Thermoplastic

promises new
The manufacture of thermoplastic composites at large volumes at reasonable cost is
the promise of the FULCRUM Thermoplastic Composite Technology. Chris Edwards of
Dow Chemical discusses the advantages of the technology and its potential markets.
pultrusion
synergies
F
ibre reinforced composites are not
new. Every undergraduate text on
materials reminds us of the Egypt-
ian use of animal hair in clay to make
tougher bricks. Yet for most users they
still have a space age and new to the
world feel. Even though we play numer-
ous sports with equipment made from
composites, the material is still the new
-kid on the block. For those who under-
stand the efficiency and potential
composites offer, the material offers a
tantalizing dream of the day when com-
posites will be as ubiquitous as wood,
steel and concrete. Yet the advancements
are relatively slow to come.
For many years Goldsworthy and
others have forecast that the advantages
Different profile shapes are possible.
brought by the use of thermoplastics,
instead of thermosets as the matrix for
composites, would be the breakthrough
to herald rapid growth and development
of new applications. We believe that to
be true but only part of the answer. The
other part lies in how composites are
used and how the industry thinks of
itself. We will attempt to deal with that
in the second half of this article.
One problem lies in
overcoming perceptions.
Thermoplastic composites
have a reputation of being
expensive relative to their
long established
thermoset cousins.
But first, the elusive thermoplastic
matrix. The reasons for the wide avail-
ability of thermoset composites and
scarcity of thermoplastic composites are
simple. An effective composite depends
on the matrix to act as a glue to surround,
adhere to and join each and every one of
its constituent fibres. Only if they are
effectively joined can- the composite
develop close to its full potential proper-
ties. The fibres within composites are typ-
ically small diameter (S-20 urn) glass,
carbon or aramid; by default the glue
needs extremely low viscosity to be able
to flow through the fibres during the
manufacturing process. Thermosets do
this well since they start lifeas monomers
or very low molecular weight species
with inherently low viscosity and only
assemble themselves into the full poly-
mer in siru, literally reacting around the
fibres to form a cohesive, three-
dimensional, cross linked ma&ix encap-
sulating all the fibres. Thermoplastics on
the other hand, start life as very long
chain molecules. Indeed, they rely on the
length of their chains for their properties
because their physical form, strength and
toughness is determined not by cross-
links between molecule chains as with
thermosets, but by the entanglement
resulting from the length and complexity
of their chains.
During normal processing for thermo-
plastics, for example by injection mould-
ing, the long chains are encouraged to
form themselves into the desired shape by
a combination of heat, pressure and shear.
The heat causes free space between the
molecules. The shear, caused as molecules
start to slide over each other, encourages
them to align thereby reducing the
entanglement and allowing the pressure
to drive them to flow into the mould.
Variations on this simple theme work
well for a multitude of plastic articles
from compact discs to car bumper facias.
Unfortunately, the very nature that makes
them so useful for injection moulding is a
huge hindrance for the manufacture of
composites (by any process but in this
instance we will focus on pultrusion).
Whereas injection moulding is an inher-
ently high pressure, high shear process
34 Rf/NFORCEDp/ustics April 2 00 1 0034-36 1710 1 I$ - see front matter 0 2001
Ekevier Science Ltd. A// rights reserved.
Thermoplastic pultrusion promises new synergies
pultrusion is just the opposite. Any
attempt to use high pressure to force the
viscous thermoplastic between the
individual reinforcing fibres is self defeat-
ing because the same pressure we try to
use to move the thermoplastic is by
default applied to the fibres and simply
pushes them closer together thereby
needing even greater pressure to cause the
polymer to flow - a vicious cycle.
Once this problem was recognized,
multiple attempts have been made to
improve the situation. Most have
focused on one of two routes:
l Dramatically reduce the viscosity of
the thermoplastic by reducing its
molecular weight. Unfortunately
while this works to an extent, it is
also somewhat self defeating since
the thermoplastic properties depend
on having a high molecular weight
and before the molecular weight
becomes low enough for convenient
processing the properties of the
thermoplastic start to fall off rapidly.
There is little point in being able to
pultrude a composite with a matrix
that will behave like candle wax
instead of a high-end polymer.
l Recognize this limitation and use
various means to assemble the poly-
mer and the fibres into such intimate
contact before melting the thermo-
plastic that it barely has to flow at all.
