-1   
-2!    
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-. ()&* -4 , 
43  5)6 -5  3  1
& 5)6 -6 :  ';)
  = 3>1? -7
)&)& 3A -8>&= >

  

& ?  5(, CD3  (,

3& A3, ! E $3

Commercialization dates of common

synthetic polymers

Properties of alkane polyethylene

series

From Little molecules to big

molecules: wax

From Little molecules to big

molecules:polyethylene

Various polymers

Various polyolefins

The rest of olefins

Common copolymers

Polymers nomenclature

Natural polymers

Polycondensate polymers

A modern vulcanizable formulation

for tires tread

tand as a function of temperature for

tires at f=1Hz

Linear polymers

More polymers

Various glassy polymers

O CH3

CH CH2

Poly methyl acrylate

H3C

C O

CH2

Poly ethyl methacrylate

C
CH3

CH3

Poly n-butyl methacrylate

CH2

CH3

O CH2

O CH2

C O

C O

C
CH3

CH2

CH
n

CH3

Poly isobutyl methacrylate

CH3

O CH2

O CH2

C O

C O
CH2

CH2

CH
n

Poly n-propyl methacrylate

C
CH3

Poly isopropyl methacrylate

  

 
 3: )* '& $ $

 
  5I : )* '& $ $

Calculation of the RMS chain length.

Preliminary description of polymer

chains

Length of coil

Soft and hard segments

There are three factors determining

whether a polymer is glassy, rubbery or
fiber-forming:

1-chain flexibility
2-interchain attraction
3-regularity of the polymer
(their impact on
Tg,Crystallinity and may be on
Tm)

Chain tacticity

Trans and cis conformations

Cis and trans

Cis

Cis and Trans

Theory of crystallization

Chain tacticity

Chain tacticity

a-linear b-branched c-crosslinked

A chain foldng

A lamella stack

Lamella formation

Lamella formation

A crystalline thermoplstic

differential scanning calorimetry

Tg & Tc and Tm

DSC measurements

is-PP DSC

Description of crystallization process for

polymers

Crystallization and Avrami equation

F=copression factor

Avrami eqn.

Crystallization coefficient

logG vs Tx/Tm

SANS a way to characterize

molecular relaxation

Rearrangement of crystalline during necking

Crystal growth rate

Thermal and physical properties of

PP

Morphology of crystallites in
polymers

Kinetics of crystallization

Kinetics of crystallization

Maximum Growth rate

Maximum crystallization value for

PP

Maximum crystallization value for

PP

Calculation the amount of

crystallization for PP

Physical properties of wet PET yarn

wound at different speeds

Gibbs free energy of oriented and

unoriented state

Polymer molecular orientation

Physical properties of PET as a function of

draw ratio

Orientation of Polymers

Orientation of Polymers

Orientation of Polymers

Orientation of Polymers

WAXS of i-PP extrusion film

extension

WAXS of i-PP extrusion film

extension

WAXS of i-PP extrusion film

extension

 !   Tg

CH3

OH
CH2 CH2 O

CH O

n
Poly methoxy methylene

Polyethylene oxide

CH

CH2
n

Poly vinyl alcohol

Heat evolve for glass transition and

crystallization

Tg for glassy polymers

Tg of glassy polymers
O CH3

CH CH2

Tg=7

H3C

C O

CH2

Tg=100

C
CH3

CH3
CH3

Tg=8

CH2

O CH2

O CH2

C O

C O

C
CH3

CH2

n
CH3

CH3

O CH2

O CH2

Tg=-40

C O

C O
CH2

CH2

CH
n

Tg=-20

CH

Tg=50

C
CH3

Trans isomerism

+
Gauche

and

Gauche

ttg to gtt
ttt to gtg

The variation of the energy of the n-butane molecule

CH3CH2CH2CH3 as a function of the torsion angle of the central
CC bond measured from the eclipsed conformation.

Fringed micelles crystallites

Chains in folded shape

X-ray

Solution growth single crystals

A:amorphous B:Chain folded

C:chain extended D:Fringed micelle

Crystal growth of polyethylene oxide

out of melt after 1 min

Change of compliance with time

Stress-relaxation.
The upper graph shows the applied strain as a functionof time and the
lower graph the resulting stress.

Creep of a viscoelastic solid under a

nconstant stress.

WAXS of PS and PE

PS

PE

Various configuration

A fibre pattern from oriented syndiotactic polypropylene, drawn to a

draw ratio of about 5 at 109.8C.

Small-angle X-ray scattering from unoriented polypropylene. The SAXS

scattering is the dark halo of diameter at its darkest equal to about half the side of
the outer square. This diameter corresponds to about 18.

