Green Propulsion: Trends and Perspectives

Environmentally friendly alternatives could reduce the risk and cost of propulsion systems.
Aerospace has been investigating possible candidates for national security space systems.

John D. DeSain

The propellants used in space programs pose environmental concerns in four main areas: ground-
based impacts, atmospheric impacts, space-based impacts, and biological impacts. Ground-based
impacts range from groundwater contamination to explosions caused by mishandling of
propellants. Atmospheric impacts generally come from the interaction of propellant exhaust with
the atmosphere. Space-based impacts generally focus on debris and effects on spacecraft.
Biological impacts tend to focus on the toxicology and corrosiveness of propellants.

Space system developers have long sought to mitigate these impacts, because doing so could
potentially reduce both cost and riskespecially the costs and risks associated with propellant
transport and storage, cleanup of accidental releases, human exposure to toxic substances,
infrastructure requirements for handling hazardous propellants, and orbital debris. The continued
use of highly toxic propellants that generate environmental pollutants keeps program costs high
but the cost of developing and qualifying green alternatives also tends to be high. This has
traditionally slowed development even when a green propellant provides potential performance
benefits.

Also, the term green propellant is often confusing, as many assume a green propellant has no
environmental impact. Such a propellant is generally beyond the realm of physical possibility.
All propellants affect the environment in some way. For instance, all launch vehicles produce
exhaust. The components of this exhaust can include soot, carbon dioxide, alumina, inorganic
chlorine, water vapor, sulfates, and nitrogen oxides. All of these have an environmental impact,
and may contribute to climate change, ozone destruction, or upper atmospheric contrails,
depending on the atmospheric layer in which they are deposited; however, the severity and
duration of the impact can vary greatly. Given this fact, a green propellant is more correctly
viewed as one that seeks to minimize or eliminate a critical environmental impact in one or more
of the four main areas. A green propellant is likely to have its own environmental impacts, which
may be equal to the current technology in certain areas. For example, many green propellants
seek to eliminate hydrazine because of its biologic impact, but they still present atmospheric or
space-based effects.

The Aerospace Corporation has been investigating the potential for green propulsion systems
with an eye toward helping space system designers minimize environmental impacts while
improving overall efficiency and economy.
The Air Force Office of Scientific Research and NASA launched the first test rocket fueled by an
aluminum-ice (ALICE) propellant in 2009. The vehicle accelerated to a speed of 330 kilometers
per hour and reached an altitude of nearly 400 meters. Courtesy US Air Force and Steven Son,
Purdue University.

Ammonium Perchlorate Replacements

Hydrocarbon-based solid fuels have been used as rocket propellants in combination with the
solid oxidizer ammonium perchlorate for several decades. Solid rocket motors are commonly
used in launch-on-demand systems, boost-phase launch-assist systems, and small-lift launch
vehicles. Unfortunately, much of the environmental impact (both ground and atmospheric) from
the launch vehicle fleet comes from the ammonium perchlorate in solid rocket motors.
Perchlorate leaching from discarded motors and from manufacturing operations can diffuse into
groundwater, which can pose a health hazard for humans. The hydrogen chloride and chlorine
produced during launch can destroy stratospheric ozone. Many of the exhaust components (soot,
carbon dioxide, alumina, inorganic chlorine, stratospheric water vapor, and nitrogen oxide) can
also contribute to climate change, either directly or through their reactions with other
atmospheric species. In addition, perchlorate-based solid motors present safety challenges
because they cannot be shut down once ignited.

Several green propellants are being developed as replacements for ammonium perchlorate in
solid rocket motors. One potential candidate that has been gaining in popularity is ALICE
(aluminum-ice). It combines the fuel, composed of nanoparticles of aluminum, with the oxidizer,
oxygen, stored as water. The mixture is maintained below the waters freezing point, so that it
behaves like a solid propellant. ALICE has a higher theoretical specific impulse than
conventional perchlorate-based solids. In 2009, NASA and the Air Force Office of Scientific
Research launched a small suborbital demonstration vehicle powered by ALICE. The propellant
has also been proposed for use on interplanetary return missions, as both water and aluminum
could potentially be produced in situ on many interplanetary landing sites. ALICE produces
hydrogen and alumina as its main exhaust; while these are generally billed as environmentally
friendly, stratospheric alumina has the potential to reduce ozone concentrations. ALICE does
present some risk of explosion (as all propellants that combine fuel and oxidizers do), but this
risk has been shown to be relatively low. Alone, neither aluminum nor water is hazardous.

