Polymer and Ceramic

Processing

Outline

Polymer Processing Techniques

Polymer Additives
Ceramic Fabrication Methods
Glass Forming
Particulate Forming
Cementation

Forming Processes for Polymers

Compression Molding
Injection Molding
Extrusion
Blow Molding

Processing Details

Blow Molding Techniques

Extrusion
[hose and tubing, belts, rope and cable covers,
sheeting and films]

Foaming Techniques
Foam molding offers the possibility of increasing the
size of a part without increasing weight and reducing
the weight of a part with controlled change of
properties. Chemical foaming involves mixing a
chemical blowing agent with pellets prior to the pellets
being fed into the feed throat of the molding machine.

Injection Molding
Most engineering thermoplastic parts are fabricated
by injection molding.

http://www2.dupont.com/Plastics/en_US/Knowledge_Center/Processing/processing_methods.html

Polymer Formation
Thermoplastic - can be reversibly cooled &
reheated, recycled; heat until soft, shape, then
cool.
examples: polyethylene, polypropylene,
polystyrene.
Thermoset - when heated, forms a molecular
network (chemical reaction), degrades (doesnt
melt) when heated.
examples: urethane, epoxy

Additives for Plastics

Fillers
Pigments
Stabilizers
Antistatic Agents
Flame Retardants
Plasticizers
Reinforcements
Catalysts

Polymer Additives
Improve mechanical properties, processing, durability.
Fillers - Added to improve tensile strength & abrasion
resistance, toughness & decrease cost. Examples: carbon
black, silica gel, wood flour, glass, limestone, talc.
Plasticizers - Added to reduce the glass transition
temperature Tg below room temperature. Presence of
plasticizer transforms brittle polymer to a ductile one.
Commonly added to PVC.
Stabilizers Antioxidants, UV protection
Lubricants - Added to allow easier processing polymer
slides through dies easier (sodium stearate).
Colorants - Dyes and pigments
Flame Retardants - Substances containing chlorine,
fluorine and boron.

More Additives
Antimicrobials: Used to control the build up of bacteria, fungi and
algae on the surface of plastic products. A wide range of chemical
and natural compounds are used as antimicrobials. An example
would be naturally occurring silver ions used in products like cell
phones or organic acids in food-related products.
Antistatics: Used to minimize static electricity. These types of
additives can be mixed with the resin or applied to the surface of the
product. Antistatic additives are common to a wide variety of
products ranging from cosmetics to industrial goods to sensitive
electronic parts.
Fibers: Used to increase strength and stiffness. The most common
type of fibers added for strength would be carbon and glass. Glassreinforced plastic is more commonly known as fiberglass.

Processing Plastics Compression Molding

Thermoplastics and thermosets
polymer and additives placed in mold cavity
mold heated and pressure applied
fluid polymer assumes shape of mold

Processing Plastics Injection Molding

Thermoplastics and some thermosets

when ram retracts, plastic pellets drop from hopper into barrel
ram forces plastic into the heating chamber (around the
spreader) where the plastic melts as it moves forward
molten plastic is forced under pressure (injected) into the mold
(die) cavity where it assumes the shape of the mold

Barrel
http://en.wikipedia.org/wiki/Injection_mold

10

Plastic Injection Molding

Operate 30 plastic injection molding machines from 22 tons to 550 Tons and 60
oz. shot capacity. Many machines are capable of multiple core pulls for complex
plastic injection molded parts.
Plastic injection molding group services mid-sized manufacturing companies in
the energy, electronics, life science, aerospace, food and beverage, industrial and
construction markets. As a custom plastic injection molder we seek diversity in
many markets and focus our skills on part geometry for molding, material and
product application.
Our plastic injection molding group processes most commodity and engineering
injection molded resins including PS, PE, PP, ABS, SAN, PC, PVC, PBT, PPS,
TPO, TPU, POM, Nylon 66, Nylon 11 and many custom compounded engineering
resins.

http://www.blackwellplastics.com/PlasticRodExtrusion.html

Processing Plastics Extrusion

Thermoplastics

plastic pellets drop from hopper onto the turning screw

plastic pellets melt as the turning screw pushes them
forward by the heaters
molten polymer is forced under pressure through the
shaping die to form the final product (extrudate)

12

Extrusion of Plastics
In the extrusion of plastics, raw thermoplastic material in the
form of small beads (resin) is gravity fed from a top mounted
hopper into the barrel of the extruder. Additives (colorants and
UV inhibitors in either liquid or pellet form) are often used and
can be mixed into the resin prior to arriving at the hopper.
The material enters through the feed throat (an opening near the
rear of the barrel) and comes into contact with the screw. The
rotating screw (normally turning at up to 120 rpm) forces the
plastic beads forward into the barrel which is heated to the
desired melt temperature of the molten plastic (which can range
from 200C/400F to 275C/530F depending on the polymer).
In most processes, a heating profile is set for the barrel where
three or more independent PID controlled heater zones
gradually increase the temperature of the barrel from the rear
(where the plastic enters) to the front. This allows the plastic
beads to melt gradually as they are pushed through the barrel
and lowers the risk of overheating which may cause degradation
in the polymer.
13