Examples of this route include powder
impregnation, solvent impregnation
and co-mingling of polymer and rein-
forcement fibres. All of these methods
work but bring other limitations in
terms of production flexibility and
cost.
The journey to develop the resin and
production process for FULCRUM*
Thermoplastic Composite Technology
(*FULCRUM is a trademark of The Dow
Chemical Co) started with the premise
that, while there were many lessons to be
learned from previous work, it would
never be viable to produce a composite
with low matrix properties and it was not
desirable to add steps or complexity
beyond the current process. The approach
instead was to seek out and further devel-
op ways of driving the thermoplastic
viscosity to an acceptably low level at
which it would be able to wet out fibres at
least comparably with its thermoset
counterparts. This was ultimately
achieved by the use of an engineering
thermoplastic polyurethane (ETPU) resin.
Although the ETPUs used as matrices
for Fulcrum are true thermoplastics in
the sense that they can be repeatedly
reprocessed, they also have a behaviour
not seen in most other thermoplastics -
as they are heated into their processing
range their molecular weight begins to
fall rapidly. This lower molecular weight
melt also has a very-low viscosity -
perfect for flowing between small dia-
meter fibre reinforcements. Additionally,
the urethane chemistry has excellent
affinity for glass so that the resin not
only comes into intimate contact, but
also effectively wets out and adheres to
the glass. Once the resin Ts in place and
the composite formed it is then cooled.
During this phase the reactive chemistry
of the ETPU completes the work in a
manner similar to thermosets by rebuild-
ing the mole-cular weight Pack to a
similar high level as the stating point.
The combination of the unique live
nature of the ETPU polymer and the
development of machines for its process-
ing via a process very analogous to
thermoset pultrusion have created the
means to manufacture .thermoplastic
composites in large volumes at reason-
able cost.
The advantages of composites in
general and especially thermoplastic
composites have been repeated many
times. The advantages are explained in
detail in the box on pages 37-38. The rest
of this article will explore how these
advantages are translated into a brighter
future for composites.
Once the advantages and production
capability of a new product have been
demonstrated, a long and often painful
route to the development of significant
volume sales still remains. Many exciting
new technologies fail to meet their
promise or are unjustly consigned to
niche status not because of failings in the
technology, but because of inability to
get to suitable economies of scale or
penetrate complex and often conserva-
tive markets.
The solution is complex and multi-
faceted, and the following are some of
our key learnings.
Apr i l 2001 REINFORCEDplastics 35
Thermoplastic pultrusion promises new synergies
Think big
One problem lies in overcoming percep-
tions. Thermoplastic composites have a
reputation of being expensive relative to
their long established thermoset cousins.
In part, this comes about because some
of the first thermoplastic composites
were targeted at aerospace applications
and were based on high temperature,
high performance but extremely expen-
sive resins such as polyether ether ketone
(PEEK). In part, it is also because of the
relations to price and volume produc-
tion. No company likes to enter any mar-
ket at a loss so there is a strong prefer-
ence to enter in niches capable of
supporting a higher price. The danger is
that the product becomes bogged down
in those niches and never gets the
chance to work its way into the high vol-
ume applications which have the poten-
tial to change the face of an industry.
Fulcrum technology has a strong eye on
the future and a great deal of effort has
been put into addressing the ability to be
competitive in higher volume markets.
In evaluating one specific application for
literally tens of millions of metres of pro-
file it became clear that while the cus-
tomer was extremely enthusiastic about
the performance and other benefits that
the technology brought, it had a very
strong perception, fed to it by numerous
ind-ustry experts, that a thermoplastic
composite could not be competitive
(indeed it would be fair to say that with-
in Dow we also had some initial doubts!).
Undaunted, it pressed on with a full
technology and economic assessment
and ultimately came to the conclusion
that when the true cost of materials,
large scale processing, scrap and
emissions were all factored in, the cost
was comparable. When the considera-
tion of the added design freedom of ther-
moplastic and the possibility of new
designs with higher functionality were
added, the scales tipped in favour of
Fulcrum technology.
Seek synergies
A second factor lies in the competitive
attitude towards other materials. Typically
everyone would like their product or tech-
nology to be the winning solution.
However, reality demands that the price-
performance balance of materials become
more and more onerous, which makes
it harder to succeed. An alternative is
to consider the range of existing mat-
erials, not as competitors to be displaced,
rather as opportunities to combine and
create synergies between old and new
while enhancing the overall system
performance.
One example of this lies in the use of
composites to enhance structural lumber.