Conceptual diagram of a standard hybrid rocket motor with a liquid oxidizer tank and a solid fuel
grain.

Performance comparison for a conventional solid rocket motor and a hybrid motor with the same
propellant mass.

Several energetic salts have also been proposed as replacements for ammonium perchlorate.
Solid motors based on ammonium dinitramide (ADN) could potentially have a 4-percent-higher
specific impulse than perchlorate-based systems without producing hydrogen chloride exhaust.
However, ADN is more prone to detonation under high temperatures and shock. Also, its density
is about 8 percent less than that of ammonium perchlorate, so its performance is lower than a
one-to-one comparison would suggest. In the late 1990s, ATK produced a solid ADN propellant
that was thermally stablebut autoignition still occurred at about 110 kelvin less than that of
comparable ammonium perchlorate propellants. NASA has been developing a solid motor based
on ADN and has been working with the Swedish Defense Research Agency to investigate a solid
fuel that would overcome the limitations of current formulations. Hydroxylammonium nitrate
(HAN) is another energetic salt that has been proposed as an ammonium perchlorate
replacement. In 2007, Raytheon and Aerojet demonstrated a 150-pound thruster based on HAN.

Hybrid rockets have also been investigated as a green alternative to perchlorate-based solid
rockets. Hybrid propulsion systems use a solid hydrocarbon fuel (typically a polymer) and a
liquid oxidizer. They have several advantages over conventional perchlorate-based solids in that
they are nontoxic and nonhazardous, they can be shipped as freight cargo, and they can be shut
down in case of an on-pad anomaly. They also have better performance attributesthey can be
throttled for thrust control, they can potentially be restarted on demand, and they have higher
achievable specific impulse. The disadvantage of hybrid motors is that many of the oxidizers
would need a propellant management system, which often adds mass and cost to the vehicle
although some proposed self-pressurizing oxidizers could eliminate

this as a liability. Hybrids produce exhaust products similar to those of conventional liquid
motors, with carbon dioxide, soot, water vapor, and nitrogen oxides as potential components.
Soot levels may be similar to those of conventional solids that also use solid hydrocarbons as
binders. Because the solid fuel and liquid oxidizer are not mixed initially, they have a lower
explosion risk than conventional solid motors. Scaled Composites has produced a hybrid launch
vehicle, SpaceshipTwo. The vehicle, designed to perform only suborbital human space flights, is
being tested, and commercial passenger flights are expected to start in 2011.

Kevin Dorman and John DeSain testing green propellant.

Hydrazine Replacements
Hydrazine is a multipurpose propellant that can be used as a hypergolic bipropellant with
nitrogen tetroxide or in a monopropellant thruster with a catalyst. Hydrazine derivatives are still
used as bipropellant fuels in launch vehicles in several countries. The United States no longer
flies rockets based on bipropellant hydrazine derivatives, but small hydrazine monopropellant
thrusters are often used by spacecraftand these are the applications that are typically targeted
for green replacements. Hydrazine storage is a concern on the ground. Because of its toxicology,
it is costly to handle. The atmospheric impact is not a large driver in hydrazine research, but the
space environment is a cause for concern. Hydrazine is naturally unstable, and unvented
hydrazine tanks have been known to rupture in space, posing a debris risk at the end of mission
life.

The Swedish company ECAPS produced a satellite thruster based on an aqueous ADN solution
that produced higher specific impulse than monopropellant hydrazine. It was used on the
formation-flying Prisma satellites. Thus, ADN is a potential replacement not only for perchlorate,
but for hydrazine monopropellant as well. Similarly, HAN can potentially be used in aqueous
solution as an alternative to hydrazine.