Processing Plastics Blown-Film Extrusion

The manufacture of plastic film for products like shopping bags is
done using a blown film line.
This process is the same as a regular extrusion process up until
the die. The die is an upright cylinder with a circular opening similar
to a pipe die. The diameter can be a few cm to more than 3 m
across. The molten plastic is pulled upward from the die by a pair
of rollers high above the die.
Changing the speed of these rollers changes the gauge (wall
thickness) of the film. Around the die sits an air-ring. The air-ring
cools the film as it travels upward. In the center of the die is an air
outlet where compressed air can be forced into the center of the
extruded circular profile, creating a bubble.

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Ceramic Fabrication Methods

Glass
A glass is an inorganic non metallic material that does
not have a crystalline structure. Such materials are said
to be amorphous and are virtually solid liquids cooled at
such a rate that crystals have not been able to form.
Typical glasses range from the soda-lime silicate glass
for soda bottles to the extremely high purity silica glass
for optical fibers.
Glass is widely used for windows, bottles, glasses for
drinking, transfer piping and receptacles for highly
corrosive liquids, optical glasses, windows for nuclear
applications.
Most products have been blown glass. In recent times,
most flat glass has been produced using the float
process.
Mass produced bottles and decorative products are
made using industrial scale blown glass process.

Glass Properties: Viscosity

Glass or noncrystalline materials do not solidify in the
same sense as crystalline materials. Upon cooling, a
glass becomes more and more viscous with
decreasing temperature.
Viscosity, describes a fluid's internal resistance to flow and may
be thought of as a measure of fluid friction.
-- relates shear stress () and velocity gradient (dv/dy):

glass

dy
dv

dv
dy

velocity gradient

dv / dy

has units of (Pa-s)

17

Important in glass forming

operations are the viscositytemperature characteristics of
glass.
Temperatures:
Melting Point:
viscosity = 10 Pa-s; glass is
fluid enough to be considered
liquid.
Working Point:
viscosity = 103 Pa-s; glass is
easily deformed.
Softening Point:
viscosity = 4x106 Pa-s; max
temp. glass can be handled
without altering dimensions.
Annealing Point:
viscosity = 1012 Pa-s; good
atomic diffusion; stress relief.
Strain Point:
viscosity = 3 x 1013 Pa-s; below
strain point, fracture will occur
before the onset of plastic
deformation .

Glass Properties
Specific volume (1) vs Temperature (T):

Crystalline materials:

Specific volume
Liquid
(disordered)

Supercooled
Liquid

-- crystallize at melting temp, Tm

-- have abrupt change in specific
volume at Tm

Glasses:

Glass
(amorphous solid)
Crystalline
(ordered)

Tg

density

Tm

solid

-- do not crystallize
-- change in slope in spec. vol. curve at
glass transition temperature, Tg
-- transparent - no grain boundaries to
scatter light
19

Log Glass Viscosity vs. Temperature

Viscosity decreases with T

Viscosity [Pa-s]

a
ilic
ds a
se silic
fu
% x
96 yre e
P
-lim
da
so ss
gla
10 14

10 10
10 6
10 2
1
200

soda-lime glass: 70% SiO2

balance Na2O (soda) & CaO (lime)
borosilicate (Pyrex):
13% B2O3, 3.5% Na2O, 2.5% Al2O3
Vycor: 96% SiO2, 4% B2O3
fused silica: > 99.5 wt% SiO2

strain point
annealing point
Working range:
glass-forming carried out

Tmelt
600 1000 1400 1800 T(C)
20

Some glass blowing is

done by hand.
The process is completely
automated for the
production of glass jars,
bottles and light bulbs.
From a raw gob of glass,
a parison (temporary
shape) is formed by
mechanical pressing in a
mold.
This piece is inserted into
a finishing or blow mold
and forced to conform to
the mold contours by the
pressure created from a
blast of air.
Drawing is used to form
long glass parts (sheets,
rods, tubing and fibers)
that have a constant cross
section.

Glass Blowing

Sheet Glass Forming

Sheet forming continuous casting
sheets are formed by floating the molten glass on a pool of
molten tin

22

Heat Treating Glass

Annealing:
-- removes internal stresses caused by uneven cooling.

