other
factors must be evaluated in order to accurately evaluate any propellant system beyond its estimated or laboratory
performance. Even the most powerful propellants are useless without functioning subsystems, ground handling and
storage compatibility, and a tolerable level of related safety. The key issue, like with liquid rockets, is obtaining the
necessary tanks, fluid flow systems, and turbo pump units.

Ignition and combustion must be taken into account. Because of the high combustion temperature that may occur,
cooling is an issue. When contemplating liquid hydrogen as a high-energy space-age fuel, it's important to examine
the impact of low propellant bulk density and low-temperature storage requirements on propellant tank design and
size. The resultant tankage is comparably considerable in all circumstances due to the low specific gravity of liquid
hydrogen.

The capacity of conventional propellant tanks must be just 19.47 percent of that of a comparable LOX-LH2 stage to
carry the same total weight of fue[5]. The fluorine-hydrogen stage tanks only need to be around half the total
capacity necessary for the LOX-LH2 system. It should go without saying that the bulk density of the propellants has
a significant impact on the weight of the tanks and, as a result, on the payload performance capability j of any given
system.

Although cryogenic liquids (such as hydrogen) are among the best propellants currently available for both chemical
and nuclear rocket stages, their low temperature properties provide unique challenges in tank and fluid system
design. Heat transfer to these cryogenic liquids from the sun, planets, planet atmospheres, and other components of
the rocket vehicle is unavoidable throughout an interplanetary space voyage[5]. As a result of the heating, the
propellant vaporizes and is lost by venting. The potential benefit of using cryogenic propellants would be lost unless
these losses are minimal. As a result, these low-temperature liquids must be protected from an unfavorable heating
environment.
Other Potential Rocket Fuels
Metallic Hydrogen

Metallic hydrogen is a phase of hydrogen in which it behaves like an electric conductor. It is a theoretical concept
which can be obtained during an extreme condition. During this state the hydrogen is in atomic form.

A paper has claimed that metallic hydrogen can be obtained by compressing the hydrogen between diamonds, since
it is the hardest material. However, diamond has some roughness at a microscopic level which can rupture diamond
at extreme pressure. So, to smoothen the surface aluminum layer was coated on the surface. For the confirmation of
the metallic form of hydrogen, a light ray was struck to the hydrogen. The reflection of light after striking the
metallic hydrogen conforms to the formation of metallic hydrogen. This claim was countered by an argument that
the reflection was from the metallic layer which is pretty logical.

During metallic form hydrogen is in atomic form and when it comes to molecular form, a tremendous amount of
energy is released which is around 216 MJ/Kg[8]. During this reaction the exhaust gas is only hydrogen gas which is
the lightest gas. Comparing this method to other; Hydrogen and oxygen can produce 10 MJ/Kg and TNT 4.2 MJ/Kg.

Metal Organic Framework

MOFs are 3D coordination polymers which are crystalline and porous in nature. Metal-organic frameworks (MOFs)
are advanced materials of principal importance in gas separation, storage, and catalysis but have also been explored
as energetic materials[8]. In principle, MOFs should offer a highly modular platform for developing solid hypergolic
ignition and fuel systems, where the ignition and combustion properties of the solid fuel can be fine-tuned by
variation of both organic and inorganic components of the MOF.

However, exploration of MOFs and coordination polymers as energetic materials has so far focused only on
properties relevant to explosives or pyrotechnical materials, such as thermal and shock sensitivity. Hypergolicity,
which is a critical property of a potential fuel or propellant, has not been investigated in context of MOFs or
coordination polymers in general

The surface area of 1 kg of MOF is equivalent to the surface area of a football field. It consists of metal center and
ligand (ion or neutral molecule that bonds to central metal atom or ion)[8].

Classification of ligands

Based on anchoring sites or how many bond it can form, ligands are classified into:

1. Mono dentate: can form one bond with a functional group. Eg Benzoic acid
2. Bi-dentate: can form two bonds with a functional group. Eg Terephthalic acid
3. Tri-dentate: can form three bonds with a functional group. Eg 1,2,3-Benzenetricarboxylic acid, 1,3,5-
benzenetricarboxylic acid, etc.
Types of ligands to form MOFs
To form a polymer, ligands must bi-dentate or more and must have symmetric structure. Since, to form a continuous
chain at least two bonds are necessary. Eg benzoic acid which is bi-dentite can be used to synthesize MOF.
Similarly, in case of multi dentate ligands the position of the functional group must be symmetric or not, the
concentration of ligands during the synthesis stops the further formation of polymers. Eg both 1,2,3-
benzenetricarboxylic acid and 1,3,5 benzenetricarboxylic acid are tri-dentate but only 1,3,5 benzenetricarboxylic
acid is used for MOF synthesis[6].

Application Of MOF[8]

MOF has a wide range of applications some of them are mentioned below:

1) Supercapacitor: Researchers have built a high-capacity energy device using a metal-organic framework.
2) Electro catalyst: used to modify the rate of an electrochemical reaction occurring on an electrode surface.
3) Photocatalysts:  MOFs can be used as ideal photocatalysts because both the metal nodes and organic linkers
can be readily modified to improve photon absorption and catalytic activity
4) Biomedical application: It has a high drug loading capacity so it can be used as drug delivering vehicles.
5) Hydrogen storage: Due to its high surface area, porosity, and flexible and tunable porous structure 1000l of
hydrogen can be stored per Kg MOF at ambient condition.
6) Carbon capture: Similarly, it can also be used to store the carbon dioxide before it releases to the
atmosphere.

