PROCESSING THERMOPLASTIC 24

COMPOSITES
James L. Throne

24.1 INTRODUCTION
Machinery

Thermoplasticpolymers are seldom converted

into products without the time-dependent Product Requirements Shape or P a r t
Production
application of temperature, pressure, shear or Requirement
Electrical
other types of mechanical manipulation. The Environmental
mechanical manipulation of plastics is called Rigidity
Tempera tu r e
'polymer processing'. Many polymer Possible
processes and combinations of polymer Polymer Families Processes

processes are used in modern commercial

manufacturing. The selection of a process to
produce a thermoplastic polymer product
from pellets, powder, or other granular forms

I ti
begins with general characteristicsof the prod-
uct itself. The two primary concerns to be met F i b e r Type
F i b e r Length
in the manufacture of any polymer product Other Adducts

are:
0 Will the finished part meet all required, Concerns

specified and desired design criteria? I

0 Can the product be produced at the mini-
mum cost for the projected market size?
The first concern focuses primarily on the
ability of the polymer to meet mechanical and
environmental challenges throughout its func-
tional lifetime. This is shown as the left branch
of the Fig. 24.1 schematic'. The second concern
deals with the economic ability to process the
acceptable polymers into the useful product,
and this is shown as the right branch of Fig.
24.1.
Commercial polymers are rarely pure. Even
'neat' polymers or polymers that contain no
Handbook of Composites. Edited by S.T. Peters. Published
in 1998by Chapman & Hall, London. ISBN 0 412 54020 7
Compound Grades
I
Economics 1
F i n a l Polymer
Fig. 24.1 A schematic for choosing the proper poly-
mer and an attendant process'.
fillers, reinforcements or foam cells, usually
have one or more adducts or additives that
alter the basic characteristics of the polymer.
Table 24.1 gives a short list of some of the
adducts used with thermoplastics*. Some of
these, such as coupling agents, are vital in
achieving the desired final solid mechanical
performance of other adducts, such as fillers
and reinforcements. Typical fillers used in
526 Processing thermoplastic composites
Table 24.1 Adducts in thermoplastic polymers’
Antioxidants
Antistatic agents
Colorants and pigments
Coupling agents
Flame retardants
Fillers
Foaming agents
Heat stabilizers
Mold release agents
Odor suppressors
Plasticizers
Processing aids
Emulsifiers
Lubricants
Reinforcing fibers
Ultraviolet stabilizers
Viscosity depressants
thermoplastic polymers are given in Table
24.23. Typical fibrous reinforcements used in
thermoplastic polymers are given in Table
24.34. Filled, reinforced and foamed thermo-
plastics offer great breadth of solid mechanical
properties. In many cases, they offer substan-
tial processing challenges, as well. Nearly all
thermoplastic processes shape the polymer in
its fluid state (The most notable exception to
this is thermoforming, where forming occurs
when the polymer is in a rubbery state.
However, thermoforming depends on the pro-
duction of sheet that is produced by
calendering or extruding the polymer in its
fluid state.) Fillers and reinforcing fibers
increase the viscosity of the polymer, making
it more difficult to shape. As expected, pro-
cessing difficulty increases with increased
filler or reinforcement loading.
There are more than twenty major types of
polymer processes5.Not all these processes are
suitable for thermoplastics and not all thermo-
plastic processes are suitable for filled,
reinforced or foamed thermoplastics. Table
24.4 lists most of the thermoplastic processes
that are used with neat, filled or reinforced
poIymers. Several of these processes are dis-
cussed in detail shortly. As is apparent, fillers
and fibers increase the polymer processing dif-
ficulty. In certain instances, as with continuous
reinforcing fibers, conventional thermoplastic
processing cannot be used.
Part geometry is one way of classifying suit-
able polymer processes, Table 24.56. This
classification is further amplified in Table
24.67. Again, not all these processes are suit-
able for processing all polymers with all
combinations of fillers or reinforcements. As
noted in Fig. 24.1, the cost of the polymer is
only one aspect of the overall economics of
product manufacture. Table 24.7 gives a rela-
tive comparison of the process costs for filled
and reinforced polymers8.
Extrusion and injection molding are the pri-
mary methods for producing foamed, filled
and discontinuous-fiber reinforced thermo-
plastics. As an example of the growth in
molding thermoplastic composites, in the
1950s esentially all injection molded thermo-
plastics were neat or unfilled and
unreinforced. By the early 1990s, filled,
foamed and reinforced polymers accounted
for,more than 25% (wt) of all injection molded
parts. In certain instances, blow molding and
rotational molding are possible.
Thermoforming or rubbery sheet deformation
is now being applied to continuous fiber rein-
forced polymers. These processes are
described below, with the objective of compar-
ing general operating conditions of neat
polymers with thermoplastic composites. The
technical details of these processes are given
elsewhere9-I4.Two axioms apply:
0 Axiom I: If the neat polymer is processed in
conventional polymer processing equip-
ment, composite versions of that polymer
are usually processed in adapted or modi-
fied versions of that equipment.
0 Axiom 11: Processing is always more diffi-
cult with composite versions of processable
neat polymers.
An important corollary also applies:
 Rheology,fiber flow and fiber orientation 527

Table 24.2 Fillers for thermoplastic polymers3

Silica products Metallic oxides

Minerals Zinc oxide
Sand Alumina
Quartz Magnesia
Novaculite Titania
Tripoli Beryllium oxide
Diatomaceous earth Aluminum trihydrate
Synthetic amorphous silica
Wet process silica Other inorganic compounds
Fumed coloidal silica Barium sulfate
Silica aerogel Silicon carbide
Molybdenum disulfide
Silicates Barium ferrite
Minerals Mica
Kaolin (China clay)
Mica Metal powders
Nepheline silicate Aluminum
Talc Bronze
Wollastonite Lead
Asbestos Stainless steel
Synthetic products zinc
Calcium silicate Carbon
Aluminum silicate
Carbon black
Glass channel black
Glass flakes Furnace black
Hollow glass spheres Ground petroleum coke
Cellular glass nodules Pyrolized products
Glass granules or cullet Intercalated/exfoliated graphite
Calcium carbonate Cellulosic fillers
Wood flour
Chalk
Limestone Shell flour
Precipitated calcium carbonate Comminuted polymers

0 Corollary I: Adding foam, fillers or rein- economic importance of polymer processing

forcements to neat polymers will never
improve their processability.
24.2 RHEOLOGY, FIBER FLOW AND FIBER
ORIENTATION
Rheology is the study of polymer flow. Shear
flow and elongational flow dominate polymer
processing. The great length of polymer chains
results in extensive entanglements and com-
plicates the study of neat polymer flow. The
and the technical challenge of predicting
molten polymer response to applied load have
resulted in an incredibly rich literature15z1.
Neat polymer melts are considered as vis-
coelastic non-Newtonian fluids. Viscosity is
the measure of fluid resistance to applied load.
The viscosities of oil and water are material
constants, independent of shear rate. Fluids of
this type are called Newtonian fluids. In
steady-state shearing flow, polymers typically
exhibit shear-dependent viscosities, as with
528 Processing thermoplastic composites

Table 24.3 Fibers for reinforcing thermoplastics differences. Shear rate-dependent viscosity
and normal stress differences represent poly-
Cellulose fibers mer material functions and are not material
a-Cellulose constants.
Pulp preforms
Cotton flock
Jute
Sisal
Rayon 'p
a
Synthetic organic fibers
Polyamide (nylon, PA)
Polyester (PET)
Polyacrylonitrile(PAN)
Polyvinyl alcohol (PVOH)
E
v)

Carbon fiber l o 2 2

Asbestos fiber m-' mo m1 lo2 m3

Shear Rate, s-'
Fibrous glass
Filaments Fig. 24.2 Shear-rate dependent viscosity of low-
Chopped strand density polyethyleneat 180°C(356°F) with titanium
Reinforcingmat dioxide filler in volume YO.(Adapted and redrawn
Glass yarn from Ref. 22 by permission of the Academic Press.)
Glass ribbon
Whiskers
Aluminum oxide (Corundum)
Titanium dioxide The inclusion of particulates further compli-
Boron cates the rheological behavior of polymers
Boron nitride (Fig. 24.2). The effect of filler loading on
Boron carbide steady-state shear viscosity of polymers is
Metallic fibers approximated by:
Aluminum
Stainless steel zw = Y + K j " (24.1)
Copper
Tungsten where zw is the shear stress at the wall, f is the
shear rate, and Y, K and n are empirical con-
stants. This Hershel-Bulkley is the
power-law equivalent of the Bingham model
for Newtonian plastic fluids. As anticipated,
low-density polyethylene in Fig. 24.2=. When increasing particle surface area to volume
the shearing force on a Newtonian fluid is increases the viscosity of the polymer, even at
released, the fluid resistance instantaneously the same loading level and particle size distri-
ceases. When the shearing force on a poly- bution (Fig. 24.325). Increasing particulate
meric fluid is released, the fluid exhibits a loading levels usually decreases polymer vis-
measure of time-dependent reorganization, coelasticity as measured by the first normal
the extent of which depends on the extent and stress difference (Fig. 24.426).
duration of the applied forces. Viscoelastic flu- It has been suggested that the shear-rate
ids exhibit fading memory of deformation dependent viscosity of particulate and fiber-
history. This is manifested by normal stress filled polymers can be predicted from a
 Xheology,fiberflow and fiber orientation 529

Table 24.4 Effect of adduct type on thermoplastic polymer processability

Degree of difficulty (0 = Easy, 9 = Difficult, X = Not done)

Polymer process Neat Filled" Short-fiber Longlfiber Continuous Continuous
reinforced reinforced organicfiber inorganic
reinforced fiber
reinforced
Extrusion 0 3 5 8 b b
Sheet
Single screw
Extrusion 5 8 b b
Profile
Single screw
Extrusion 4 5 b b
Profile
Twin screw
Extrusion 5 7 b b
Compounding
Twin screw
Extrusion 2 5 8 X X X
Foam
Pultrusion X X X X 9 8
Injection molding 1 3 6 8 X X
Injection molding 2 4 7 X X X
Foam
Blow molding 2 X
Thermoforming 1 9
Compression molding X 5
Rotational molding 2 X

a Short aspect-ratio adducts.