Tempering:
-- puts surface of glass part into compression
-- suppresses growth of cracks from surface scratches.
-- sequence:
before cooling

hot

initial cooling

at room temp.

cooler
hot
cooler

compression
tension
compression

-- Result: surface crack growth is suppressed.

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Tempered Glass
Fully tempered glass is roughly 4 times stronger
than annealed glass of the same thickness and
configuration; residual surface compression must
be over 10,000 psi for 6mm thickness, according
to ASTM C 1048.
Tempered glass is manufactured through a
process of extreme heating and rapid cooling,
making it harder than normal glass.
The typical process to produce tempered glass
involves heating the glass to over 1,000 F, then
rapidly cooling to lock the glass surfaces in a
state of compression and the core in a state of
tension.
When glass cools down to ambient temperature,
the center plane of the glass contracts more than
the surfaces. The contraction of the center plane
pulls the surfaces into compression and the glass
becomes very strong.
Tempered glass cannot be cut or drilled after
tempering, and any alterations, such as edgegrinding, sandblasting or acid-etching, can cause
premature failure.

Tempering Process
Fabrication occurs on electrically
heated horizontal furnaces that heat
the glass to a uniform temperature of
roughly 1200F.
Ceramic rolls convey the glass
through these furnaces at speeds
regulated to ensure temperature
uniformity and minimal optical
distortions.
When the glass exits from the
furnace, it is rapidly cooled by a
series or air nozzles. This rapid
cooling puts roughly 20% of the glass
surface into a state of compression,
with the center core in tension.

Shattered Tempered Glass

The brittle nature of tempered glass
causes it to shatter into small ovalshaped pebbles when broken. This
eliminates the danger of sharp edges.
Due to this property, along with its
strength, tempered glass is often referred
to as safety glass.
Tempered glass breaks in a unique way.
If any part of the glass fails, the entire
panel shatters at once. This distinguishes
it from normal glass, which might
experience a small crack or localized
breakage from an isolated impact.
Tempered glass might also fail long after
the event that caused the failure.
Stresses continue to play until the defect
erupts, triggering breakage of the entire
panel.

Heat Strengthened
Glass
Heat-strengthened (Hs) glass has
been heated and cooled and is
generally twice as strong as
annealed glass of the same
thickness and configuration.
Hs glass has greater resistance
to thermal loads than annealed
glass and, when broken, the
Hs glass must achieve residual
fragments are typically larger
surface compression between
than those of fully tempered
3,500 and 7,500 psi for 6 mm
glass.
glass, according to ASTM C 1048.
It does not require the strength of Hs glass cannot be cut or drilled
fully tempered glass, and is
after heat-strengthening and any
intended for applications that do
alterations, such as edge-grinding,
not specifically require a safety
sandblasting or acid etching can
glass product.
cause premature failure.

Annealed Glass
Float glass (also called
flat glass) has not yet
been heat-strengthened or
tempered.
Annealing float glass is the process of controlled cooling
to prevent residual stress in the glass. It is part of the float
glass manufacturing process.
Annealed glass can be cut, machined, drilled, edged and
polished.
To anneal glass, the glass is heated and kept for a defined
period of time to relieve internal stresses.
Carefully cooled under controlled conditions to ensure that
no stresses are reintroduced by chilling/cooling.

Glass Properties

100KHz
2
251000C
3
201000C
1

BBlownWare
CCast
DDrawnSheet
EExtruded

FFrit&PowderedGlass
GGob&Strip
KSpecialCane
MMultiform

PPressedWare
RRolledSheet
SGround&Polished
TTubing&Rod
UPanels

Different techniques
for processing
advanced ceramics.

The space shuttle makes use of

~25,000 reusable, lightweight,
highly porous ceramic tiles that
protect the aluminum frame from
the heat generated during re-entry
into the Earths atmosphere.

Typical steps encountered in

the processing of ceramics.

Green ceramic - A ceramic

that has been shaped into a
specific form but has not yet
been sintered.

Mechanical Properties of Advanced

Ceramics

Typical Porcelain Composition

(50%) 1. Clay
(25%) 2. Filler e.g. quartz (finely ground)
(25%) 3. Fluxing agent (Feldspar)
-- aluminosilicates plus K+, Na+, Ca+
-- upon firing - forms low-melting-temp. glass

CEREC Technology
An optical 3D image is acquired with a small
camera, directly in your mouth.
The computer and CEREC 3D software
converts the digital picture to a three dimensional
virtual model of your prepped tooth. Your dentist
then designs your restoration right on screen
using the software.
This software can handle single tooth restoration:
crowns, inlays (fillings), onlays (partial crowns),
and veneers. After the design is complete, the
data is transmitted via a wireless radio signal to
the CEREC Milling Unit.
Diamond coated instruments mill a ceramic block
to reproduce the design.
This is done during a single appointment using
Computer Aided Design/Computer Aided
Manufacture (CAD/CAM).
http://www.sirona.com/ecomaXL/index.php?site=SIRONA_COM_cadcam_systems

