ICH404: Polymer Technology

Prepared by Dr. Lukman B. Abdulra’uf

Large scale industrial polymerisation processes; mechanical properties of polymers; Introduction to polymer
rheology, polymer processing – injection, extrusion, calendaring, compression and transfer; moulding of
thermoplastics; important methods of processing thermosets; polymer morphology

1. Ebewele, R. O. (1996). Polymer science and technology. Boca Raton: CRC Press
2. Goodwin, J. W. and Hughes, R. W. (2012). Rheology for Chemists. Cambridge: RSC Publishing
3. Guo, Q (ed). Polymer morphology: principles, characterization and processing. New Jersey: John Wiley & Sons

Introduction to Polymer Rheology

Rheology is defined as the science of deformation and flow of matter resulting from application of a force. The
deformation can be shear (parallel internal surface slide past one another), elongation or a combination of
deformations. It deals with those properties of materials that determine their response to mechanical force. For
solids, this involves elasticity and plasticity, for fluids, it involves viscosity measurements.

Its measurements provide useful information on the behavior of various products in addition to knowledge of the
effects of processing, formulation changes and ageing phenomenon.

Rheometers: are specific devices that are used to measure the rheological properties of matter and evaluation of
fluid models.

Properties of Deforming Polymers

a. Stress relaxation behaviours: polymers are composed of macromolecules, and these large molecules have the ability
to slide past each other, hindered only by intra-molecular forces and molecular entanglements, they tend to relax stresses that
arise when subjected to a deformation. Hence, as a mass of polymer is subjected to a stress, the molecules tend to move in an
effort to relax those stresses. If these stresses are caused by a constant strain, the initial stress caused by this deformation
relaxes in a given time interval, sometimes referred to as relaxation time.

b. Shear thinning behaviour: At low rates of deformation, the entangled molecules have a hard time sliding past
each other, resulting in a relatively high viscosity. Polymer melts exhibit this behavior over a range of small rates
of deformation. However, as the rate of deformation increases, the molecule are disentangle. The disentangled
molecules can slide past their neighbors with more ease, resulting in an overall lower viscosity. This phenomenon
is referred to as shear thinning behavior, or structural viscosity

c. Normal Stresses in shear flow: The tendency of polymer molecules to “curl-up” while they are being stretched
in shear flow results in normal stresses in the fluid. In the rod climbing experiment, a rotating shaft causes the
polymeric solution to move towards the shaft and not away from it. As a result, the polymer starts to move up the
rotating shaft. As the polymer molecules are stretched by the devices shear stresses resulting in normal stresses.

d. Stress overshoot during start-up flow: When a polymer sample that is initially at rest is suddenly subjected to
a deformation rate, its stress response presents a slight stress overshoot, to a maximum value, before decreasing and
reaching a steady state value. The cause for this stress overshoot is the polymer melt’s initial higher resistance to
deformation resulting from molecular entanglements. Once the polymer deformation exceeds a certain value, the
molecules begin to disentangle, reducing the resistance to deformation, causing the stresses to relax to a steady state
value.

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e. Melt strength (Melt fracture): When a polymer is forced to deform and move at speeds that result in processing
times shorter than the relaxation time of the polymer, the stresses will build up until they exceed the melt strength,
leading to so called melt fracture. Another form of melt fracture may occur during elongational deformation, when
the drawing speed is too high, the stresses build up before having a chance to relax, until the thread rips, or fractures.

Polymer Processing: is the activity performed on polymeric materials to increase their usefulness. It involves
shaping, synthesis, transformation, compounding, functionalization, and stabilization of materials. The combination
of these operations determines the final properties and performance of any polymeric product. It involves creating
structures using polymers by changing their viscosity and rheological properties.

Polymer processing may be divided into two broad areas. The first is the processing of the polymer into some form
such as pellets or powder. The second type describes the process of converting polymeric materials into useful
articles of desired shapes.