Ammonia Borane
Since their discovery in the early 1930s, hypergolic propellants have been a mainstay of liquid rocket systems. This
class of propellants consists of combinations of fuels and oxidizers that, upon contact, self-ignite through heat
generated by chemical reactions between the fuel and oxidizer. This can simplify the overall complexity of rocket
systems employing these propellants due to the elimination of a dedicated ignition source. While a wide range of
fuel and oxidizer combinations exhibit this property, only a select few have offered the physical properties and
performance necessary to make them viable in fielded rocket systems[5]. While these propellants can be reliable and
improve the versatility of systems using them, they are generally toxic and highly hazardous to handle.
Unfortunately, few viable alternatives have been found due to the complexity of the reactions governing hypergolic
ignition making it difficult to predict the hypergolic characteristics of fuels/oxidizers based on their
physical/chemical properties.
Historically, hypergolic propellant systems have utilized fuels based on hydrazine and its derivatives (e.g.
monomethyl hydrazine, unsymmetrical dimethyl hydrazine, etc.). While these fuels are well characterized and offer
the performance generally required for these systems, they are highly toxic and hazardous to handle prior to use. As
such, there is a strong motivation to develop alternative fuels that offer similar (or better) performance while being
less hazardous than the fuels currently in use.
One fuel of interest as a hypergolic solid fuel is ammonia borane (NH3BH3)[6]. Under typical atmospheric
conditions, ammonia borane is a stable solid material with 19.6 percent hydrogen by mass. Though much of the
research related to ammonia borane has focused on its potential as a solid-state hydrogen storage medium, its high
hydrogen density makes it an attractive fuel for use in rocket systems also. Though it was first synthesized by Shore
and Parry in 1955 [16], the hypergolic behavior of ammonia borane has only recently been reported by Gao and
Shreeve [8]. Initial results published by Gao and Shreeve suggested ignition delays on the order of 80 milliseconds
when tested with white fuming nitric acid (WFNA[7]). However, further 35 investigations by Ramachandran et al.
found consistent ignition delays as short as 2 milliseconds when used with WFNA. These are some of the shortest
ever reported for solid hypergolic fuels and could enable ammonia borane to serve as a viable replacement for
existing hypergolic liquid fuels.

In the time since it was first synthesized, new synthesis methods have been developed that have the potential to
improve the yield of ammonia borane production while simultaneously helping to reduce the cost of synthesis.
Ramachandran et al. recently published a water-promoted synthesis procedure that produced high yields of ammonia
borane with the potential for use in large scale production.At the same time, this procedure is both more cost
efficient and safer than previous synthesis methods. These recent developments make ammonia borane more
feasible for use in hybrid propulsion systems.

Conclusions

HTPB has long been the standard fuel for designing and testing hybrid rocket engines, although no hybrid rocket has
ever flown commercially, with the exception of SpaceShip 1. Complex grain cross-sectional geometries with large
ports and wetted surface areas must be used to achieve the required thrust level. The mixture of 50 percent Paraffin
Wax and 50 percent HTPB produces the best results.[6] A fuel made by combining HTPB and Paraffin wax, on the
other hand, would be non-toxic, easy to cast, and have a higher regression rate. It would also have increased
structural capabilities, increased resistance to melting, and a simpler fuel core shape with a tolerable regression rate.
The high density and boiling point of hydrazine make it an excellent rocket fuel.

However, because of its high freezing point, it is inconvenient to operate, particularly in the winter. Other drawbacks
include its proclivity for explosive breakdown when heated or struck, oxidation from air reactions, and its
hygroscopic nature. Hydrogen has the highest heating value and produces a lot of gas when it burns. The biggest
disadvantage of liquid hydrogen is its low boiling point, which makes storage and transportation problematic.
Another significant disadvantage is the low density.

MOFs are made up of clusters of metal ions and an organic molecule called a linker. They induce hypergolic
behavior in MOFs by using acetylene and vinyl substituents to unlock the latent energetic properties of electron-
deficient linkers in a ZIF[8]. This strategy also uses the formation of coordination bonds to enhance the hypergolic
reactivity of the ligand, which is intrinsically different from approaches used to design other types of energetic (e.g.,
explosive and pyrotechnic) MOFs, where the formation of an extended structure often leads to ligand stabilization,
in the form of reduced heat and shock sensitivity, sometimes accompanied by increased heat of detonation due to an
energetic ligand being trapped in a non preferred conformation. The modularity of MOFs permits modification of
the hypergolic properties (ID, flame color, and duration) of the fuel, including achieving ultrashort IDs, without
changing its overall structure. Simillary, discussed propellants like metallic hydrogen, ammonia borane, MOFs.
Although under investigation the ability to achieve and fine-tune hypergolic performance, combined with the
absence of hydrazine-based carcinogens or explosive components, should make these propellent materials promising
candidates for safer, environmentally friendly propellants.

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