Electric propulsion offers another potential green alternative. Electric thrusters encompass a wide
range of designs, including arcjets, resistojets, ion thrusters, and Hall thrusters. They use a
magnetic field to trap injected electrons that are used to ionize an injected gasusually xenon.
Electric thrusters have the advantage of high specific impulse (compared to chemical thrusters),
and they can potentially use much less propellant than a hydrazine vehicle to achieve the same
maneuver. The main disadvantages are that they require an electric power source and generally
offer only low thrust, which means they take longer to deliver a satellite to orbit. Many satellites
have appropriate power generators onboard for other applications, so electrical thrusters need not
add massbut the longer delivery time can make them unattractive for certain missions. Thus,
many satellites that use electric thrusters still must have hydrazine onboard for certain
maneuvers. The xenon released from electric propulsion is generally not an environmental
hazard, although the ionic plume can affect the space environment. Electric propulsion has been
used by Russian satellites for a long time and is gaining acceptance in the United States; the
technology is flying or will fly in many major U.S. Air Force programs and has helped lower the
amount of hydrazine needed for these missions.

Testing of a hybrid motor with a built-in swirl pattern created via stereolithography.

Several potential bipropellant formulations that use liquid oxygen (LOX) are being produced as
potential hydrazine replacements. In general, these propellants are much less toxic than
hydrazine derivatives; however, the cryogenic (< 91 kelvin) nature of liquid oxygen makes it
hazardous to produce and difficult to store for long periods. Some of the first launch vehicles
ever developed used LOX formulations, and kerosene/LOX and hydrogen/LOX engines are still
in use today. LOX-based formulations are less popular for spacecraft propulsion because they
require bulky tanks and feed lines and need large amounts of energy for refrigeration. Still,
LOX/hydrocarbon fuels offer higher specific impulse than hydrazine monopropellant. Specific
impulse is a way to describe the efficiency of rocket and jet engines. It is the ratio of the thrust
produced by an engine to the rate of fuel consumption: it has units of time and is the length of
time that one unit weight of propellant would last if used to produce one unit of thrust
continuously. Thus an engine with a higher impulse would be more efficient because it would
produce more thrust for the same amount of fuel used. Several different designs of
LOX/hydrocarbon fuels have been demonstrated recently. For example, an 870-pound
LOX/ethanol reaction-control thruster was developed and test-fired by Northrop Grumman in
2003, and Aerojet has also tested a LOX/ethanol reaction-control thruster. In 2007, XCOR and
ATK test-fired a 7500-pound motor based on LOX and methane; the pressure-fed engine was
sponsored in part by NASAs Advanced Development LOX/Methane Engine program. In 2008,
the Pratt & Whitney Rocketdyne RS-18 monopropellant thruster was modified to use
LOX/methane and was tested by NASA at White Sands, New Mexico. Methane engines have
performance close to that of traditional LOX/kerosene engines, but generally have lower fuel
density. An advantage of methane over kerosene is the possibility to use a fuel-rich gas generator
without soot formation; it also features a high cooling efficiency. Methane is injected in a
gaseous state, thus lowering the risk of combustion instabilities. One reason for the renewed
interest in LOX for spacecraft is the potential for in situ resource use during planetary missions.

High-test hydrogen peroxide has always been attractive as a monopropellant, as its

decomposition products are water and oxygen. It can also be used as part of a bipropellant. In the
past, hydrogen peroxide was used for satellite propulsion, but fell out of use as good catalysts for
hydrazine thrusters became available. One major drawback of hydrogen peroxide is that storage
becomes more difficult as the purity increases. A purity of at least 67 percent is needed to
generate sufficient energy from a thruster. Several sub- marine accidents have resulted from
unintended explosions of hydrogen peroxide propellants used in torpedoes. Still, hydrogen
peroxide has been safely used by Russian Soyuz launch vehicles (82 percent purity) for more
than 40 years to drive the main turbine pump in the gas generator and in the reaction-control-
system thrusters used for the descent phase. Hydrogen peroxide was also used as the oxidizer in
the British Black Arrow launch vehicle. As a monopropellant, hydrogen peroxide has a
performance about 20 percent lower than hydrazine. The volume specific impulse achievable
with 90 percent hydrogen peroxide is higher than for most other green propellants because of its
high density. The most significant technological challenge for creating hydrogen peroxide
monopropellant thrusters has always been the development of effective, reliable, long-lived
catalytic beds. Also, alternative decomposition techniques are still needed to fully exploit the
higher performance offered by 98 percent hydrogen peroxide. Current research is generally
focused on microthrusters for small satellites. Lawrence Livermore National Laboratory
developed a microthruster that uses 85 percent hydrogen peroxide; it flew on a 25-kilogram
satellite. For the last decade, General Kinetics has offered 3-, 6-, and 25-pound force
monopropellant and bipropellant thrusters and gas generators based on hydrogen peroxide.

