CHAPTER 0

0.
(polymer)
(many parts). , .. (rubbers),
.

repeating unit (part)
, (polyethylenes repeating
unit) CH2 -CH3.
:

(strength) (stiffness)

(temperature limitations)

, (deform continuously) (i.e.

"creep"- )

, . ,
, ?

1981

6
3
(!), 20x10 m ,

.
:

/
(minimum fabrication and finishing).

.. ,

: - 00- 2

, .. (flexible)
(transparent).

(fiber-reinforced
composites) (high performance) (long
service life). , ..
Stealth fighter-bomber 65% .
3% Boeing 767 ,
Boeing 777 10% .

(aerospace applications).

(automotive applications).

.

0.1. (POLYMER STRUCTURE)

,
(simple repeating unit), :
.....AAAAAAAAAA.....
(vinyl polymers).
CH2

CH
R

R => H

> POLYETHYLENE (PE)

: - 00- 3
R => CH3

R =>
R => Cl

> POLYPROPYLENE (PP)

(phenyl)

> POLYSTYRENE (PS)

> POLYVINYL-CHLORIDE (PVC)

, (linear)
(branched) ( 0-1):

(a) (LINEAR)
-AAAAAAAAAAAAA-

(b) (BRANCHED)

-A A A A A A A A A A A A A A A A
A
A
A
A
A
A
A
A
A
A
A
A
A
A A A A A
A

( - dendritic structure).
Cayley (n-Cayley tree), n ,
(propagated multiple generations).
(level of branching)
(branching frequency), , 1000
(backbone carbon atoms).

: - 00- 4

0-1: (branched structures)

(c) (CROSS-LINKED)

-A A A A A A A A A A
A
A
A
-A A A A A A A A A A
A
A
A
-A A A A A A A A A A

A A A A A A A A A A
A
A
A
A A A A A A A A A A
A
A
A
A A A A A A A A A A

(3-D network structure), ..

/ / (vulcanized rubber).
.

0.1.1. (TACTICITY)
(side/pendant groups) ( )

(crystallinity) .
(orientations)

: - 00- 5

(tacticity). : (isotactic),
(syndiotactic) (atactic).
(polypropylene, PP). PP (i-PP) (ethyl groups)
, PP (s-PP)
(alternate sides). PP,
(Bernoulian or Markov chain). 0-2
.
i- s- ,
. (PS),
(PVC) (PMMA).
- . ,

. (LLDPE)

.

Figure 0-2. .

: - 00- 6
0.1.2. (CRYSTALLINITY)
0-3 - .
(ordered crystals)
(amorphous regions).
.
.
() .

0-3. - (semi-crystalline)

0.2. (POLYMER TYPES)

(THERMOPLASTICS):
(PS, PE, PVC, LLDPE, HDPE).
(THERMOSETS):
. .
(cross-linking).
, .. .
(phenol formaldehyde), (epoxies)
(polyurethanes).

: - 00- 7
(ELASTOMERS): (cross-linked network
structures) (deformability),
(complete recoverability)
(flexibility) (entanglement density) (..
(natural rubber) (cross-linked)
). => (RUBBERS).
(plastics).
. (compounded)

(pellets), (granules), (powder), (flakes)
.
: (additives), (fillers)
(reinforcements) ().
(additives) :
(colorants)
(flame retardants)
(stabilizers) ,
.
(lubricants)
(formability)
(processing aids)
.
(fillers):
.
(reinforcements) (glass or carbon fibers)
(strength) (stiffness).

: - 00- 8
0.3. (GLASS TRANSITION)
(MELTING POINT)
(ordered) (random) .
(glass
transition temperature), Tg, ..
(hard and rigid). (crystalline polymers)
Tg,
0oC
. (low mobility)
(well-packed) .

(3-D ordered arrays). ,
, Tm. :
Tg/Tm=0.6.
(strength)
(transparency).
(opaque) .

, ,

(15 - 80%).

0-1.
Tg - . 04
Tg.

: - 00- 9

0-1. Tg Tm

Tg
o
C

Tm
o
C

o
C

HDPE

-100

135

160 - 240

LDPE

-100

110

160 - 240

PP

-15

165

180 - 240

PVC

80

240

170 - 200

PS

100

180 - 240

Rubber

-70

35

90 - 110

PET

70

265

275 - 290

NYLON-66

40

265

275 - 290

NYLON-6

40

220

230 - 260

PMMA

115

200 - 250

0-4.
(specific volume) .