Compounding Processes
These are the processing stages between the manufacturing of the crude polymer and the final molding step. The
process include storage, transportation. metering, mixing, plastication and granulation.
1. Mixing: it allows obtaining a homogeneous mixture of polymer and additives. The additive is distributed
uniformly throughout the crude polymer, without any unnecessary stressing. Mixing can occur under the action of
gravitational forces in a tumble mixer; or in a ribbon mixer, where materials are mixed in a horizontal barrel in a
spiral manner. Such mixers are collectively known as cold mixers. When the polymers are heated by contact with
heated metal components, it is called hot mixer.
2. Rolling and Kneading: it involves passing a plastic between two counter-rotating, heated rolls
wherein it is pressed into a thin layer. It is an open process in which additives can be added, and other scrap materials
may be reintroduced. PVC is one plastic which extensively employs this process. Moreover, the material
temperature can be controlled precisely and cleaning of the machine is easy.
3. Pelletizing: It is the method of producing granules of equal size and shape. This enables the optimum feed
behaviour on the processing equipment. Pelletizing can be done in hot or cold conditions. Using a pelletizing die,
strands, ribbons or sheets are formed; and after solidification, they are chopped into the desired shapes. This is one
procedure strictly followed in cold pelletizing. However, in hot pelletizing, the plasticated material is sent through
a die, and a blade that rotates on thesurface of the die plate chops the exiting strands. The melt is then cooled; and
subsequently the water is removed.
4. Shredding and Grinding: Regranulating is achieved through cutting mills. The material is added through a feed
system wherein a rotor revolves with high momentum. The system is further equipped with multiple cutting heads
that operate against stationary cutting edges. The rotating cutting heads are divided and displaced with respect to
each other in some other machines. As soon as the desired particle size is obtained, the material is ejected through
a sieve, the pores of which determine the size of the particles
5. Storage and Transportation: The storage and transportation of base polymers and intermediate products are
achieved through automatic equipment. These equipment have an edge over the manually operated ones as they
ensure improved working conditions, lower work place, lower contamination of materials and subsequent reduction
losses. Moreover, accident hazards are also reduced. Large external silos are used for the storage of polymers, either
in powder form, or in the pellet form. By incorporating vibrating frames, bunker cushions, slotted shelves or similar
techniques as ventilation, the formation of granule bridges is avoided.

Properties that Influence Polymer Processing

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1. Quality and production rate
2. Size of final product
3. Dimension accuracy and surface finish
4. Transparency, toughness, flexibility and aspect ratio

Unit Operations in Polymer Processing

1. Extrusion is a processing technique for converting thermoplastic materials in powdered or granular form
into a continuous uniform melt, which is shaped into items of uniform cross-sectional area by forcing it
through a die. The extrusion line (Fig. 10), consists of an extruder into which the polymer is poured in form
of granules or pellets and where it is melted and pumped through the die of desired shape. The molten
polymer then enters a sizing and cooling trough or rolls where the correct size and shape are developed.
From the trough, the product enters the motor-driven, rubber-covered rolls (puller), which essentially pull
the molten resin from the die through the sizer into the cutter or coiler where final product handling takes
place.

Fig. 1. Sketch of an extrusion line

Fig. 2: Parts of an extruder

Extrusion end products include pipes for water, gas, drains, and vents; tubing for garden hose, automobiles, control
cable housings, soda straws; profiles for construction, automobile, and appliance industries; film for packaging;
insulated wire for homes, automobiles, appliances, telephones and electric power distribution; filaments for brush
bristles, rope and twine, fishing line, tennis rackets; parisons for blow molding.

2. Injection Molding: is one of the processing techniques for converting thermoplastics, and recently,
thermosetting materials, from the pellet or powder form into a variety of useful products. Injection molding consists
of heating the pellet or powder until it melts. The melt is then injected into and held in a cooled mold under pressure
until the material solidifies. The mold opens and the product is ejected. The injection molding machine must,
therefore, perform essentially three functions:
1. Melt the plastic so that it can flow under pressure
2. Inject the molten material into the mold.