Nitrous oxide is similar to hydrogen peroxide in its usability as an oxidizer in a bipropellant or as

a monopropellant. Nitrous oxide offers potentially 80 percent of the specific impulse of
hydrazine. Unlike other nitrogen oxides, it is nontoxic, noncorrosive, and stable under ordinary
conditions; however, like most monopropellants, it can explode under certain conditions, so
handling and shipping are a concern. Nitrous oxide is easily liquefied under pressure and is often
stored as a liquid. High vapor pressure (50 atmospheres at room temperature) enables self-
pressurization of the propellant tank, which can save weight. The reaction productsnitrogen
and oxygenare not hazardous. Catalysts are generally used to accelerate the decomposition of
nitrous oxide because the decomposition temperature tends to be high. Developing space-
qualified monopropellant catalysts are an issue with nitrous oxide, although some progress has
been made on small resistojet thrusters for microsatellites. A monopropellant based on nitrous
oxide is being developed by Firestar Engineering with support from NASA and DARPA
(Aerospace has been involved in reviewing the safety testing program). It has higher
performance than hydrazine, and may soon fly on the International Space Station. Much of the
current investigation has focused on the use of nitrous oxide as the oxidizer in hybrid
bipropellantsalthough in this application, ozone destruction from the nitrogen oxides in the
exhaust would have to be considered.

Another hydrazine alternative, cold-gas thrusters, has been used on satellites for many years,
both for maneuvering and for attitude control. They are suitable for applications that require very
low total impulse. Cold-gas thrusters offer a wide range of chemical propellants because the gas
need not be a combustible to provide thrust. Nitrogen has been used in many designs and has a
specific impulse of 68 seconds. The main disadvantage of cold-gas thrusters is their low
performance; however, for nanosatellites (where space is limited), their simplicity is an
important advantage. Low-thrust propulsion engines using cold-gas thrusters are commercially
available from various sources. (see sidebar, The National Environmental Policy Act).

Examples of Aerospace Research

Aerospace has a long history of investigating electric propulsion systems. Early programs
focused on hydrazine arcjets, ion engines, and Hall-efffect thrusters. More recent work has
complemented the corporations expertise in small satellites.

For example, a recent study verified the feasibility of a two-stage air-breathing Hall thruster. The
system would be used to compensate for the increased orbital drag acting on a satellite at lower
altitudes. A small, responsive satellite flying at lower altitudes could achieve better optical
performance or present simpler design constraints. A key aspect of the thruster design was an
ionization stage based on electron cyclotron resonance.
The Aerospace Corporation has developed a paraffin wax fuel grain that can be hypergolically
ignited. Hypergolic propellants spontaneously ignite when they come into contact and thus do
not need a separate ignitor. The photograph shows the 2010 test firing of a hypergolic paraffin
wax/gaseous oxygen motor at The Aerospace Corporation hybrid rocket test stand.

For many years, Aerospace scientists have been working with cold-gas microthrusters
manufactured from photo-sensitive glass-ceramic materials. The technology would be suitable
for a miniature spacecraft. The material has also been investigated for use in arrays of one-shot
microthrusters that could be individually activated on orbit. More recent work geared toward the
propulsion needs of CubeSats has focused on the use of a UV laser to activate a solid polymer
and produce usable exhaust; the use of a laser to permit the combustion of solid propellants at
pressures that would otherwise be too low; the use of ADN monopropellant; and electrolysis of
wateressentially a fuel cellto generate hydrogen gas as propellant.

Another intriguing study examined the introduction of a liquid hydrocarbon (n-heptane) and a
gaseous oxidizer in a modified shock tube to create a pure gas-phase fuel and oxidizer mixture.
Also, plans for new research facilities at Aerospace include the capability of studying liquid-
oxygen/liquid-hydrogen thrusters.

Aerospace has developed a hybrid motor sizing code to answer fundamental questions such as:
What is the performance gain or loss that will result from using hybrids instead of conventional
perchlorate solids or liquids? What materials and design techniques could be used to increase
payload-to-orbit capability? What is the estimated cost, and how does that compare with a
conventional launch vehicle?