Pultrusion replaces conventional extrusion for continuous filament thermoplastic polymers.

temperature-invariant master curve: polymer temperature needed for the viscosity

determination (K),T, = Tg + 50 (K), and T is
MFI, -
log,oMFL, - the glass transition temperature (K)27. &e
1 experimental results for many polymers and
8.86 (T, - Ts) 8.86 (T, - Ts) filler and fiber types show good agreement
- with the master curve.
101.6 + (T, - Ts) 101.6 + (T, - Ts) (24.2) Blow molding and thermoforming are poly-
where MFI is the melt flow index determined mer processes that employ melt or rubbery
using a melt flow indexer die of L / D = 3.8, phase stretching. Elongationalviscosity shows
according to ASTM D1238. T , is the ASTM rec- an increase in value with increasing filler load-
ommended test temperature (K), T2 is the ing in a manner similar to shear viscosity, Fig.
530 Processing thermoplastic composites

Table 24.5 Part geometry as means of classifying

processes for filled and reinforced thermoplastic
polymers6

Linear forming
Extrusion (sheet)
Extrusion (profile)
Pultrusion
Formation of a solid body by injecting
into a cavity
Unfoamed injection molding
Foamed injection molding
Formation of a hollow object
Blow molding
Rotational molding
Sheet forming
Thermoforming

24.528.As a first approximation, the elonga- 104 I , I , , , I 1 I , 1 1 1 1 ,

tional viscosity for filled polymers is 10-2 10-l 100

determined in a fashion similar to that for
shear viscosities, using equation (24.1)29.For
many neat polymers, the elongational viscos-
ity is proportional to three times the shear
viscosity. For filled polymers the proportional-
ity is substantially greater than three and is
usually shear rate-dependent34
Fiber flow in a shear field is far more com-
plex than particulate flow. Independent fiber
closed-orbit rotation as a consequence of
shear is dominant in very dilute suspensions.
Shear Rate, s-’
Fig. 24.4 Shear-rate dependent first normal stress
difference for polystyrene at 180°C (356°F)with car-
bon black filler in volume %. (Adapted and
redrawn from Ref. 26 by permission of Academic
Press.)
As fiber concentration increases, fiber interac-
tion inhibits independent fiber motion. At
moderately high fiber concentration or for

Fig. 24.3 Shear-rate dependent vis-

)
cosity of polypropylene at 200°C
(392°F) with two types of fillers
having particle sizes of 44pm or
less. (Adapted and redrawn from
m3
m-3 m-* 1 6 o, , , Ref. 25 by permission of Academic
Shear Rate. s 1 Press.)
 Thermal properties offlled and reinforced thermoplastics 531
005 01 02 03 0 4 05 07
Elongation Rate, s”
Fig. 24.5 Elongation-dependent elongational vis-
cosity for polypropylene at 200°C (392°F) with
calcium carbonate in volume %. (Adapted and
redrawn from Ref. 28 by permission of Academic
Press).
long fibers, fiber interaction acts to momen-
tarily align fiber segments into bundles. The
nature of the polymer flow field then deter-
mines whether these momentarily aligned
fiber bundles remain oriented as the product
is produced. Increased shear implies
increased fiber interaction. Fibers not oriented
in the flow direction are subjected to
increased bending stresses around the fiber
bundles. The result is fiber length degrada-
tion. In addition to increased normal stress
difference with increasing fiber loading, fiber
reinforced polymers exhibit substantial shear
stress and normal stress difference overshoot
at flow inception. These overshoots are attrib-
uted to the interactions of fibers moving from
an isotropic random state to the more ordered
shear flow state31. Depending on flow
strength and fiber aspect ratio and volume
fraction, these overshoots can be sustained for
several minutes.
24.3 THERMAL PROPERTIES OF FILLED AND
REINFORCED THERMOPLASTICS
Most polymer processes depend on energy
interchange between the environment and the
interior of the melt or solid polymer. Fillers,
reinforcing fibers and cells dramatically affect
the thermal properties of polymers. Typically,
polymers have lower thermal conductivities
than inorganic fillers and fibers and higher
thermal conductivities than gases that are
used as foaming agents. Thermal conductivity,
heat capacity, density and thermal diffusivity
are the most important.
24.3.1 THERMAL CONDUCTIVITY
10
Both the solid and fluid thermal conductivities
of a filled polymer depend on the relative filler
content and the shape of the filler. The
Halpin-Tsai equation modified by N i e l ~ e n ~ ~
yields useful values:
kc - 1+AB$ (24.3)
kP 1 - BO$
where A = kE - 1, and & is the Einstein coeffi-
cient, Table 24.833. $ is the filler volume
fraction, P is the maximum packing fraction,
Table 24.9%, k, is the thermal conductivity of
the composite, kp is the thermal conductivity of
the neat polymer, and kf is the thermal con-
ductivity of the filler. B and (T are given as:
(24.4)
(24.5)
The Einstein coefficient, k,, is a measure of the
shape of the filler particle. kE = 2.5 for regular
shapes such as spheres and becomes large for
fibrous or acicular particles. The packing frac-
tion, P, for uniformly sized particles varies in
value from 0.52 for random packing to 0.91 for
532 Processing thermoplastic composites

Table 24.6 Classification of polymer processes by size and shape for filled and reinforced thermoplastic
polymers7
_______

Processes 2 2 3 4 5 6 7 8 9 2 0 2 1
Blow molding Hollow, Platen x x X X
thin
wall
Calendering Sheet Width of X X
roll,
Compression molding Platen X X X x x x
Sheet extrusion Sheet Width X X
of roll,
Die
Profile extrusion Linear Die X
Injection molding Platen X X X x x x x x
Injection molding Platen X X x x x x x
(foam)
Pultrusion Linear Die X
Rotational Hollow X x x x x
Molding
Thermoforming Thin wall Platen X X
1 = Shape limitation
2 = Factor limiting maximum size
3 = Complex shapes
4 = Controlled wall thickness
5 = Open hollow shapes
6 = Closed hollow shapes
7 = Very small items
8 = Plane area greater than 1m2
9 = Inserts
10 = Molded-in holes hexagonal packing. For fillers with random
11 = Threads sizes, P is typically about 0.85 to 0.9.
Thermal conductivity is a tensor quantity,
with unique values in each of the three princi-
pal directions. Because filled polymers are
Table 24.7 Ranking of polymer processes according relatively isotropic, the principal values of
to unit costs thermal conductivity are usually equal. For
continuous carbon graphite filament compos-
Process cost ites, the thermal conductivity in the fiber
direction is usually much greater than that in
Calendering
Injection molding Very low the transverse directions. The packing frac-
tions are determined from Table 24.9 for the
Blow molding fiber and crossfiber directions. For random
Foam injection molding mats, the typical packing fraction value is
Profile extrusion Low
Rotational molding about 0.5 in the cross-fiber direction.
Sheet extrusion
Thermoforming 24.3.2 HEAT CAPACITY
Compression molding Medium
The polymeric heat capacity or specific heat is
Pultrusion the isobaric change of enthalpy with tempera-
Machining High ture:
 Thermal properties of filled and reinforced thermoplastics 533

Table 24.8 Values of the Einstein coefficient, k,, for various types of fillers33

Filler type k,"

Spheres, one size, maximum packing 2.50
Spheres, random close packing 2.50
Spheres, random loose placing 2.50
Rods or ellipsoids, random packingb
Aspect ratio = 2 2.58
=4 3.08
=6 3.80
= 10 5.93
Mixed sizes, irregular shapes, minimum surface area 4.00
Mixed sizes, plates flakesc 5+
Agglomerates of spheresd 2.5/$,
Agglomerates, generally'. kd40
a
Correction factors for the mechanical case of Poisson's ratio, Y , of the matrix:
V Factor
0.50 1.00
0.40 0.90
0.35 0.87
0.30 0.84
0.20 0.80
At high rates of shear and low @a, for the rheological case, these shapes tend to orient and to reduce &.
These values may be approximated from oil absorption data or more precisely determined by intrinsic viscosity.
@, is the volume fraction of the agglomerate that is spherical.
e
@ is the volume fraction of particles in the agglomerate and k, is the appropriate value for the particle shape.
These values are generally less than the maximum packing fraction for the particular particle shape.

