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Polymer Synthesis


Title: PowerPoint Presentation Author: Frank Crossman Last modified by: Frank Crossman Created Date: 8/6/2005 4:23:51 PM Document presentation format – PowerPoint PPT presentation

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Title: Polymer Synthesis

Polymer Synthesis Manufacturing SystemsFrank
Crossman and Robert Milligan
  • Overview
  • From our current knowledge of the chemical makeup
    of the Mars regolith and atmosphere, we develop a
    sequence of chemical processes that produce
    sufficient quantities of  chemical precursor and
    reagent stocks to
  • (1) allow the synthesis of some important
    polymers for construction of a small permanent
    settlement in a two- Earth year time period and
  • (2) provide the chemical industry infrastructure
    necessary to replicate that settlement in
    subsequent two-year cycles in arithmetic
    increments of settlers every two years. 

  • We describe the synthesis manufacture of three
    polymers which represent three uses of structural
    polymers on Mars
  • polyethylene for piping and a variety of general
    storage containers. A pellet extruder and die
    system will be used to produce piping and joints,
    blown bottles, and other structural shapes from
    extruded sheet and assembled by thermal welding.
  • polyester to provide a matrix for glass fiber
    reinforced composites used for habitat module
    construction. Glass reinforced polyester matrix
    composites will be used where structural strength
    is critical such as in the habitat pressure
    vessels. The cylindrical pressure vessel
    structures will be fabricated in a wet filament
    winding machine and the polyester matrix will be
    cross-link cured at room temperature.
  • epoxy for use as a structural adhesive for metal,
    glass, and composite joints.

Challenges in Polymer Manufacture on Mars
Imagine awaking in your bed one morning to
discover that all man-made polymers in your daily
life had disappeared. You have no sheets, no
toothbrush, no computer, no microwave, no phone.
You might have some cotton undergarments
remaining Now imagine that you awakened in a
world where oil is non-existent as well. Now you
have no oil power, no gas heat, and no petroleum
chemical stocks from which most chemicals and
polymers are derived. The challenge is to
synthesize and manufacture polymers from scratch
using available in-situ minerals and gases on
Mars with chemical processing equipment that is
sized to the Mars Homestead needs.
Sizing the Chemical Plant
  • Phase 2 Design studies have estimated the
    quantity materials needed to build a habitat
    sufficient to house 12 settlers.
  • 115 tonnes of fiber glass polyester composite,
  • 46 tonnes of polyethylene
  • 5 tonnes of epoxy adhesive
  • These materials are produced during a 400 day
    period at average daily production rates of
  • 70 kg/day - Unsaturated polyester resin and
    styrene for crosslinked polyester
  • 116 kg/day - Polyethylene
  • 12 kg/day - Epoxy
  • The size of the chemical reactor to produce 45 kg
    of unsaturated polyester resin (a viscous liquid)
    in a one batch a day process is
  • Volume mass/density 45/1.2 0.038 cubic
    meters or 9.4 gallons
  • Conclusion The chemical plant needed to produce
    these quantities is more than laboratory scale
    but less than that of many pilot plants on Earth.

Pdc Machines, Inc.
To Polymers working forward from known Mars
  • The known in-situ Mars resources that we start
    with are small in number and rely on the
    existence of a chemical processing capability
    already established on Mars to produce the bare
    necessities of life including methane for fuel
    and oxygen to breathe.
  • The 12 chemical building blocks are
  • CO2 (carbon dioxide) and N2 (nitrogen) from the
    atmosphere of Mars
  • H2O (water), NaCl (salt), and hydrated CaSO4
    (gypsum), silica, alumina, magnesia from the
    regolith of Mars
  • CO (carbon monoxide), CH4 (methane) from the
    making of methane fuel
  • H2 (hydrogen) and O2 (oxygen) from the
    electrolysis of water to obtain oxygen
  • (see R. Zubrin, The Case for Mars, 1996)