Many materials attempt to compete
against lumber, but the plain fact is, wood
is one of the best and certainly most cost
effective structural materials that exists -
put simply it is cheap modulus. Compo-
sites competing against wood typically
succeed in specialized niches.
Now consider wood not as the com-
petitor, but as a material that has the pos-
sibility to be enhanced. Wood has good
properties but by no means perfect. The
thermoplastic composites have signifi-
cantly higher strength and modulus but
even allowing for this, it is not, and
never will be, a cost effective alternative
as a direct substitute for wood. However,
if instead of competing against wood we
consider combining with wood, we get a
very different answer. Small amounts of
the thermoplastic composites laminated
with wood, in the outer fibres where the
stresses are highest, can significantly
enhance the performance of the wood.
The idea is not new, Dagher and others
have been proposing this approach for
many years. Fulcrum technology takes
the synergy further with greater shape
freedom, more flexibility to use existing
industry standard adhesives and laminat-
ing techniques. In addition, it brings the
benefits of a thermoplastic matrix with
sufficient toughness and ductility to
accept the high impa& joining tech-
niques used for lumber and comply with
the variations in material dimensions
imposed by the changing moisture
content of wood.
Several major programmes are under
way with major players in the lumber
industry to develop specific products
such as laminated veneer lumber for
industrial applications.
Seek partners
Another example of seeking synergy lies
in the reinforcement of concrete. The
reason is simple; a major problem exists
with the corrosion of steel, especially in
structures that see a significant exposure
to salt environments. The salt enters
through minor fissures, accelerates
corrosion of the steel, which then
expands and causes the concrete to spa11
and crack, requiring repair or in extreme
cases leading to failure of the structure.
This application has been creating excite-
ment in the composites industry for
many years, and several companies have
thermoset composite rebar products on
the market. Whilst these currynt prod-
ucts are adequate they have some diffi-
culties in a number of key areas. One
area is the ability to make cost effective
bends. With a thermoset matrix, any
bends have to be fabricated as the bar is
being made, a relatively costly and
inflexible operation. With Fulcrum, how-
ever, it is possible to manufacture
straight bar at high speed and with great
efficiency and then post form the bar in
a subsequent operation which can be
carried out in a more localized operation
allowing greater manufacturing and
logistic efficiency. Whilst Fulcrum tech-
nology may one day be a competitor for
all thermoset rebar as well as epoxy coat-
ed, galvanized and stainless steel, the ini-
tial approach is much more aimed at
cooperation with the existing embryonic
composite rebar market. Dow is actively
engaged in setting up partnerships which
would allow the bending capability of
Fulcrum technology to be used to
enhance existing rebar systems. It is
believed that this kind of cooperative
approach, aimed at helping the growth
of the whole composite rebar industry,
will generate more success than an
antagonistic approach in which over
enthusiastic competition may delay the
broader acceptance of the whole princi-
pal of composite rebar.
36 REINFORCEDplastics April 200 1
Thermoplastic pultrusion promises new synergies
The advantages of Fulcrum thermoplastic composite technology
There are four key areas of different-
iation and advantage:
Mechanical properties
Composites of any kind are used largely
because of the enhanced mechanical
properties they offer. On a most basic
leve&?his is first of all strength and
stiffness. Unidirectional glass fibre
composites, whatever the matrix, typ-
ically achieve strengths in the range
800-1400 MPa and stiffnesses in the
range 25-40 GPa.
The thermoplastic composites pro-
duced via Fulcrum technology are no
different in this respect. The difference
however starts to be seen in some of
the second order properties, for exam-
ple impact and damage resistance.
Figure 1 shows the load/deflection
curve from a falling weight impact test
for the thermoplastic composites and a
typical thermoset composite with
similar fibre architecture. There are
two distinct differences: first, the total
area under the curve is considerably
greater for the specimen made via
Fulcrum technology; second, the load
and deflection at which the specimen
starts to accumulate damage is consid-
erably lower for the thermoset
composite.
The explanation is relatively sim-
ple. The matrix in the thermoset com-
posite has low elongation (a few %)
and is brittle. The toughness the com-
posite has is due to its ability for the
fibres to share loads and act as crack-
stoppers, however damage initiation
and ultimate failure is limited by the
crazing and failure of the low elonga-
tion, brittle matrix.
The ETPU matrix on the other
Figure 2: Nlustrotion af of f -ax i s dam& e
t ohwaac e of thermoplastic composite&
hand is extremely tough and ductile,
. .
its ultimate elongation is greater than
_ .