: - 00- 10

0.4.
,
, .
:
(Number-Average) Mn
(Weight-Average)

Mw

z (z Average)

Mz

z+1 (z+1 Average)

Mz+1

Mi ni,
niMi ni:

n M
n
i

Mn =

(number-average).
Mi wi, :
wi =

ni M i
nM
weight of M i
= i i =
ni Mi W total weight

ni M i = W wi
,

ni = W

wi
Mi

Mn :
Mn =

n M
n
i

w
w
M
i
i

: - 00- 11

n M
=
n M
i

Mw

=
i

w M
w
i

(weight-average).

n M
=
n M

Mz

w M
=
w M

z (z-average).

M z +1

n M
=
n M

w M
=
w M

z+1 (z+1 average).

: 99%
M=20,000 1% M=109. Mn, Mw, Mz and Mz+1.
:
Mn =

1
w =
= 20,202
0.99
0.01
w
+
M 20,000 10
i
i

Mw =

w M
w
i

0.99 20,000 + 0.01 109

107
1

0.99 20,0002 + 0.01 109

109
107

0.99 20,0003 + 0.01 1027

109
0.99 20,0002 + 0.01 1018

Mz

w M
=
w M
i

M z +1

w M
=
w M

i
3

(most probable, Gaussian)

wi =

M
M
exp
dM
2
Mn
Mn

: - 00- 12
M dM 2 . ,

Mn = Mw /2 = Mz /3 = Mz+1 /4
Mw/Mn (polydispersity).
, Mw ~ 10,000 - 400,000.
.
PS:

Mw /Mn ~ 2.5 - 4

PP:

Mw /Mn ~ 5 - 10

PE:

Mw /Mn ~ 5 30

m-PE :

Mw /Mn ~ 2

, (dilute solution viscosity), ,

0
= KM u
c 0 C
0

lim

=
o =
C =
K, =
Mv = (viscosity-average molecular weight)
0-5
. (MWD)
, (intrinsic viscosity).
. Dealy and Larson (2006)
.

: - 00- 13

Number of Molecules (ni)

Mn

Mv
Mw
Mz
Mz+1

Molecular Weight (Mi)

0-5: .

0.5.

(tensile test). ,
" " " "

= E

( Hooke)

E = Young ,
=

L L0
L0

: - 00- 14

(N/m2)

L0
L (m)
0-6:

E => N/m2 = Pa. -

(tensile modulus, E)
Hooke .

Slope = E

0-7: - .

0-3 GigaPascals
- GPa (Giga = 109).
0-3:
LDPE

0.2 GPa

HDPE

1.0 GPa

NYLON-66

2.0 GPa

PVC

2.5 GPa

PS

3.4 GPa

Steel

210 GPa

: - 00- 15

STEEL

PLASTICS

0-8: .

,
(weak cohesive forces of Van der Waals)
(entangled) (coiled) .

(super-strong plastics)
(align) .
(carbon-carbon

bonds)

(single-filament)

!!! (260 GPa 210 GPa).

, ..
() (extrusion and drawing) (fibers)

: - 00- 16
. ,
(curl up).
.

0.6.

PE

(flexible), (leathery), HDPE

LDPE

PP

(tough)

PS

(hard), (brittle), (transparent)

PC

(hard, tough), (transparent)

,.
Glass

Glass
Transition
Region

Semi-Crystalline
Polymers

Log E
Rubbery
Melt
Amorphous
Polymers

Tg

Temperature

Tm

0-9: .

: - 00- 17

(none for glass, a

lot for melt).

0-9 :

1. (Glass)
2. (Glass transition region)
3. (Rubbery plateau)
4. (Melting region)
5. (Liquid melt)

Tg ,

(heat capacity), Cp,

differential scanning calorimetry (DSC).

Tg

(flowable like a liquid).

To Tm .

(rule of thumb): Tg (Kelvin) ~ 0.5Tm 0.67Tm.

0.7. (TIME-DEPENDENCE)

v
. , to PVC
(>1 mm/s) (<0.05 mm/s).

: - 00- 18

Fast extension
Stress

break

Slow extension

break

Strain
0-10: -

(simple tensile test)

, ,
. ,
(creep), ..
0-11.

Polymer

Strain
Steel

Time, Hours
0-11: (creep behavior)

: - 00- 19

, .. .

0.8. (TENSILE MODULUS)

(TENSILE STRENGTH)

(tensile modulus), E,

-.

(tensile strength)

(rupture) ( = F/A).
:
~ 1 GPa
~ 20 MPa

(tensile strength versus tensile modulus).
. ,

(flexural modulus), (compressive strength), (impact
strength), , (creep).