The sizing code shows that as payload weight increases, hybrids become more competitive with
conventional solids. The LOX and helium tanks (used as a pressurant) are the primary reason
that hybrids have a larger inert mass than solid rockets. Future systems that use self-pressurizing
oxidizers or composite oxidizer tanks would significantly improve hybrid system performance.

Enhancing the burn rate of the solid propellant would also boost hybrid motor performance. With
this in mind, Aerospace has been examining the use of fuel additives to create novel fuel grains.
These additives may increase burn rates and overall performance and could also enable a restart
capability. Currently, hybrid rocket motors are ignited by explosive squibs or gas flames. The
squib systems can only be restarted if the squib is replaced, which is not possible for upper stages
already in flight. External flame sources are possible on upper stages, but these add weight.
Hypergolic fuel grains, which ignite spontaneously upon contact with the oxidizer, provide the
simplest and most reliable form to start and restart a motor. Studies at Aerospace have
demonstrated that the addition of lithium aluminum hydride (LiAlH4) to paraffin wax produces a
fuel grain that ignites upon contact with several different chemicals. A 50-pound-thrust paraffin
wax/gaseous oxygen motor was constructed and tested at Aerospace, demonstrating the
feasibility of hybrid motors that use LiAlH4 doped paraffin wax and nitric acid as a hypergolic
ignition system.

Hypergolic propellants are extremely useful on orbit, where conventional solids are rarely used.
Aerospace has been researching a novel approach to fabricating fuel grains that could be used to
create hybrid motors for CubeSats. In this approach, a fuel grain is built up using a form of rapid
prototyping called stereolithography, in which patterns in successive layers of a liquid
photopolymer are cured to produce a three-dimensional structure. Complete control of the three-
dimensional grain shape allows the design of a hybrid motor that is highly filled and where the
ports are not limited to straight, axially constant shapes, as is the case for motors produced by
typical casting methods. Aerospace has fabricated and tested several fuel grains using gaseous
oxygen. A novel deposition apparatus has been set up that will allow printing of paraffin wax
motors as well. Positive results have been shown, and the technology is at Technology Readiness
Level 3.

Future Technology
Some proposed technologies would eliminate propellants entirely. These tend to be far-reaching
and have generally been demonstrated only in small-scale ground tests, if at all. They include
concepts such as space elevators, laser propulsion, nuclear propulsion, and kinetic rail guns.
Aerospace scientists have even proposed the ejection of microminiature spacecraft, instead of
chemical exhaust products, to provide thrust; the satellites could even be programmed to return
to the host craft, enabling long-term reuse. Though intriguing, these proposals do not appear
likely to affect the space industry in the near future.

One exception is the solar sail. Originally proposed almost 50 years ago, solar sails use pressure
from the solar wind and solar radiation to propel the spacecraft. Current technology uses
ultrathin mirrors, and future crafts could potentially use a sail that acts both as a solar panel and
as a propulsion device. Solar sails are generally not practical for Earth orbits, where atmospheric
drag would overcome the forces produced, although solar sails that rotate with the craft could
possibly make them suitable for some orbital use. The Japanese IKAROS satellite launched in
2010 uses a solar sail as its primary mode of propulsion; it will travel to Venus and then to the far
side of the sun. Several other solar sail projects are currently in the works and may soon fly.

Solar sails such as this one use pressure from the solar wind to propel spacecraft through
interplanetary space. Courtesy of NASA/MSFC/D. Higginbotham.

Summary
Ultimately, the fate of green propulsion will depend on its ability to satisfy the two main drivers
for its developmenthigher performance and lower costs. U.S. space agencies have already
begun the move toward green propellants with the acceptance of LOX/hydrogen and
LOX/kerosene launch vehicles and greater use of electric propulsion for spacecraft. Currently,
the atmospheric impact from launch vehicles remains low, but only because launch rates remain
low. Limiting environmental impacts is a key part of achieving the high launch rates that would
be needed to pursue ambitious space architectures, as doing so would help achieve the cost
efficiency needed to make rapid launches financially possible. Green technology could also make
interplanetary missions more efficient and sample-return missions from distant bodies more
feasible. Green technologies arent just a future possibilitythey are already a part of the space
architecture, and further growth seems highly likely.