1000/6 though the modulus is not Others include higher
#
off-axis
significantly lower. This allows much properties (typically 2-2.5 times the
greater ability to transfer loads and equivalent thermoset system) greater
absorb deflections without initiating off-axis compliance (ability to tolerate
damage. imposed deflections without cracking
This enhanced toughness and dam- or splitting) - see Figure 2. ;,
age tolerance is just one of a
number of properties for which the Design freedom
thermoplastic matrix brings benefits. While pultrusion is one of the most
highc
efficient means for manufacture of
composites, it has one huge limitation
- it can only produce twodim&rsional
profiles.
Of course the same is true for many
other large volume production process-
es with other materials -
thermoplastic extrusion, aluminium or
magnesium extrusion, steel roll form-
ing, even wood profiles. However, all of
these other methods also offer the
possibility to post shape the final
component in other ways. Thermosets
do not easily have this possibility, any
shaping must be completed before the
resin is cured. While there are many
innovative ways to get around this
problem, it remains a fundamental
limitation of the process and one that a
thermoplastic matrix can largely over-
come. By their very nature thermo-
plastics can be heated and reformed, a
0.0 6.2 0.4 0.6 0.8 1 .o 1 .2
Dk3placement (cm)
e I: Force-defiactiott carve far thertnOprastlc composites and
zr energy absarptbtt aad later onset of &mage.
1.4 1.8-1.8 2.q
equivalent thermmets, showi ng
-J
April 200 I REINFORCEDplastics 37
Thermoplastic pultrusion promises new synergies
Figures 3 [left) and 4 (right): Nlcrstration of the feasibility of post formin@ the composites aad rbe
need to effectively manage fibre placement.
r
significant step away from the limita-
tions of their thermoset cousins.
Figure 3 shows bends formed into
1.2 cm diameter bar. This illustrates not
only the freedom but also that there are
limitations in forming even thermo-
plastic composites.
The first set of bars shows simple
bends and illustrates one fundamental
limitation of bending any kind of com-
posite - the fibres themselves cannot be
stretched or squashed in the process. If
the bend is attempted without consid-
ering that the outer part of the curve
must be longer than the inner, then the
inevitable happens: since the outer
fibres cannot stretch and the inner
fibres cannot compress they follow the
path of least resistance and the inner
fibres buckle. This is not a disastrous
limitation, even allowing for the buck-
ling, the bends still retain a substantial
1
part of their properties but since the
properties are all-important we can go
further in reducing the loss.
Figure 4 shows the same bend but
this time with more consideration to
preventing the buckling. A twist
imparted to the bar during the bending
process results in an evening out of the
fibre path lengths and almost com-
*
pletely eliminates the buckling result-
ing in a more efficient use of the com-
posite. This illustrates the effect for a
simple bend. Ongoing development
work is creating the techniques and
equipment necessary for creating more
complex geometries and shaping more
difficult proflles.
The ability to form either post
pultrusion or during the pultrusion
38 REINFORCEDplastics April 200 1
process itself is one of numerous tech-
niques that have been developed for
Fulcrum to enhance a designers free-
dom to create innovative new design
solutions. -
Others include the ability to over-
mould and over-extrude, new jointing
and adhesion methods such
as heat staking, ultrasonic welding,
wider availability of suitable adhesive
packages and their use as localized
reinforcement.
Environmental benefits
Perhaps the greatest environmental
advantage of composites in general is
their extremely high specific properties.
They enable increased efficiency by
reducing component weight thus
reducing the energy required to accel-
erate and decelerate it.
The automotive industry widely
recognizes this and increasingly turns
to composites for reduced weight to
meet increasingly strict fuel economy
targets; however, the_. average tennis
player can appreciate the enhanced
efficiency just as well in larger, lighter,
higher performing racquets.
In addition, composites are relative-
ly energy efficient to produce, com-
pared with lightweight metal alluys.
However, there are two areas where
existing composites fail the envlron-
mental hurdle: they typically have high
volatile organic compound (VOC)
emissions during production and are
relatively difficult to recycle in any
meaningful way.
Until recent years, both of these
were considered relatively unimportant
and were easy to dismiss; however, as
emissions standards become more
stringent and disposal becomes not
only more expensive but also less
socially acceptable, it is becoming more
important for composites to overcome
these hurdles too.