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3. Hold the melt in the cold mold, while it solidifies and then eject the solid plastic.

Fig. 3: Diagram of a plunger-type injection molding machine

Injection Unit: The injection unit performs two functions: melting of the pellet or powder and injection of the melt
into mold.
Clamping Unit: The clamp unit or press end of the injection molding machine performs three functions: opens and
closes the mold at appropriate times during the molding cycle; ejects the molded part; and provides enough pressure
to prevent the mold from opening due to the pressure developed in the mold cavity as it is filled with the melt by
the injection unit.
Auxiliary Systems: It contains the hydraulic and control systems. The hydraulic system, transmits and controls the
power from the electric motor to the various parts of the machine. Machine functions are regulated by a careful
control of the flow, direction, and pressure of the hydraulic fluid.
Injection molding is used to produce a variety of useful products. Forks, spoons, computer, television, and radio
cabinets.

3. Blow Molding: the process consists of a sequence of steps leading to the production of a hollow tube or parison
from a molten thermoplastic resin. This is then entrapped between the two halves of a mold of the desire desired
shape. Air, usually at about 100 psi, is blown into the soft parison, expanding it against the contours of the cold
mold cavity. The part is cooled and removed from the mold, and where necessary the excess plastic material or
flash accompanying the molded part is trimmed and reclaimed for reuse. The blow molding process therefore
involves essentially two properly synchronized operations: parison formation from the plastic material and blowing
the parison into the shape of the desired part.

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Fig. 4: Schematic diagram of the blowing stage. (a) The molten, hollow tube — the parison or preform — is placed
between the halves of the mold; (b) the mold closes around the parison; (c) the parison, still molten, is pinched off
and inflated by an air blast that forces its wall against the inside contours of the cooled mold; (d) when the piece
has cooled enough to have become solid, the mold is opened and the finished piece is ejected
Types of Blow Bolding
Blow molding can either be extrusion blow molding which is characterized by scrap production or injection blow
molding which is versatile and scrap free.
a. Extrusion Blow Bolding: extrusion blow molding, an extruder, is used to plasticize the resin and form the
parison. The process may be continuous or intermittent. In the continuous process, a continuous parison is formed
at a rate synchronized with the rates of part blowing, cooling, and removal.
Two general mold clamp mechanisms are used for part formation from the extruded parison.
-In the first arrangement or shuttle system, the blowing station is situated on one or both sides of the extruder. As
soon as an appropriate length of parison is extruded, the clamp mechanism moves from the blowing station to a
position under the die head, captures and cuts the parison, and then returns to the blowing station for part blowing,
cooling, and removal. This ensures that there is no interference with parison formation.
-In the second or rotary system, a number of clamping stations are mounted on a vertical or horizontal wheel. As
the wheel rotates at a predetermined rate, blowing stations successively pass the parison head(s) where it is
entrapped for subsequent part formation.
b. Injection Blow Molding: this process is a non-continuous cyclic process consisting essentially of two phases.
In the first phase, a preform is molded by injecting melted plastic into a steel mold cavity where it is kept hot and
conditioned. In the second or subsequent phase, the preform is metered into the blow mold where the blowing
operation takes place to form the final part. The major advantages of injection blow molding are the quality of the
molded part and productivity. There is no flash production. Therefore, the molded part neither has a pinch-off scar
from flash nor requires additional trimming or other finishing steps for waste retrieval. Also, the molded parts show
hardly any variation in weight, wall thickness, and volume from the accurately molded preform
Blow molding is a process used extensively for the production of bottles and other hollow plastic items with thin
walls.