: - 00- 20

Specific strength (106 N m kg-1)

5.0
4.5
superdrawn
UHMW - PE

4.0

gel-spun
polyethylene fiber
(optical)

thermotropic liquid
crystal polymer fiber
aramid fiber 29
Kevlar 49

3.5
3.0

high-strength
carbon fiber

2.5
2.0

S-glass

1.5

'ultradrawn'
polyethylene fiber
(typical)
boron fiber

E-glass

1.0

rigid rod ordered

polymer fiber (liquid
crystal)

high-modulus
carbon fiber

SiC (ceramic fiber)

steel
aluminum
liquid crystal

0.5
0.0
0.0

0.5

ultrahigh-modulus
carbon fiber

1.0

1.5

2.0

2.5

3.0

3.5

Specific tensile modulus (108 N m kg-1)

0-12:

: - 00- 21
0.9. (RHEOLOGY)

( )




. ,
, . Hooke
.
.
(rheology)

(study of flow and deformation of matter).

0.10.

. Eugene Bingham, ,
.
.
.
/ .
Hooke ,

= G

(stress)

(strain)

: - 00- 22
G

(property of a solid)

(Newton's law of
viscosity),

= &

&

& d / dt .

:
Hooke ,
(Hookean) .
,
.
, ,
(Hooke's law)
(Newton's law).

"silly putty" or "bouncing putty" ( ):

, .
.
, .
(time
dependent modulus), G(t).

: - 00- 23

0.13: silly putty ,

(); (), .

-.
, .
, . (yield
stress), (
, shear thinning behaviour - viscosity decreases with shear rate).

0-14: .
( , yield stress).

: - 00- 24
(normal stress effects):
, (inertial forces) .
, .
() (hoop
stresses), ,
.

0.15:
. -
() (hoop stresses, normal stresses).

(tubeless or ductless
siphon).
(high extensional viscosity).

0.16: ,
.

: - 00- 25

1. : (relaxing modulus), G(t).

2. (shear thinning or thickening viscosity), (& ) .

3. , T11-T22 > 0, T22-T33 < 0.

4. (extensional thinning or thickening viscosity),

E (& ) .

: - 00- 26

(Rheology)
Dealy J.M., Rheometers for Molten Plastics, Van Nostrand Reinhold NY (1983).
Dealy J.M. and K.F. Wissbrun, Melt Rheology and Its Role in Plastics Processing, Van Nostrand
Reinhold, NY (1990).
Dealy J.M., and R.G. Larson, Structure and Rheology of Molten Polymers, Hanser, Munich (2006).
Macosco C.W., Rheology: Principles, Measurements and Applications, VCH, London (1994).
Tanner R.I., Engineering Rheology, Clarendon Press, Oxford (1985).
Bird R.B., R.C. Armstrong and O. Hassager, Dynamics of Polymeric Liquids: Vol. 1, Fluid Mechanics,
Wiley, New York (1987).

(Polymer Processing and Engineering)

Tadmor Z. and C.G. Gogos, Principles of Polymer Processing, Wiley, New York (1979). A wealth of
information on extrusion, injection molding, etc., it includes just about every important reference on
polymer processing till about 1978.
OBrien K.T., Application of Computer Modeling for Extrusion and Other Continuous Polymer
Processes, Hanser Publishers, Munich (1992).
Michaeli W., Extrusion Dies, Hanser, Munich (1992).
Rauwendaal C., Polymer Extrusion, Hanser, Munich (1986).
Hensen F., Plastics Extrusion Technology, Hanser, Munich (1988).
Collyer A.A. and D.W. Clegg, Rheological Measurements, Elsevier, London (1988).
Isayev A.I., Injection and Compression Molding, Marcel Dekker, New York (1987).
Kennedy P., Flow Analysis Reference Manual, Moldflow Pty Ltd., Kilsyth, Melbourne (1993).
Manzione L.T. (Editor), Applications of Computer-Aided Engineering in Injection Molding, Hanser,
New York (1987).
Crawford R.J., Plastics Engineering, Pergamon Press, New York (1987).
Morton- Jones D.H, Polymer Processing, Chapman and Hall, New York (1989).
Michaeli W., Einfuehrung in die Kunststoffverarbeitung (in German) Hanser, Munich (1992).
Agassant J.-F., P. Avenas and J.Ph. Sergent, La Mise en Forme des Matieres Plastiques, Tec-Doc
(Lavoisier), Paris (1986).
Birley A.W., B. Haworth and J. Batchelor, Physics of Plastics, Hanser, New York (1992).
Sperling L.H., Introduction to Physical Polymer Science, Wiley, New York (1992).
Corish P.J. (Editor), Concise Encyclopedia of Polymer Processing and Applications, Pergamon Press,
New York (1992).