All the rest of the required chemicals and
polymers are derived from this short list of
pre-existing chemicals.
The end products
Case 1 Polyethylene flake remelted/formed
Polyethylene thermoplastic
Case 2 Bisphenol A Epichlorohydrin Diamine
accelerator Crosslinked Epoxy Adhesive
Case 3 Glass fiber Unsaturated Polyester Resin
Styrene Peroxide initiator Glass Fiber
Reinforced, Crosslinked Polyester Composite
For this presentation well detail the materials
needed for the third case- glass fiber reinforced
composites for pressure vessels.
Working backward from crosslinked polyester
  • Unsaturated Polyester Resin (1) which is derived
  • Maleic anhydride (2) which is derived from
  • butane (3) ( O2 VPO catalyst) which is
    derived from
  • butene (4) ( H2 Raney Ni catalyst) which is
    derived from
  • methanol (5) ( Zeolite catalyst) which is
    derived from
  • CO, H2, CO2
  • and Ethylene glycol (6) is which derived from
  • oxirane (7) ( steam) is which derived from
  • ethylene (8) ( Ag and Al2O3 catalysts) which
    is derived from
  • methanol
  • Styrene (9) which is derived from
  • ethylbenzene (10) ( Fe catalyst) which is
    derived from
  • benzene (11) ( Zeolite catalyst) which is
    derived from
  • CO2, O2, H2, H2O
  • and ethylene (12) which is derived from
  • methanol

Working backward to the basic 12 chemicals
  • And as the reaction initiator
  • Methyl ethyl ketone peroxide (13) which is
    derived from
  • 2-butanone (14) which is derived from
  • 2-butanol (15) which is derived from
  • butene
  • and hydrogen peroxide(16) which is derived from
  • sulfuric acid (17) which is derived from
  • SO2 (18) ( O2, H2O Vanadium dioxide
    catalyst) which is derived from
  • Gypsum thermal decomposition
  • and HCl (19) which is derived from
  • sulfuric acid
  • and NaCl

Soa total of 19 chemicals derived from the 12
basic chemicals have been identified for the
production of crosslinked polyester on Mars.
Summary all polymer precursor chemicals
8 inorganic chemicals
  • Proceeding in a similar fashion with the backward
    derivation of polyethylene and epoxy to the 12
    basic chemicals, we discover that we need a total
  • 8 inorganic chemicals produced on Mars
  • 30 organic polymer precursor chemicals produced
    on Mars
  • 15 recoverable catalysts imported initially from
    Earth in small quantity

15 Imported Catalysts
30 Organic polymer precursor chemicals
The analysis of each chemical reaction and the
sequencing of these reactions has been carried to
the level of detail shown on this slide and the
Aliphatic Organic Synthesis Sequence
Patent Pending
Manufacturing the glass fiber
  • Glass fiber is the least energy intensive fiber
    to produce on Mars.
  • Three main types of fiber glass
  • C glass (uncommon) used in corrosive
    environments. It is a soda-lime-borosilicate
  • E glass used in printed circuit boards. Has the
    greatest number of components.
  • S glass used in aerospace for its high strength
    and resistance to moisture. It has the highest
    strength and modulus of all these fibers and it
    is the simplest composition of only silica,
    alumina, and magnesia or simply magnesium

Since we want the strongest fiber, and it is the
simplest composition using compounds that we know
exist on Mars, we will make S glass fiber.
Homogenizing the glass composition
  • The first steps -
  • homogenizing the glass composition and
  • controlling the outflow temperature so that the
    viscosity of the drawn glass is constant

Drawing the glass fiber
  • Next steps
  • Pulling fibers from the melt
  • drawing them down from 1 mm to 10.0E-6 m, a
    reduction ratio of 100
  • Organosilane coatings are applied to protect the
    filament surfaces and also to promote better
    wetting and bonding between the glass filaments
    and the thermosetting resin during the filament
    winding process.
  • taking them up as a single strand on the forming
    winder or to fiber chopper