Table 24.9 Effect of filler particle shape and packing type on maximum
packing fraction, P, for uniformly sized particlesM

Particle shape Packing type Maximum packing fraction, P

Sphere Hexagonal close packing 0.7405
Sphere Face-centered cubic 0.7405
Sphere Body-centered cubic 0.60
Sphere Simple cubic 0.5236
Sphere Random close packing 0.637
Sphere Random loose packing 0.601
Fiber Parallel hexagonal packing 0.907
Fiber Parallel cubic packing 0.785
Fiber Parallel random packing 0.82
Fiber Random orientation 0.52

are constant. The enthalpies of most amor-

= (%) P
(24.6) phous polymers such as polystyrenics, acrylics
and polyimides are nearly linearly dependent
The specific heats of fillers and reinforcements on temperature and so their specific heats are
534 Processing thermoplastic composites
nearly constant. Semicrystalline polymers
such as polyolefins, liquid crystal polymers
and polyketones have enthalpies that exhibit
the effects of melting and so their specific
heats are temperature-dependent. The specific
heat of a mixture of materials is given as:
(24.7)
where xi is the weight fraction and cp, is the
specific heat of the ith species.
24.3.3 COMPOSITE DENSITY
The density of a mixture of materials is given ( L / D ) ratios range from 15:l to 48:l with 18:l
as:
(24.8) schematic of a typical singlescrew extrudes6.
where pc is the density of the mixture, xi is the ing four sequential segments37,38:
weight fraction and pi is the density of the ith
species.
24.3.4 THERMAL DIFFUSMTY
Thermal conductivity is the key material prop-
erty in steady state heat transfer. The heat flux,
9, is proportional to the thermal driving force
as:
dT
9 =k- (24.9)
dx
where T is temperature and x is distance
through the composite.
The proportionality is thermal conductivity.
In transient heat transfer, thermal diffusivity is
the proportionality, as:
(24.10)
where t is time and a is thermal diffusivity,
given as:
a = - -k- - (24.11)
PCP
For most filled and reinforced polymers, ther-
mal diffusivity increases with increasing
adduct loading. Thermal diffusivity also
increases with increasing void fraction in cel-
lular composite^^^. As a result, the rates of heat
addition and of heat removal increase with
increasing adduct loading.
24.4 EXTRUSION
Extrusion is a means of producing continuous,
linear products in a steady state fashion. Both
single-screw and twin-screw extrusion
processes are used to produce sheet and pro-
files from composite thermoplastics.
Single-screw extruder length-to-diameter
to 30:l being usual. Twin-screw extruder L / D s
range from 12:l to 30:l. Figure 24.6 is a
The process is generally characterized as hav-
0 Solids conveying, where the polymer pel-
lets, flake, powder or granules are conveyed
from the extruder hopper to the conveying
flights of the extruder. The particulates are
compacted and begin to heat by shearing
contact with the metal screw and barrel.
Table 24.10 tabulates the polymer character-
istics that are important during solids
conveying. Methods of determining some
of these properties are discussed in Sections
24.2 and 24.3.
0 Plasticating or melting, where the gap
between the barrel and the root of the screw
is reduced, the polymer melts and the com-
pressed solid cake breaks up. The degree of
compression usually depends on the mor-
phological nature of the neat polymer.
Crystalline polymers need greater compres-
sion ratios than amorphous polymers.
Polymers with particulate adducts need a
lower compression ratio than neat poly-
mers. Table 24.10 also includes the polymer
properties that are important in plastica-
tion.
0 Melt pumping, where the fully fluid
polymer is pressure- and temperature-
 Extrusion 535

Table 24.10 Polymer properties important in extrusion

Solids conveying
Frictional coefficients of particulate polymers with various metallic surfaces
Temperature-dependent thermal properties of particulate polymers:
Thermal diffusivity
Thermal conductivity
Heat capacity
Bulk density
Polymer density
Temperature dependent modulus of polymer
Temperature dependent yield strength of polymer
Plasticating
Temperature dependent and shear rate dependent melt viscosity,
Density of polymer melt
Density of polymer cake in solid bed
Polymer melt thermal conductivity
Melt pumping
Melt viscosity dependency on
Temperature
Shear rate
Pressure
Polymer melt thermal conductivity
Viscous dissipation
Thermal and shear degradation potential
Extruder die
Polymer shear sensitivity
Degradation potential - temperature limitation
Melt fracture potential
Extrudate swell
Rheological characteristics
Normal stress difference
Temperature dependent elongational viscosity

conditioned for the extruder die. The pri-
mary polymer property is shear viscosity.
Other important properties are given in
Table 24.10.
0 Extruder die, where the polymer melt is
shaped a n d presented to the take-up
equipment39. The extruder die shape
depends on the product being produced.
For example:
- if the extruder die is slot-like, the result-
ing product is a planar sheet;
- if the extruder die is cylindrical, the
resulting product is a rod;
- if the extruder die is annular, the result-
ing product is a hollow pipe or tube. This
tube or pipe is also a parison for extru-
sion blow molding;
- if the extruder die is irregular, the result-
ing product is called a profile. Some of
the major polymer properties that are
important in profile extrusion are given
in Table 24.10.
Extrusion dies are dissipative. That is, the
polymer exhibits pressure drop through the
die equal to that provided at the tip of the
extruder screw.
536 Processing thermoplastic composites

\ H o m b F e e d Throat Thermocouple Well Barrel

I I 'Main Thrust Bearing

Heate; Band

Q
Motor

Fig. 24.6 Schematic of conventional single screw extruder without extrusion die. (Redrawn from Ref. 36 by
permission of Carl Hanser Verlag.)

Twin-screw extruders are used extensively
in producing linear composite products. Figure
24.7 is an illustration of a cylindrical intermesh-
ing twin-screw d e ~ i g n ~ ~ lTwin-screw
~l.
extruders are classified according to the relative
screw rotational directions, whether the screws
intermesh and the relative screw speeds, Table
24.11. Comparative twin-screw performance is
given in Table 24.12. Despite some important
shortcomings, twin-screw extruders are desired
for low shear and controlled feed rates, impor-
tant aspects of compounding composite
thermoplastics as well as extruding them into
uniformly consistent products.
Increasing time in the shear field results in a
linear decrease in fiber length (Fig. 24.847).
Fiber length degradation is much less influ-
enced by screw speed than mixing time. As a
result, twin-screw compounding extruders
provide less fiber length degradation than do
tandem compounding single screw extruders.
In fiber-reinforced extruded products, the
average fiber orientation for discontinuous
fibers is up to about 20" from the axis4s.The
orientation is the result of converging flow
from the extruder screw tip to the die end.
(Converging flow is one of the standard die
design critia for neat polymer extrusion.
Accelerating flow allows molecuIar alignment
in the axis direction and tends to minimize
extrudate swell shear d e ~ e n d e n c y ~ ~ . )
Extrudate swell decreases with increasing

Cornpresnion Precompression
Metering Gas-Meit Mixing Preheating Feed
I_ \ I L & L
I- I I

Fig. 24.7 Schematic of standard configuration of cylindrical twin screws40.(Redrawn by permission of Carl
Hanser Verlag.)
 Extrusion 537

10
I 1 I I
0 10 20 33 40
TiO, Volume Percent 96

Post-Injection Molding
Fig. 24.9 Effect of volume fraction of titanium diox-
m ide on extrudate swell ratio for high-density
0 e polyethylene at 180°C (356°F). Capillary L / D = 28
and shear rate = 10 s-l. (Redrawn from Ref. 50 by
permission of Academic Press.)
05 10 15 2.0 ' 25

Mixing Length, Diameters

Fig. 24.8 Effect of residence time in shear field on

glass fiber length in injection molding and extru-
~ion~ (By
~ . permission of Society of Plastics
Engineers.)

Table 24.11 Classification of twin-screw extruders

Intermeshing screws'
Corotating screws
Low speed extrusion for profiles, foams, filled polymers, short-fiber profiles
High speed extrusion for compounding and devolatilization
Counter-rotatingscrews
Conical extrusion for profiles
Cylindrical extrusion for profiles
Non-intermeshing screwsb
Counter-rotating separated screws
With blades for kneading, compounding
High speed for in situ polymerization
Corotating screws
Not used in practice
Counter-rotating tangential screws
High speed for compounding, devolatilizing
Low speed for plasticating fluffy, bulky regrind
a
Intermeshing screws are also classified as h l l y or closely intermeshing or partially intermeshinp
Non-intermeshing screws are also classified as separated non-intermeshing and tangential non-intermeshing
screws4z.
538 Processing thermoplastic composites
filler loading (Fig. 24.950)and with increasing
fiber orientation in the hoop direction.
Orientation in the extrusion direction is
desired for profiles that are designed for
strength in the bending direction. For pipe and
tubing, on the other hand, the strength in the
hoop direction is half that in the axial direction
for an isotropic polymer. Reinforcement and
hence fiber orientation is desired in the hoop
or cross-extrusion direction. This is achieved
by using a diverging die section following the
converging section (Fig. 24.1O5I).The amount
*-
Annular Die
Fig. 24.10 Expanding mandrel extrusion die with
converging section for extrusion of highly fiber-
reinforced polymers. (Redrawn from Ref. 50 by
permission of Society of Plastics Engineers.)
Hopper
f r l
\
Plasticating Screw
Nozzle
Non-Return Valve
Fig. 24.11 Schematic of plasticating and injection portion of conventional reciprocating screw injection
molding machine. The nozzle inserts into the sprue of the mold mounted on the press shown in Fig. 24.12.
(Redrawn from Ref. 55 by permission of Carl Hanser Verlag.)
of hoop reinforcement is related to the channel
width expansion52.
24.5 INJECTION MOLDING FILLED AND
REINFORCED THERMOPLASTICS
Injection molding is a means of producing dis-
crete products on a cyclic b a ~ i s ~The ~,~~.
injection molding machine consists of two
major parts: the plasticating and pumping sec-
tion, and the clamping mechanism.
24.5.1 THE PLASTICATING AND PUMPING
SECTION, FIG. 24.1155
A single Archimedean screw similar to an
extrusion screw acts to convey and compress
the solid thermoplastic, plasticate and melt the
polymer and melt convey or pump the poly-
mer melt through a non-return valve or check
ring to an accumulation region ahead of the
screw. As the polymer accumulates between
the screw tip and the nozzle, it pushes the
screw backward away from the nozzle, effec-
tively shortening it. When a suitable amount
of polymer is accumulated, the mold is closed,
the nozzle abuts the sprue, the screw advances
and the melt is pushed into the mold. Injection
molding screws have L / D ratios of 15:l to 30:l.
Hydraulic Piston
W
\
Frame Electromechanical Drive
 Injection molding filled and reinforced thermoplastics 539