Most thermoplastic composites
have low to zero emissionsi during
production and can be considered
recyclable. Work on KllcrUm
composites has demonstrated that not
only would the composite be reeclable
but in many applications post-
industrial scrap, from cut-outs * vr off-
cuts for example, is actually a gluable
resource. It is capable of being reused in
injection or compression m&ding
applications and brlnglng properties
comparable with some of the; work-
horse structural resins of the mdustry
such as glass filled polyamide. .
Production capability
In general composites reside at the high
performance, low volume end !of the
materials market. One reason for this is
that they are relatively expensive, but
the history of multiple new materials
has shown that todays expensive niche
can be tomorrows large volume mat-
erial if produced in sufficient volume.
But to cross that threshold into volume
production and to be able to: drive
down the cost-experience curve needs
the ability to produce efficiently in
large volumes.
Thermoset composites are some-
what limited in this respect. The in situ
reaction of monomers which allows
efflclent wet-out of fibres itself becomes
a limitation to production speed. The
time and temperature necessary to
complete the thermoset reaction
control the process. Typically this
means line speeds in the range of 0.9-
1.8 m/min (3-6 ft/min), whereas
Fulcrum technology has demonstrated
line speeds in excess of 9 mfmin
(30 ft/min) and has the capacity to go
even faster.
A further example of cooperation
and the advantages of a broad approach
to the market lies in licensing. Fulcrum
technology has already been licensed a
number of times to a broad base of
processors, including Polygon Co
(South Bend, Indiana, USA), Bemis
Man-ufacturing (Sheboygan Falls, Wis-
consin, USA) and Top Glass (Milan,
Italy).
In addition to licensing the tech-
nology, Dow also assists in finding and
developing applications for it. A typical
example, though not yet commercial, is
Bete Flemming, a supplier of sailboat
batons. When it approached Dow to
discuss the possibility of manufacturing
the batons via Fulcrum, Dow quickly
recognized the potential of the tech-
nology in the application and the fit
between the companys requirements
and the capabilities of Bemis Manu-
facturing. Dow brought the two compa-
nies together, and within a few weeks
Bemis had built a new die and supplied
the first experimental product to Bete
Flemming. Dow continues to assist,
providing help in the methods of form-
ing and fabricating of the final parts.
We are all looking forward to the day we
can celebrate the success of the applica-
tion on a sailboat while watching the
wind fill the sails to the perfect airfoil
generated by the sail batons made with
Fulcrum!
Dow also tries to use all efforts possi-
ble to help speed the success of the
licensees. Top Glass already had a clear
vision of a number of applications when
it began building its line but initially no
ability to supply product. One of its
applications is the forming of rods into
complex components for agricultural
machinery. To speed up its development
efforts Dow supplied the company
product for prototype fabrication by its
customer. This allowed the prototyping
to go on in parallel with Top Glass build-
ing what we hope will be the first of
many lines.
The exchange is not just one
way. Polygon, the first licensee of the
Thermoplastic pultrusion promises new synergies
technology, has also supplied product
to Dow on many occasions to augment
our capabilities and enable testing of
profiles which Dow did not currently
have the ability to produce.
As all of these developments come
to fruition, Fulcrum has the ability not
only to enhance the capabilities of the
existing industry but to dramatically
increase its size. Our aim is not to
compete against thermoset composites,
but to seek and bring to fruition multi-
ple applications new to the world of
composites. One day with the help of
our partners, licensees (and even our
competitors) we believe the. thermo-
plastic composites industry will match
and surpass the existing thermoset
composites industry. n
Chris Edwards, Dow Plastic& tel: +l-
517-636-l 025; fax: +l-517-638-9845;
e-mail: cedwards@dow.com; website:
www.dowfi&um.com.
Dow Plastics+ delivers this long-SQught
combination! Using a unique engineering
thermoplastic polyurethane matrix, weve
bent the rules of composite technology
to create a new-to-the-world composite
and manufacturing system.
Toughness and damage tolerance.
Weight and cost advantages. Greater
productivity and design freedom.
FULCRUM Thermoplastic Composite
Technology is an extremely attractive
alternative to many traditional structural
materials, including wood, aluminum,
steel, and thermoset composites.
Not only do we bend the rules, we will
bend over backward to help you take
advantage of this exciting breakthrough.
To receive technical information, a sample
of the product, newsworthy items, and
tradeshow participation, please visit our
website at: www.dowfulcrum.com.
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April 200 1 REINFORCEDplastics 39