Ceramic Materials
When creating CEREC restorations, you can choose from
feldspar ceramics, glass ceramics and high-performance
polymers.
They are biocompatible, clinically tested, durable and metalfree. Problems due to corrosion and incompatibility can be
virtually ruled out.
The ceramic materials fulfill stringent standards in terms of
fracture toughness, abrasion, aesthetics and machinability.
Sirona has developed its own range of machinable ceramic
blocks for the CEREC and inLab CAD/CAM systems.
Sirona inCoris materials consists of partially sintered
framework ceramics they provides the basis for
manufacturing high-precision all-ceramic crowns and bridge
restorations made of aluminium and zirconium oxide.

Slip Casting
A liquid clay body (a slip) is poured into a plaster mold and allowed to form a
layer on the inside cavity of the mold.
In a solid cast mold, ceramic objects like handles and platters are surrounded by
plaster on all sides with a reservoir for slip, and are removed when the solid
piece is held within.
For a hollow cast mold, once the plaster has absorbed most of the liquid from
the outside layer of clay the remaining slip is poured off for later use.
The cast piece is removed from the mold, trimmed and dried. This produces a
green piece that is then fired, with or without decoration and glaze.
The technique is suited to the production of complex shapes, and is commonly
used for toilets, basins, figurines and teapots. The technique can also be used
for small scale production runs.
pour slip
into mold

absorb water
into mold

green
ceramic

solid component

pour slip
into mold

drain
mold

hollow component

green
ceramic

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Hydroplastic Forming
Hydroplastic forming - Processes where a moist
ceramic clay body is formed into a useful shape.
Mill (grind) and screen constituents: desired
particle size.
Extrude the mass.
Dry and fire the formed piece.
Ao
force

container

ram

billet

container

die holder
extrusion

Ad

die
36

Drying and Firing

Drying: as water is removed - interparticle spacings decrease
shrinkage.

wet body

partially dry

completely dry

Firing:
-- heat treatment between
900-1400C
-- vitrification: liquid glass forms
from clay and flux flows
between SiO2 particles. (Flux
lowers melting temperature).

micrograph of porcelain

Drying too fast causes sample to warp or crack due to non-uniform shrinkage
Si02 particle
(quartz)
glass formed
around
the particle

70 m

37

Kaolinite
Clay is inexpensive.
Kaolinite is a clay mineral with the
chemical composition Al2Si2O5(OH)4.
It is a layered silicate mineral, with one
tetrahedral sheet linked through
oxygen atoms to one octahedral sheet
of alumina octahedra.
When water is added to clay, water
molecules fit between layered sheets,
reducing degree of van der Waals
bonding; (Can shear along vdW bonds
more easily).
When external forces are applied, clay
charge
particles are free to move past one
neutral
another, becoming hydroplastic.
Adding water to clay enables extrusion
and slip casting.
Kaopectate, paper, pipes (smoking).

Shear

charge
neutral
Structure of
Kaolinite Clay

weak van
der Waals
bonding
4+

Si
3+
Al
OH
2O
Shear

Kaolin

Powder Pressing
Used for clay and non-clay
compositions.
Powder (plus binder)
compacted by pressure in a
mold.

Microstructure of a barium magnesium

tantalate (BMT) ceramic prepared using
compaction and sintering. (Courtesy Heather
Shivey.)

Uniaxial compression - compacted in single direction

Isostatic (hydrostatic) compression - pressure applied

by fluid - powder in rubber envelope

Hot pressing - pressure + heat.
40

Sintering
Sintering occurs during firing of a piece that has been
powder pressed, powder particles coalesce and pore size is
reduced.

Typically, ceramics with a small grain size are stronger than

coarse-grained ceramics.

Finer grain sizes help reduce stresses that develop at grain

boundaries due to anisotropic expansion and contraction.

Aluminum oxide powder:

-- sintered at 1700C for 6 minutes.

15 m41

Tape Casting
Tape casting - A process for making thin sheets of ceramics
using a ceramic slurry consisting of binders, plasticizers, etc.
The slurry is cast as tape with the help of a blade onto a plastic
substrate. Used for integrated circuits and capacitors
Slip = suspended ceramic particles + organic liquid

Ceramic Fabrication Methods - Cementation

Hardening of a paste: paste
formed by mixing cement
material with water.
Formation of rigid structures
having varied and complex
shapes.
Hardening process: hydration
(complex chemical reactions
involving water and cement
particles).
Production of Portland cement:
mix clay and lime-bearing
minerals
calcine (heat to 1400C)
grind into fine powder

43