Manufacturing Methods for Composites
  • Using pressure and elevated temperature to aid
    infiltration of matrix around fibers
  • Autoclave Cure - Best properties, but requires
    massive pressure vessel/oven
  • VARTM (vacuum assisted resin transfer molding) -
    Uses woven dry fiber preforms and a massive
    weaving machine to create them. Best properties
    for very large structures (a/c wings) uses the
    pressure differential of 1 atm on Earth to pull
    the resin into a preform of fibers. But on Mars
    the ambient pressure differential will be 1/2
    bar or less.
  • Low pressure and low temperature cure processes
  • Filament winding
  • Open Mold processes
  • Sprayup
  • Hand layup

We will use filament winding and sprayup
Filament winding the pressure vessel modules
A Filament Winder is like a lathe with a long
cutting arm that adds material (fiber and
resin) instead of removing material The
composites filament winding area may have to be
30 m high to accommodate vertical winding of
Homestead modules A large crane is required to
support the mass and to maneuver it from vertical
to horizontal
Sprayup Method for low pressure chambers
This method of building up a 15 chopped fiber
reinforced structure could have real value for
the internal walls of low pressure underground
chambers. It is a fast and non-labor intensive
method of providing a seal.
Polyethylene Part Manufacture
  • Polyethylene can be synthesized in three steps
    (1) methane to (2) ethylene to (3) polyethylene
    pellets or flake.
  • As a thermoplastic it can be remelted and
    re-extruded as sheet, piping, bottles. Extrusion
    machines and dies are complex and will need to be
    imported from Earth initially.
  • PE is limited to use at low temperatures due to
    creep/viscoelastic deformation.
  • It is chemically resistant to the point of being
    difficult to bond to other parts except by
    welding or by mechanical joining.

Extrusion product lines are compact
  • We have analyzed the requirements to establish a
    chemical processing and polymer manufacturing
    plant on Mars capable of producing, over a period
    of 400 days, 166 tonnes of glass reinforced
    polyester composites for pressurized habitats,
    polyethylene piping and sheet, and a quantity of
    epoxy adhesive for general structural bonding
  • The route to polymer precursor formulation uses
    syntheses that do not rely on a petroleum
    precursor, the basis for much of todays chemical
  • Based on literature and patent searches, we have
    established the reaction sequence and conditions
    (temperature, pressure, catalyst, reactants,
    products) to produce the polymer end products.
  • In the process we have also established the
    production of a range of organic and inorganic
    chemicals and reagents that have other uses such
    as in the extraction and refining of metals and
    ceramics from the Mars regolith.

The authors want to express their gratitude to
Mark Homnick, Bruce MacKenzie, and Joseph Palaia
the founders of the Mars Foundation, without
whose support and encouragement this project
would not have been undertaken.
Next Step Design the Chemical Plant
  • Plant design will use several batch reactors
    that operate in different T,P ranges
  • Most reactions occur at less than 550 deg C and
    5 bar

The Next Step
  • The next step requires a chemical engineering
    plant design that is unique to Mars.
  • The reaction products must be stored and/or fed
    as reactants to the next reaction sequence.
  • Reaction chambers should be designed for
    production of several different chemical products
    that share similar reaction temperature and
    pressure conditions.
  • The reaction sequences must be prototyped to
    establish the reaction kinetics - optimum
    temperature pressure conditions, catalyst type,
    and the yield of each reaction. While many
    individual chemical processes on Earth are
    licensable, they are designed for very large
    automated, continuous production in facilities
    that occupy hundred of acres. It is not evident
    that the Mars facility can take advantage of this
    prior art.
  • The Mars Homestead chemical processing plant will
    involve a total plant size that is on the order
    of a small pilot plant on Earth.
  • Like most pilot plants The Mars Homestead
    chemical processing plant will likely use batch
    rather than automated, continuous processing of
    chemicals, and this must be accomplished in a way
    that will not be human labor intensive. It will
    of necessity require robotic support and
    automated sensing and control equipment.
  • The Mars Foundation is soliciting the help of a
    Chemical Engineering group
  • at a university or research institute.
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