Table 24.12 Advantages and disadvantages of twin-screw extrudersM

Advantages
Controlled compaction of powders in feed zone
Powder feeding independent of friction with screw or barrel
Starved feed decouples feed rate, screw speed and extent of viscous shear heating
Rapid but gentle heating and plasticating of thermally sensitive polymers
Kneading action provides superior thermal and melt mixing and homogenization
Control of pressure build-up by proper element selection
High outputs at low speeds, minimizing shear heating
Ability to custom design processing sections
Gas injection easy to locate
Addition of adducts, fillers, reinforcing elements relatively straight forward
Comparatively little wear on extruder elements when processing aggressive fibers, fillers
Comparatively little fiber attrition
Disadvantages
Equipment cost per unit output very high
Output limited when compared with tandem extruders
Screw wear harder to predict
More difficult to mix gases into polymer melts in direct gas injection
Maintenance tends to be specialized, expensive
Although flexibility in changing mixing elements touted, no real way of determining a priori what
mixing elements are best for optimum throughput"
Pressure build-up entering the die is less effective
The thrust bearing remains the primary mechanical weakness
a Recently, computer models have been developed to aid in understanding polymer flow in certain elements such as for-
ward pumping screw elements, backward pumping screw elements and kneading disc elements45.Owing to the
complex geometry, twin-screw extruder configuration and element design has not achieved the sophistication of sin-
gle screws46.

The length ratio of solids conveying to plasti-
cating to melt pumping is 50:25:25. Injection
molding screw compression ratios are usually
the same as those for extrusion.
24.5.2 THE CLAMPING SECTION
Figure 24.1256shows a fully hydraulic clamp,
one method of holding the mold halves closed
against the pressure of the injecting melt. The
clamp consists of a stationary platen and a
moveable platen. The platens are guided open
and closed along tie bars. The polymer is intro-
duced through the sprue, a hole in the
stationary platen. The moveable platen con-
tains a means of applying pressure to hold the
mold halves closed. Hydraulic and mechanical
methods are common means although new
electric drives are considered to need less
maintenance. In addition, means for ejecting
the part from the mold cavity are usually
attached to the moveable platen. The polymer
is transferred from the accumulator section of
the screw into the mold cavity by ram-
advancement of the screw at relatively high
shear rates of 100-10000 s-l, with transfer
times of seconds. Since polymers are com-
p r e ~ s i b l eat~ ~injection pressures and exhibit
decreasing density with increasing tempera-
pressure is applied to the polymer in the
mold cavity, runner system and transfer lines
after the cavity is filled, until the polymer cools
sufficiently to hydraulically seal the mold cav-
ity. This packing pressure is most important in
540 Processing thermoplastic composites

Tailstock Platen

Oil Inlet for Closin

Oil Inlet for Opening

L Traversing LMoving Platen Stationary Platen

Cylinder

Fig. 24.12 Schematic of hydraulic clamping portion of conventional injection molding machine. (Redrawn
from Ref. 56 by permission of Carl Hanser Verlag.)

Table 24.13 Polymer properties important in injection molding

Particulate polymer frictional coefficients

Solid and liquid polymer thermal properties
Thermal diffusivity
Thermal conductivity
Heat capacity
Particulate bulk density
Pressure and temperature dependent melt density
Polymer shear sensitivity
Degradation potential - temperature limitation
Shear and temperature dependent viscosity over the shear rate range of 0-10 000 s-I
Melt fracture potential
Extrudate swell
Rheological characteristics
Normal stress difference
Temperature dependent elongational viscosity
Melt compressibility
Volume expansivity
Isothermal compressibility
Pressure dependent shrinkage
Crystallization kinetics
Heat of crystallization
Rate of crystallization
 Injection moldingfilled and reinforced thermoplastics 541

the injection molding of all polymers, includ-
ing heavily filled and reinforced compounds.
A tabulation of polymer properties impor-
tant in injection molding is given as Table
24.13. Note that many of these properties are
important in extrusion, as well.
For filled and reinforced polymers, mold
design is critical. There are several elements to
a mold:
result exhibit differential shrinkage values that
increase with increasing loading (Fig. 24.13j9).
As a first approximation, the flow of a filled
molten thermoplastic can be considered simi-
lar to the flow of the neat polymer, regardless
Cross-Flow

Sprue and runner system. The sprue

directs the polymer from the injection
molding machine nozzle into the mold
body through the stationary platen wall.
The runner system directs the molten poly-
mer to the appropriate cavities.
The gate. Polymer flows into a mold cavity
through a constriction called a gate. The

?
size and location of the gate are critical to
injection mold part performance, as noted
below.
; Diameter

Mold temperature control. Coolant lines

are normally placed parallel to the machine
platens. Adequate coolant flow to all part
surfaces is important in minimizing part
distortion and warpage. Warp = CuplDiameter
Part removal system. Typically, parts are
I I
molded under substantial pressure of
10-15 MPa. Ejector pins and rings are used
to press the part from the mold surface after
the mold has opened. In addition, other
Cross-Flow -
I
devices such as sliding cores and unscrew- Relative Measure
ing devices are employed to meet certain of Warp
design criteria.
Crystalline neat polymers exhibit greater over-
all shrinkage and more differential shrinkage
0.5
than amorphous neat polymers. Filled poly-
mers exhibit lower overall shrinkage but may W
4-
show substantially greater differential shrink-
age, called warp or cupping, than neat 10 20 40
polymers. Typically, the value for shrinkage of
a filled or reinforced polymer is less than that Glass Fiber Content, %(wt)
for the neat state of the polymer, and the value
shows substantially less injection-pressure sen-
Fig. 24.13 Differential shrinkage, cupping and
sitivity. Fiber-reinforced polymers exhibit warping of glass fiber reinforced polyacetal
reduced in-flow shrinkage and greater cross- homopolymer (polyoxymethylene).(Redrawn from
flow shrinkage than neat polymers and as a Ref. 59 by permission of Carl Hanser Verlag.)
542 Processing thermoplastic composites

of the loading level. The amount of force
needed to transfer the polymer from the injec-
tion molding machine to the mold cavity
increases with increase in apparent shear vis-
cosity. Since the transfer pressure is usually
fixed by the machine hydraulic system, the
transfer rate usually decreases with increasing
mold system (Fig. 24.1463).(It has been mathe-
matically shown that the fountain flow effect
holds for cylindrical and planar flow field&.
Even at very high fiber loading, individual
fibers or fiber aggregates align themselves
with the flow streamlines6z.)As is apparent
from Fig. 24.15@,there is no appreciable shear

--
filler loading. Usually, sprue, runner and gate field in the center core. As a result, fiber
dimensions are increased to accommodate the
wall
lower compressibility of the filled polymer
melt. Solid particles tend to migrate away
from planes of highest shear. Since shear is
Shear Rate
greatest near the mold confining surfaces,
parts of highly filled polymers tend to have
resin-rich surface layers. These layers are typi-
cally 10-100 p in thickness. Similarly, weld
lines or planes perpendicular to meeting flow
fronts, also tend to be resin-rich and are usu-
L- Centerlune

ally weaker than regions on either side of the

weld line60. Increasing levels of filler tend to
minimize the problem of jetting, where a neat
polymer forms a thread rather than a radial
disk as it enters a mold cavity from the gate.
For fibrous reinforcements, where the L I D
aspect ratio is greater than about lO:l, orienta- wan
tion during flow is very important. The fiber Fig. 24.15 Typical shear rate and velocity profiles
rotation attempted in the shear field is compli- for nonisothennal flow during injection mold filling
cated by the fountain-like flow of the of a cavity. (Redrawn from Ref. 64 by permission of
polymeric mass as it advances through the Society of Plastics Engineers.)