4. Rotational Molding: is a process used for producing hollow, seamless products having heavy and/or complex
shapes. In rotational molding a premeasured amount of powder or liquid polymer is placed in the bottom half of
the mold, and the two halves of the mold are locked together mechanically. The mold is then rotated continuously
about its vertical and horizontal axes to distribute the material uniformly over the inner surface of the mold. The

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rotating mold then passes through a heated oven. As the mold is heated, the powdered polymer particles fuse
forming a porous skin that subsequently melts and forms a homogeneous layer of uniform thickness.
Fig. 5: Diagram of rotation molding

5. Thermoforming: is a process for forming moderately complex shaped parts that cannot be injection molded
because the part is either very large, too expensive or has very thin walls. It consists essentially of two stages:
elevation of the temperature of a thermoplastic sheet material until it is soft and pliable and forming the material
into the desired shape using one of several techniques.

Thermoforming techniques may be grouped into three broad categories: vacuum, mechanical, and air blowing
processes: Vacuum forming; Mechanical forming, Air blowing process.
a. Vacuum Forming: The plastic sheet is clamped in place mechanically and heated. A vacuum is then placed
beneath the hot elastic sheet, and this makes atmospheric pressure push the sheet down onto the contours of the
cold mold. The plastic material cools down, and after an appropriate time the cooled part is removed.
b. Mechanical Forming: In this case, a hot sheet is stretched over a mold or matched molds without the use of air
or pressure. In matched mold forming, the heated sheet is clamped over a female mold or draped over the mold
force (male mold). The two molds are then closed. The resulting part has excellent dimensional accuracy and good
reproduction of the mold detail, including any lettering and grained surfaces.
c. Air Blowing Process: It involves using of a compressed air to form the sheet. In one variation, a plastic sheet is
heated and sealed across the female cavity. Air at controlled pressure is introduced into the mold cavity. This blows
the sheet upward into an evenly stretched bubble. A plug which fits roughly into the mold cavity descends on the
sheet. When the plug reaches its lowest possible position, a vacuum or, in some cases, air under pressure is used to
complete part formation.

6. Compression Molding: In compression molding, a preweighed amount of material is loaded into the lower half
of a heated mold or cavity. The force plug (plunger) is lowered into the cavity, and pressure, which can range from
20 to 1000 tons, is applied to the powder. Under heat and pressure, the powder melts and flows into all parts of the
mold cavity, the resin cross-links thus ecoming irreversibly hardened. After an appropriate time, the mold is opened
and the part is ejected while still hot (usually under gravity) and allowed to cool outside the mold.

Figure 6: Diagram of compression molding

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7. Transfer Molding In transfer molding, a measured charge of preheated thermoset material is placed in separate
or auxiliary heated chamber called the pot. A plunger is then used to force the molten material out of the pot through
the runner system into the closed mold cavity where curing occurs. As the material enter the mold, the air from the
mold cavity escapes through vents located strategically on the mold. At the end of the cure cycle, the entire shot,
including the gates, runners, sprues, and excess material remaining in the pot (referred to as cull) is ejected
simultaneously with the molded part. Transfer molding has comparatively shorter cycle and loading times than
compression molding

Fig. 7: Diagram of a transfer molding operation

8. Casting: In casting processes, the resin material is added with an appropriate amount of hardener, catalyst, or
accelerator, mixed manually or mechanically, and then poured into a mold, which is normally coated with a mold-
release agent. Air is removed if necessary and the resin is allowed to solidify. The casting process is relatively slow
and employs comparatively cheap equipment. To facilitate the removal of the cast part from the mold, mold-
releasing agents such as high melting waxes, silicone oils, greases, and some film-forming agents are used to coat
the mold.

9. Rolling and Calendering: The rolling mills consist of two rolls that are used exclusively for the compounding
of thermoplastics. The product that results from rolling is a sheet that can be granulated after cooling or fed in
plasticated form directly into the processing equipment.
PVC and rubber are processed using this process. When the rolls are more than two in number, and the polymer is
to be shaped using these rolls; then the machine is called a calendar. The number of rolls in a calendar can be upto
seven