Fiber Bundle Orientation

Advancing Flow-Front

Flow Streamlines

Cdd Wall

Fig. 24.14 Fountain flow in injection molding, showing fiber bundle behavior along a streamline and
development of frozen layer at cold walls. (Redrawn and reinterpreted from Ref. 63 by permission of
Society of Plastics Engineers.)
 Injection moldingfilled and reinforced thermoplastics 543

bundles move preferentially from the molded;

upstream organizing region transverse to the
center axis toward the flow front. In doing so,
they orient as the advancing front is formed.
As shown in the schematic, the interface
between the molten core and the frozen skin
grows rapidly into the melt once the advanc-
ing front has passed. The oriented fibers are
aligned parallel to the flow direction. As with
extrusion, the surface at the mold surface is
resin-rich and, in many cases, essentally fiber-
free. When the mold is full, the structure
shows three, five, seven and even nine layers
in cross section (Fig. 24.16'j5,@j):
the resin-rich surface layer, up to 10 mm
(0.4 in) in thickness;
a relatively thin layer of fibers oriented in
the flow direction, with some of these fibers
tipped toward the flow axis;
a relatively thick layer of fibers oriented
transverse to the flow direction, with a sub-
stantial amount of in-plane randomness,
0 at the very center, a very thin plane of fibers
that are oriented in the flow direction.
The general nature of flow into an injection
mold cavity through a constriction or gate is
radial. Since there is substantial in-plane
stretching, fiber orientation in the gate region
of long narrow molded parts are quite similar
to fiber orientation in center-gated axisymmet-
ric molded parts. If there is no in-plane
orientation, cores typically have random pla-
nar orientation. Typically, the thickness of the
transverse fiber orientation in the core
decreases with distance from the gate. For cer-
tain polymer-fiber combinations and certain
injection speeds and mold temperature, the
resin-rich surface layer may not be apparent.
In fact, fiber prominence on molded part sur-
faces is apparent at long flow length-to-cavity
thickness ratios, in regions very near the gate
when the flow is turned as it enters the mold
cavity, at low neat polymer viscosities, for cold

-
depending on the nature of the part being polymer melts, and at slow injection rates.

Flow Direction

Transverse Orientation
Inflow Orlentation In-Flow Orientation
Fiber-Free Layer Transverse Orientation

Fig. 24.16 Schematic of the development of fiber orientation in injection molding,showing disappearance
of fiber-free surface layer and centerline transverse fiber orientation as flow proceeds into the mold cavity.
(Redrawn and reinterpreted from Ref. 65 by permission of Society of Plastics Engineers.)
544 Processing thermoplastic composites

Furthermore, the center line or plane of in-axis
fibers is usually the result of continuing injec-
tion as the flow channel freezes closed. The
resulting high shear orients the fibers in the
flow direction. This layer may not be apparent
in all fiber-reinforced parts. In very thin parts,
fibers are nearly always oriented parallel to
the mold surface67.The flow in an injection
Weld lines are particularly bothersome with
fiber-reinforced polymers. The primary con-
cern is the undesirable fiber orientation at the
interface between two advancing flow fronts
(Fig. 24.17”O). Trpically the reZative weld line
strength decreases with increasing filler load-
ing and aspect ratio71(Table 24.14).

- -
mold is mathematically modeled using
Hele-Shaw or creeping flow6*,69.

Flow Direction Flow Direction

Weld Line

Weld Line

Fig. 24.17 Fiber orientation at the interface of two impinging flow fronts, creating a weak weld line.
(Redrawn from Ref. 70 by permission of Carl Hanser Verlag.)

Table 24.14 Relative weld line strength for neat and reinforced polymer^^*,'^
~~~

Polymer Tensile strength retention for various glass loadings, YO

0 10 20 30 40
Polypropylene 86 47 34
SAN 80 40
Polycarbonate 99 86 64
Polysulfone 100 62
Polyphenylene sulfide 83 38 20
Nylon 66 (PA-66) 83-100 87-93 56-64

24.6 THERMOFORMING AND
COMPRESSION MOLDING
For neat polymers, thermoforming and com-
pression molding are different disciplines74,75.
Thermoforming begins with a formed sheet of
plastic that is heated to the rubbery state of the
polymer, usually a few degrees above its glass
transition or melting temperature. The rub-
bery sheet is then pressed with relatively little
differential force into or onto a cooled single-
sided mold and held there until the polymer
temperature is substantially below the form-
ing temperature. (In traditional vacuum
forming, the space between the sheet and the
mold surface is evacuated, thus applying dif-
ferential pressure of up to 0.1 MPa. In pressure
forming, air pressure is applied to the free sur-
face of the sheet, thus applying differential air
pressure of up to 1Ml'a76.) The desired part is
then trimmed from the web. Compression
molding is usually reserved for thermosetting
polymers, but certain thermoplastic polymers
such as UHMWPE, PTFE, and certain poly-
imides are compression molded. These
polymers are characterized as having very
high viscosities even at temperatures hun-
dreds of degrees above their melting or
processing temperature^^^. A polymer of this
type is compressed as a powder into a pre-
form, heated in a convection oven to the
processing temperature, and transferred to a
compression molding press where it is com-
pressed between heated mold halves. Typical
molding pressures are 7-35 MPa. The mold is
then cooled until the formed part temperature
is substantially below the polymer processing
t e m p e r a t ~ r eTable
~ ~ . 24.15 gives polymer prop-
erties important in thermoforming.
For filled, foamed and reinforced polymers,
the boundaries between thermoforming and
compression molding blur. Frequently, the
composite sheet forming process is simply
called stamping79.Fillers and discontinuous
fibers stiffen the polymer so that even at the
upper forming temperature of the polymer,
substantial differential force is required to
Thermoforming and compression molding 545
Table 24.15 Polymer properties important in ther-
mof orming
Temperature dependent polymer hot strength
Elastic modulus at forming temperature
Elongational viscosity at the forming temperature
Strain-rate hardening at high elongation
Other properties that are important in extruding
polymer sheet
Temperature dependent thermal properties of
rubbery solid polymer:
Thermal diffusivity
Thermal conductivity
Heat capacity
Polymer density
form the composite from the planar state to a
useful product. Mechanical means such as
matched dies, or hydraulic forces using super-
plastic aluminum or polyimide films, replace
pneumatic forces when the differential form-
ing pressures exceed 1 MPa. The foamed
polymer, on the other hand, cannot be heated
to the same forming temperature as the
unfoamed polymer without dramatic cell col-
lapse. As a result, foamed polymers are
formed at temperatures substantially below
forming temperatures for the unfoamed poly-
mers. Mechanical forces, such as matched dies,
are used for forming foamed polymer sheet
into useful products. Typically, the ratio of
polymer modulus at forming temperature to
applied pressure, E ( T ) / P , should be in the
range of 2-10 with a value of 5 most typical for
traditional thermoformingsO.As an example,
the temperature-dependent flexural modulus
of glass fiber-reinforced polyetherimide is
shown in Fig. 24.W. At 200°C (392"F), the
modulus of neat PEI is 2 MPa. The pressure
required to thermoform this polymer at this
temperature is about 0.4 MPa. For 30% (wt)
glass fiber-reinforced PEI the modulus is
7MPa and the required pressure is about
1.4 MPa. Pneumatic pressures at this level are
possible, but mechanical forming is preferred.
In many cases, the elastic modulus of the com-
posite exibits similar temperature dependency
to the elastic modulus of the polymer matrix,
546 Processing thermoplastic composites
10, I I
I I I I
0 50 103
Temperature, "c
0 xa zm
Temperature. "F
with the isothermal value of the modulus
increasing monotonically with increasing filler
or fiber loading (Fig. 24.19a2).
Thermoforming is a surface-generating
process. That is, the total area of the finished
part plus web is greater than the total area of
the initial sheet. The dominant method of gen-
erating surface is biaxial stretching of the
rubbery solid polymer. The shape of the tem-
perature-dependent tensile stress-strain curve
oo 10 20
Glass Fiber Content. %(wt)
33
Fig. 24.19 The effect of glass fiber loading on flexural
modulus of polysulfone at 25°C (77'F). (Redrawn
from Ref. 82 by permission of Carl Hanser Verlag.)
I
Fig. 24.18 Temperature dependent
150 0 flexural modulus of glass fiber rein-
forced Dolvetherimide. (Redrawn
from Rei. s'l by permission of Carl
3M Hanser Verlag.)
of the rubbery sheet is key to the forming
process. Figure 24.20 is a schematic of a temper-
ature-dependent stressstrain curve for a neat
polymer that exhibits a yield at low tempera-
t u r e ~ The
~ ~ . effect of filler and discontinuous
fiber on the shape of this curve is shown in Fig.
24.21M.Typically, the initial slope of the curve,
the tensile modulus increases, the yield point
disappears and the elongation at break
decreases rapidly with increasing fiber or filler
loading. This implies that the forming of com-
posite thermoplastics requires high
temperatures, substantial forces and the parts
40
Elongation
Fig. 24.20 Schematic of temperature dependent
stress-strain curve for a neat polymer exhibiting a
yield point.

Elongation
Fig. 24.21 Schematic of the effect of fiber content on
isothermal stress-strain curve for a polymer
exhibiting a yield point when unreinforced.
n n
Bottom Mold Half
Bottom Platen
Mold Open
Fig. 24.22 Schematic of a mold designed to slip-form continuous fiber-reinforced composite. (Redrawn
from Ref. 88 by permission of Society of Plastics Engineers.)
Thermoforming and compression molding 547
so produced are restricted to relatively shallow
draws. Typically, polymers containing nonwo-
ven continuous fiber mat and short- and
long-fiber chopped fiber mat are formable with
matched metal dies. Composites containing
woven fiber mat are not as formablea5.For very
long glass fiber- and continuous fiber-rein-
forced composites, the extensibility of the sheet
is so restricted that even shallow draw parts
cannot be formed without substantial polymer
migration (the squeezing of the polymer matrix
from the fiber bundle is called ‘percolation’),
compression buckling, pleating wrinkling and
fiber breakage when standard matched die
molding techniques are used. (Note that this
problem is not unique to fiber-reinforced ther-
moplastic composites. Paper, organic synthetic
paper and mixed fiber paper are nonwoven
fiber structures that are very difficult to form
into deeply drawn product^^,^^.) It is well
known that buckling, folding and pleating are
minimized by keeping the sheet under tension
throughout the forming process. Further, for
composites with limited extensibilities, the
material that makes up the formed shape must
come from the region outside the formed
Drive Shaft
Cartrldge Heater
Mold Closed
548 Processing thermoplastic composites

lntraply Shear
Resin Percolation Through Fiber Bundle

Transverse Squeezing Flow

F
IP
I,

Fig. 24.23 Schematic of fiber-resin matrix interaction during deformation for several types of deforma-
tions. (Redrawnand reinterpreted from Ref. 93 by permission of Society of Plastics Engineers.)

shape. Slip forming is the principal method for

accomplishingthis (Fig. 24.Zm90).The key is to
supply sufficient tension to the sheet to mini-
mize folding but not an excess amount that will
tear the very hot ~ h e e t ~ l , ~ ~ .
Bulk mechanical deformation of the rein-
forced sheet is not the only concern when
I Heater I
forming reinforced sheet93.Figure 24.23 shows
several fiber-matrix interactions that take
place locally during composite thermoform-
ing94.Intraply shear, interlaminar shear or slip
and interlaminar rotation are local shearing
effects that involve the fiber. Local resin flow
between fibers, fiber bundles and plies allow Mold Open
local distortion of the matrix. Matrix percola-
tion and squeeze flow are predominantly resin Formed Sheet
effects. Voids and delaminations are micro- I PI
scopic defects that are attributed to local
fiber-matrix interactions during forming.
Compression molding is flow molding or
‘squeezingflow’ of polymer between two mold
halves (Fig. 24.2495).The flow behavior for a
filled or short-fiber reinforced polymer mimics Mold Closed
that for the neat The flow is usually
characterized as planar radial with the wave- Fig. 24.24 Schematic of flow molding, flow form-
front being fountain-like as with injection ing or squeezing flow of nonwoven fiber-reinforced
molding. Fiber orientation is quite similar to thermoplastic resin composite. (Redrawn from Ref.
that observed with center-gated injection mold- 95 by permission of Society of Plastics Engineers.)
 Other processes forfilled and reinforced polymers 549

Compression molding is also used with halves close on the parison, pinching it
long fibers or continuous fibers. In one exam- between the mold halves. The remaining por-
ple, a fiber preform is inserted in the mold tion of the parison is then inflated against the
cavity and a heated neat polymer preform is mold walls (Fig. 24.25). Parison thickness con-
placed on top. The press is closed to 35 MPa or trol is the key to uniform wall thickness.
more, squeezing the polymer into the fiber pre- Parison thickness uniformity is governed by
form. The process works best if the polymer is extrudate swell as the polymer exits the die
crystalline and has a very low melt viscosity at and by parison sag owing to the parison
the molding temperature. Compression hanging weight. The former is a function of
molded composite parts are usually more com- the viscoelasticity of the polymer in general
plex than thermoformed composite parts. and the normal stress difference in particular.
Voids, warping, fiber prominence at the part The latter is a function of the mass of the pari-
surface intially against the mold and resin rich- son, the extrusion time and the elongational
ness at the other surface are typical problems viscosity of the polymer. Neat polyethylenes
attributed to the forming process. exhibit extensive extrudate swell. Fillers and
fibers reduce the extrudate swell in propor-
24.7 OTHER PROCESSES FOR FILLED AND
tion to the filler or fiber loading (Fig.
REINFORCED POLYMERS
24.91°1J02).Filler loading increases parison dif-
ferential weight. And fillers and fibers cause
As noted above, foamable, filled and short-
fiber reinforced thermoplastics are usually
processed in fashions similar to the neat ther- Mold Half Mold Half
moplastic. Filled and reinforced hollow Parison
structural parts are fabricated by blow mold-
ing and rotational molding. Rotational
molding is also used to produce multilayer
structures having foam cores97.
Polyolefins account for approximately 90%
(wt) of all non-disposable industrial products
produced by blow molding and nearly all
products produced by rotational molding.
Mica flake reinforced HDPE to 30% (wt) has Mold Open
been accumulator blow molded into flat struc-
380" Pinch-Off
tural parts and ducts for automotive, truck
and agricultural vehicles since the early
1 9 6 0 ~ ~ ~Graphite-filled
-'~~. HDPE is blow
molded into conductive electrical boxes and
doors. Glass fiber-reinforced HDPE is blow
molded into flotation devices, sailboards and
kayaks. Accumulator blow molding machines
are used to extrude a large quantity of plastic
in a short period of time. The filled or short-
fiber reinforced polymer is plasticated at a Formed Part

constant rate in a conventional screw Mold Closed

extruder. The melt is stored in an accumulator
until the mold is cleared, then extruded in sec- Fig. 24.25 Top view schematic of lay-flat squeezing
onds into a parison or vertical tube. The mold of extruded parison in structural blow molding.
550 Processing thermoplastic composites

Table 24.16 Polymer properties important in blow molding

Shear and temperature dependent viscosity over the shear rate range of 0-10 000 s-'
Melt fracture potential
Nonisothermal melt strength or temperature dependent elongational viscosity
Extrudate swell
Rheological characteristics
Normal stress difference
Temperature dependent elongational viscosity
Polymer strain recovery
Molecular weight dependency
Molecular weight distribution dependency
Particulate polymer frictional coefficients
Solid and liquid polymer thermal properties
Thermal diffusivity
Thermal conductivity
Heat capacity
Particulate bulk density
Pressure and temperature dependent melt density
Polymer shear sensitivity
Degradation potential - temperature limitation
Effect of orientation on gas permeability of polymer
Strain-oriented crystallinity levels and effect on
Barrier properties
Permeability
Tensile strength

I i!
II II

tlne
Shafia

C h d n Drira

Fig. 24.26 Schematic of co-axis

rotational molding for filled or
lightly reinforced p~lyolefins'~~.
 Other processes for filled and reinforced polymers 551

the parison to cool more quickly. As a result,
parison wall thickness control must be
changed radically when blow molding filled
or reinforced polymers. Table 24.16 gives a list
of polymer properties important in blow
molding.
Rotational molding is an atmospheric
process in which polymer powder is charged
to a metal clam-shell mold. The mold is rotated
about the polar or major and equatorial or
minor axes (Fig. 24.261°3),while being heated in
a forced air convection oven for several min-
utes, until the powder sticks to the mold
surface, melts and densifies into a void-free
hollow object. The mold is then air- and/or
water mist-cooled, the part removed, the mold
recharged and the process repeated.
Polyethylene is the major rotational molding
polymer, with particle sizes ranging between
50 pn and 500 pm. Coarse particle fillers hav-
ing particle sizes of about 50 pm or more, such
as CaCO,, milled glass and glass cullet are suc-
cessfully molded to loadings of 30% (wt). Fine
particle fillers such as TiO,, carbon black and
talc fluidize readily in the tumbling environ-
ment of the mold and so rarely yield useful
products. Fibers with aspect ratios of 1000 or
less can be successfully molded if the maxi-
mum fiber content is less than about 15% (wt).
Lower fiber loadings may be necessary for cer-
tain mold geometries and certain types of
polyethylenes. If the fiber loading is too high,
the fibers orient at right angles to the mold sur-
face, producing an unacceptable setaceous
inner surface104.One method of forming a hol-
low composite is to impregnate nonwoven
fiber mat with up to 30% (wt) electrostatically
charged polymer powder, then sinter the struc-
ture to fuse the powder to the fibers. The hot
structure is then manually pressed against the
mold surfaces prior to adding additional poly-
mer powder, closing the mold, rotating it,
heating it to the forming temperature, and
cooling it in standard fashion105.Evacuating
the mold through the rotating concentric shafts
is helpful in minimizing voids but is usually
quite difficult to achieve successfully. Table
24.17 gives a list of polymer properties needed
for rotational molding.

Table 24.17 Polymer properties important in rotational molding

Particle size distribution

Temperature dependent thermal properties of particulate polymer
Thermal diffusivity
Thermal conductivity
Heat capacity
Bulk density
Polymer density
Molecular characteristics
Molecular weight
Molecular weight distribution
Crystallization kinetics
Heat of crystallization
Rate of crystallization
Crosslinking characteristics
Reaction rate
Level
Zero-shear viscosity at melt temperature
552 Processing thermoplastic composites

Table 24.18 Effect of fillers on processing properties

Processing property Effect of filler

Viscosity Increases
Melt flow Decreases
Compounding Machine dependent, usually complicates the process
Processing temperature Increases
Temperature No effect or cools faster
Injection pressure Increases
Flow in injection mold Mold dependent but usually decreases
Injection mold shrinkage Decreases
Injection mold cycle time No effect
Thermoforming sheet sag Decreases
Thermoforming pressure Increases
Thermoforming depth of draw Decreases
Thermoforming part surface quality Decreases
Extrudate surface quality Decreases
Extrusion die pressure Increases
Melt extrudate swell Decreases, sometimes dramatically
Melt fracture severity Decreases
Foam cell size No effect to decreases

24.8 SUMMARY REFERENCES

Filled polymers tend to process in manners
similar to their neat polymer counterparts. The
general trend is to increase the melt viscosity
of the polymer at low shear rates and to
decrease the relative effect of viscoelasticity of
the polymer. Table 24.18 shows this for most of
the processes described above. Short-fiber
reinforcements show more local flow orienta-
tion than fillers but, by and large, process
parameters are not dramatically influenced by
their presence. Long-fiber reinforcements on
the other hand show substantial local flow ori-
entation in all polymer melt processes. This
orientation is controlled to a limited extent by
the design of the dies and molds. Table 24.18
summarizes many of the important processing
variables for filled and discontinuous fiber-
reinforced polymers. Flow of continuous
fiber-reinforced polymers is restricted to local
squeezing flow around the fiber bundles and
so thermoforming, compression molding,
stamping and diaphragm forming are the
major ways of forming these thermoplastic
composites into useful products.
1. Progelhof, R.C. and Throne, J.L., Polymer
Engineering Principles: Properties, Processes, and
Tests for Design, Munich Carl Hanser, 1993,
Figure 5.1.
2. Progelhof, R.C. and Throne, J.L., Polymer
Engineering Principles: Properties, Processes, and
Tests for Design, Munich: Carl Hanser, 1993,
Table 1.2.
3. Progelhof, R.C. and Throne, J.L., Polymer
Engineering Principles: Properties, Processes, and
Tests for Design, Munich: Carl Hanser, 1993,
Table 1.4.
4. Progelhof, R.C. and Throne, J.L., Polymer
Engineering Principles: Properties, Processes, and
Tests for Design, Munich: Carl Hanser, 1993,
Table 1.3.
5. Charrier, J.-M, Polymeric Materials and
Processing. Plastics, Elastomers and Composites,
Munich: Carl Hanser, 1991.
6. Progelhof, R.C. and Throne, J.L., Polymer
Engineering Principles: Properties, Processes, and
Tests for Design, Munich: Carl Hanser, 1993,
Figure 5.2.
7. Progelhof, R.C. and Throne, J.L., Polymer
Engineering Principles: Properties, Processes, and
Tests for Design, Munich: Carl Hanser, 1993,
Table 5.3.

8. Progelhof, R.C. and Throne, J.L., Polymer
Engineering Principles: Properties, Processes, and
Tests for Design, Munich: Carl Hanser, 1993,
Table 5.5.
9. Progelhof, R.C. and Throne, J.L., Polymer
Engineering Principles: Properties, Processes, and
Tests for Design, Munich: Carl Hanser, 1993,
Chapter 5.
10. Throne, J.L., Plastics Process Engineering, New
York: Marcel Dekker, 1979.
11. Middleman, S., Fundamentals of Polymer
Processing, New York: McGraw-Hill Book Co.,
1977.
12. Tadmor, Z. and Gogos, C.G., Principles of
Polymer Processing, New York: Wiley-
Interscience, 1979.
13. Crawford, R.J., Plastics Engineering, 2nd Edn,
Oxford: Pergamon Press, 1987.
14. McCrum, N.G., Buckley, C.P. and Bucknall,
C.B., Principles of Polymer Engineering, Oxford:
Oxford University Press, 1988.
15. Bird, R.B., Armstrong, R.C. and Hassager, O.,
Dynamics of Polymeric Liquids. Volume 1: Fluid
Mechanics, New York: John Wiley & Sons, 1977.
16. Larson, R.G., Constitutive Equations for Polymer
Melts and Solutions, Boston: Buttenvorths, 1988.
17. Han, C.D., Rheology in Polymer Processing, New
York Academic Press, 1976.
18. Ferry, J.D., Viscoelastic Properties of Polymers,
New York: John Wiley & Sons, Inc., 1961.
19. Lenk, R.S., Plastics Rheology: Mechanical
Behaviour of Solid and Liquid Polymers, New
York Wiley Interscience, 1968.
20. Middleman, S., The Flow of High Polymers:
Continuum and Molecular Rheology, New York:
Wiley Interscience, 1968.
21. Brydson, J., Flow Properties of Polymer Melts,
New York Van Nostrand Reinhold, 1970.
22. Han, C.D., Multiphase Flow in Polymer
Processing, Academic Press, 1981, Fig. 3.14, p.
101.
23. Herschel, W.H. and Bulkley, R., Measurement
of consistency as applied to rubber-benzene
solutions, Proc. Amer. SOC.Test. Mater., 1926,26,
621-674.
24. Hershel, W.H. and Bulkley, R., Kolloid-Z., 1926,
39,291-299.
25. Han, C.D., Multiphase Flow in Polymer
Processing, London: Academic Press, 1981, Fig.
3.22, p. 106.
26. Han, C.D., Multiphase Flow in Polymer
Processing, London: Academic Press, 1981, Fig.
3.24, p. 108.
References 553
27. Shenoy, A.V., Saini, D.R., and Nadkari, V.M,
Rheograms of filled polymer melts from melt-
flow index, Polym. Comp., 1983,453-63.
28. Han, C.D., Multiphase Flow in Polymer Processing,
London: Academic Press, 1981, p. 113.
29. Tanaka, H. and White, J.L., Experimental inves-
tigations of shear and elongational flow
properties of polystyrene melts reinforced with
calcium carbonate, titanium dioxide, and car-
bon black, Polym. Eng. Sci., 1980,20,949-956.
30. Chan, Y., White, J.L. and Oyanagi, Y., A funda-
mental study of the rheological properties of
glass-fiber-reinforced polyethylene and poly-
styrene melts, J. Rheol., 1978,22,507-524.
31. Kamal, M.R. and Mutel, A.T., The prediction of
flow and orientation behavior of short fiber
reinforced melts in simple flow systems, Polym.
Compos., 1989,10,337-343.
32. Progelhof, R.C. and Throne, J.L., Polymer
Engineering Principles: Properties, Processes, and
Tests for Design, Munich: Carl Hanser, 1993, p.
165.
33. Progelhof, R.C. and Throne, J.L., Polymer
Engineering Principles: Properties, Processes, and
Tests for Design, Munich: Carl Hanser, 1993, p.
166.
34. Progelhof, R.C. and Throne, J.L., Polymer
Engineering Principles: Properties, Processes, and
Tests for Design, Munich: Carl Hanser, 1993, p.
161.
35. Throne, J.L., Thermoplastic Foams, New York
Chapman & Hall, 1994, Fig. 9.108.
36. Progelhof, R.C. and Throne, J.L., Polymer
Engineering Principles: Properties, Processes, and
Tests for Design, Munich Carl Hanser, 1993, Fig.
5.3.
37. Rauwendaal, C., Polymer Extrusion, Munich:
Carl Hanser, 1986.
38. White, J.L., Twin Screw Extrusion: Technology and
Principles, Munich: Carl Hanser, 1990.
39. Michaeli, W., Extrusion Dies: Technology and
Principles, Munich Carl Hanser, 1984.
40. Throne, J.L., Thermoplastic Foams, Hinckley,
OH: Shenvood Publishing, 1996, Section 5.2.
41. White, J.L., Twin Screw Extrusion: Technology and
Principles, Munich: Carl Hanser, 1990, Chapter
7.
42. White, J.L., Twin Screw Extrusion: Technology and
Principles, Munich: Carl Hanser, 1990, p. 10.
43. Rauwendaal, Polymer Extrusion, Munich Carl
Hanser, 1986, p. 462.
44. Throne, J.L., Thermoplastic Foams, Hinckley,
OH: Shenvood Publishing, 1996, Table 5.4.
554 Processing thermoplastic composites
45. White, J.L., Twin Screw Extrusion: Technology
and Principles, Munich: Carl Hanser, 1990,
Chapter 11.
46. Rauwendaal, Polymer Extrusion, Munich: Carl
Hanser, 1986, p. 403.
47. Wall, D., The processing of fiber reinforced
thermoplastics using co-rotating twin screw
extruders, Polym. Compos., 1989, 10, 98-102,
Fig. 2.
48. Goettler, L.A., Mechanical property enhance-
ment in short-fiber composites through the
control of fiber orientation during fabrication,
Polym. Compos., 1984, 5,60-71.
49. Michaeli, W., Extrusion Dies: Design and
Engineering Computations, Munich: Carl
Hanser, 1984,110-115.
50. Han, C.D., Multiphase Flow in Polymer
Processing, London: Academic Press, 1981, p.
109, Fig. 3.26.
51. Goettler, L.A., Mechanical property enhance-
ment in short-fiber composites through the
control of fiber orientation during fabrication,
Polym. Compos., 1984, 5,137-154, Fig. 12.
52. Goettler, L.A., The extrusion and performance
of plasticized poly(viny1 chloride) hose rein-
forced with short cellulose fibers, Polym.
Compos., 1983,4,249-255, Fig. 1.
53. Rubin, I.I.,Injection Molding: Theory and Practice,
New York Wiley Interscience, 1972, p.2.
54. Progelhof, R.C. and Throne, J.L., Polymer
Engineering Principles: Properties, Processes, and
Tests for Design, Munich: Carl Hanser, 1993,
Chapter 5.
55. Progelhof, R.C. and Throne, J.L., Polymer
Engineering Principles: Properties, Processes, and
Tests for Design, Munich: Carl Hanser, 1993,
Fig. 5.19.
56. Progelhof, R.C. and Throne, J.L., Polymer
Engineering Principles: Properties, Processes, and
Tests for Design, Munich Carl Hanser, 1993, Fig.
5.21.
57. Throne, J.L., Plastics Process Engineering, New
York: Marcel Dekker, 1979, Chapter 14,
699-800.
58. Progelhof, R.C. and Throne, J.L., Polymer
Engineering Principles: Properties, Processes,
and Tests for Design, Munich: Carl Hanser,
1993, p. 97.
59. Malloy, R.A., Plastic Part Design for Injection
Molding: An Introduction, Munich: Carl Hanser
1994, Fig. 2.77.
60. Malloy, R.A., Plastic Part Design for Injection
Molding: An Introduction, Munich: Carl Hanser,
1994, p. 55.
61. Bay, R.S. and Tucker, C.L., Fiber orientation in
simple injection moldings. Part I: theory and
numerical methods, Polym. Compos., 1992, 13,
317-331.
62. Givler, R.C., Crochet, M.J. and Pipes, R.B.,
Numerical prediction of fiber orientation in
dilute suspensions, J. Compos. Mater., 1983, 17,
330-343.
63. Kenig, S., Fiber orientation development in
molding of polymer composites, Polym.
Compos., 1986,7,50-55, Fig. 4.
64. Kenig, S., Fiber orientation development in
molding of polymer composites, Polym.
Compos., 1986, 7,50-55, Fig. 5.
65. Kenig, S., Fiber orientation development in
molding of polymer composites, Polym.
Compos., 1986,7,50-55, Fig. 1.
66. Darlington, M.A. and Smith, A.C., Some fea-
tures of the injection molding of short fiber
reinforced thermoplastics in center sprue-gated
cavities, Polym. Compos., 1987,8,16-21, Fig. 4A.
67. Bay, R.S. and Tucker 111, C.L., Fiber orientation
in simple injection moldings. Part 11: experi-
mental results, Polym. Compos., 1992, 13,
332-341.
68. Advani, S.G. and Tucker 111, C.L., The use of
tensors to describe and predict fiber orientation
in short fiber composites, J. Rheol., 1987, 31,
751-784.
69. Advani, S.G. and Tucker 111, C.L., Closure
approximations for three-dimensional struc-
ture tensors, J. Rheol., 1990, 34,367-386.
70. Malloy, R.A., Plastic Part Design for Injection
Molding: An Introduction, Munich Carl Hanser,
1994, Fig. 2.46.
71. Malloy, R.A., Plastic Part Design for Injection
Molding: An Introduction, Munich: Carl Hanser,
1994, p. 55.
72. Malloy, R.A., Plastic Part Design for Injection
Molding: An Infroduction, Munich Carl Hanser,
1994, p. 54.
73. Brahmbhatt, S. and Malloy, R., An evaluation of
weld line strengths for long glass fiber rein-
forced styrene/maleic anhydride copolymer,
SPE ANTEC Tech. Papers, 1992,38,2563-2567.
74. Progelhof, R.C. and Throne, J.L., Polymer
Engineering Principles: Properties, Processes, and
Tests for Design, Munich Carl Hanser, 1993.
75. Throne, J.L., Thermoforming, Munich: Carl
Hanser, 1987.
76. Throne, J.L., Thermoforming, Munich: Carl
Hanser, 1987, pp. 34-35.

77. Anon., 1900 ultrahigh molecular weight poly-
mer compression molding techniques, Bulletin
HPE-102, Himont U.S.A., Inc., Wilmington DE,
undated.
78. Narkis, M. and Rosenzweig, N., Eds., Polymer
Powder Technology, Chichester: John Wiley &
Sons, 1994.
79. Fong, L., Xu, J. and Lee, L.J., Preforming analy-
sis of thermoformable glass fiber mats -
deformation modes and reinforcement charac-
terization, Polym. Compos., 1995,15,134-146.
80. Throne, J.L., Thermoforming, Munich: Carl
Hanser, 1987, Chapter 4.
81. Domininghaus, H., Plastics for Engineers:
Materials, Properties, Applications, Munich: Carl
Hanser, 1993, Fig. 523, p. 564.
82. Domininghaus, H., Plastics for Engineers:
Materials, Properties, Applications, Munich Carl
Hanser, 1993, Fig. 457, p. 506.
83. Domininghaus, H., Plastics for Engineers:
Materials, Properties, Applications, Munich: Carl
Hanser, 1993, Fig. 454, p. 506.
84. Domininghaus, H., Plastics for Engineers:
Materials, Properties, Applications, Munich Carl
Hanser, 1993, Fig. 457.
85. Bigg, D.M., Hiscock, D.F., Preston, J.R. and
Bradbury, E.J., Thermoplastic Matrix Sheet
Composites, Polym. Compos., 1988,9,222-228.
86. Wolpert, V.M., Synthetic Polymers and the Paper
lndusty , San Francisco: Miller Freeman, 1977.
87. d’A. Clark, J., Pulp Technology and Treatment for
Paper, San Francisco: Miller Freeman, 1978.
88. Cakmak, M. and Dutta, A., Instrumented ther-
moforming of advanced thermoplastic
composites. 111: Relative performance of vari-
ous prepregs in forming double curvature
parts, Polym. Compos., 1991,12,354-369, Fig. 3.
89. Throne, J.L., Thermoforming, Munich: Carl
Hanser, 1987, p. 28, Fig. 1.22
90. Berins, M.L., SPI Plastics Engineering Handbook
of the Society of the Plastics Industry, lnc., 5th
Edn, New York Van Nostrand Reinhold, 1991,
Figure 13-llb, p. 392.
91. Dutta, A, Niemeyer, M. and Cakmak, M.,
Thermoforming of advanced thermoplastic
composites. I: Single curvature parts, Polym.
Compos., 1991,12,257-272.
92. Cakmak, M. and Dutta, A., Instrumented ther-
moforming of advanced thermoplastic
composites. 11: Dynamics of double curvature
part formation and structure development
from PEEK/carbon fiber prepreg tapes, Polym.
Compos., 1991,12,338-353.
References 555
93. O’Bradaigh, C.M. and Pipes, R.B., Issues in
diaphragm forming of continuous fiber rein-
forced thermoplastic composites, Polym.
Compos., 1991,12,246-256.
94. OBradaigh, C.M. and Pipes, R.B., Issues in
diaphragm forming of continuous fiber rein-
forced thermoplastic composites, Polym.
Compos., 1991,12,246-256, Fig. 2a-2b.
95. Bigg, D.M., Hiscock, D.F., Preston, J.R. and
Bradbury, E.J., Thermoplastic matrix sheet
composites, Polym. Compos., 1988, 9, 222-228,
Fig. 6.
96. Progelhof, R.C. and Throne, J.L., Polymer
Engineering Principles: Properties, Processes, and
Tests for Design, Munich Carl Hanser, 1993, pp.
471475.
97. Shutov, F., lntegral/Structural Polymer Foams,
Berlin: Springer Verlag, 1986, Chapter 10.
98. Peters, D.L., Kowalski, R.C. and Hughes, J.K.,
Blow molded reinforced HDPE for structural
applications, SAE Tech. Paper No. 830077,
1983.
99. Rosato, D.V. and Rosato, D.V., Eds., Blow
Molding Handbook: Technology, Performance,
Markets, Economics. The Complete Blow Molding
Operation, Munich: Carl Hanser, 1989, p. 481.
100. Rathgeber, J., Evolution of an imaginative tech-
nology - double wall blow molding, in Blow
Molding Handbook: Technology, Performance,
Markets, Economics. The Complete Blow Molding
Operation, Munich Carl Hanser, 1989 (D.V.
Rosato and D.V. Rosato, Eds), pp. 828-829.
101. Han, C.D., Multiphase Flow in Polymer
Processing, London: Academic Press, 1981,
Figure 3.26, p. 109.
102. Minagawa, N. and White, J.L., The influence of
titanium dioxide on the rheological and extru-
sion properties of polymer melts, J. Appl.
Polym. Sci., 1976, 20, 501-523.
103. Throne, J.L., Rotational molding, in Polymer
Powder Technology, (M. Narkis and N.
Rosenzweig, Eds.), Chichester: John Wiley,
1994, Fig. 3.
104. Ramazzoti, D.J., Rotational molding, in PZastzcs
Engineering Handbook of the Society of the Plastics
Industry, Inc., (J. Frados, Ed.), 4th Edn, New
York Van Nostrand Reinhold, 1976, p. 353.
105. Crawford, R.J., Rotational moulding of plastics,
Prog. Rubb. Plast. Technol., 1990,6(1),1-29.