Melting of alkane series reaching

polyethylene

Entanglement: a-not entangled

b-entangled

Molecular weight and molecular

weight distribution

Molecular weight distribution

Molecular weight

Modulus-Temp behavior of polymers

Different kind of materials

Stress-strain behavior of various

polymers

Various types of impurities at the interfaces

Above and below Tg

Factors affecting Tg

Groups attached to the backbone which increase the

energy required for rotation.
Rigid structures, e.g. phenylene groups, incorporated in
the backbone of the molecule.
The packing of substituents around the main chain (c.f.
PTFE with polyethylene).
Secondary bonding between chains, e.g. hydrogen
bonding.
Primary bonding between chains, e.g. cross-linking.
Length of side chains.
Molecular weight.
Copolymerisation.
Plasticisation.

Factors affecting Tg

By copolymerization.
By introduction of groups in an irregular
manner.
By chain branching.
By lack of stereoregularity.
By differences in geometrical isomerism.

Methods of measuring Tg

Plastics identification codes

Polymer synthesis and structure

Initiation

Propagation

Termination

Step Polymerization

Synthesis of PET

Synthesis of Nylon46

 
'


" #$
 

Rotation around C-C

Trans-guache conformation

Gauche minus
Gauche plus
trans

Energy versus bond rotation in

methyl succinic acid

The 25-MHz 13C spectra of polypropylene in 1,2,4-trichlorobenzene at 140C.

The 25.2-MHz 13C spectra of polypropylene in 1,2,4-trichlorobenzene at

120C.

The 25.2-MHz 13C spectra of polypropylene in 1,2,4-trichlorobenzene at

120C.

Crosslinking

Molecular properties of polymers

during strain

Trans-Gauche transition in polypropylene

Polymers

Relation between Tg and Tm

Polymer solutions

Triangle shape

Ps in different solvents

PS in different solvents

Ps/Acetone/n-propyl laurate

Critical solution temperature

Cohesive energy of polymer and

solvents

Polymer solubility

SP for several polymers

Finding solubilty parameters of

polymers using swelling coeffficient
PU/PS 50:50

PS
PU

m=weight of swollen sample

m0=weight of dry sample
=density of solvent

Meassurement of the solubility

parameters using intrinsic viscosity
PIB
PS

Definition of average molecular weight

a. number average molecular weight ( Mn )

Ni M i
Mn= N
i
(colligative property and end group analysis)

b. weight average molecular weight ( Mw)

Mw =

WiMi
Wi

(light scattering)

Definition of average molecular weight

c. z average molecular weight ( MZ )

MZ=NiMi3
NiMi2

(ultracentrifugation)
d. general equation of average molecular weight :
M=

NiMia+1
NiMia

( a=0 , Mn
e. Mz > Mw > Mn

a=1 , Mw

a=2 , Mz

Polydispersity index : width of distribution

polydispersity index (PI) = Mw / Mn 1

Determination of molecular weight

a-Absolute method :
mass spectrometry
colligative property
end group analysis
light scattering
ultracentrifugation.
b. Relative method : solution viscosity
c. Fractionation method : GPC

Gel Permeation Chromatography

Size exclusion chromatography

Modules of GPC instrumentation

Calibration of GPC, for

polyvinylacetate and polystyrene

Universal calibration for gel permeation chromatography.

THF, tetrahydrofuran.
Log([
]M)

109

107

108

Polystyrene (linear)
Polystyrene (comb)
+ Polystyrene (star)
Heterograft copolyner +
Poly (methyl methacrylate) +

Poly (vinyl chloride)

Styrene-methyl methacrylate graft copolymer
Poly (phenyl siloxane) (ladder)
Polybutadiene

106

105
18
20
22
24
26
Elution volume( 5 ml) counts, THF solvent)

28

30

Molecular weight (M)

Typical semilogarithmic calibration plot of molecular weight versus

retention volume.
106

105

104

103

Retention volume (Vr) (counts)

Universal calibration method (method 1)

[]1M1 = []2M2
to be combined Mark-Houwink-Sakurada
equation
logM2 = (

1
1 + a2

)log( KK1 ) + (
2

1 + a1
1 + a2

)logM1

Typical gel permeation chromatogram.

Dotted lines represent volume counts.

Detector
response

Baseline

Elution volume (Vr) (counts)

GPC calibration plot of PS in THF at

25C

Mn and Mw from the height or area

of GPC curve

GPC calibration (method 2)

PS distribution for stationary phase phenogel

M; and the mobile phase butanone

Mw determin. of Polymethyl
methacrylate in blends (RI and UV
detectors)

Molecular Weight and Polymer Solutions

1 Number average and weight average molecular weight
2 Polymer solutions
3 Measurement of number average molecular weight
4 Measurement of weight average molecular weight
5 Viscometry
6 Molecular weight distribution

End-to end distance

Number Average and Weight Average Molecular Weight

A. The molecular weight of polymers

a. Some natural polymer (monodisperse) :

All polymer molecules have same molecular weights.
b. Synthetic polymers (polydisperse) :
The molecular weights of polymers are distributed
c. Mechanical properties are influenced by molecular weight
much lower molecular weight ; poor mechanical property
much higher molecular weight ; too tough to process
optimum molecular weight ; 105 -106 for vinyl polymer
15,000 - 20,000 for polar functional group containing polymer (polyamide)

Expansion of chain

Example of molecular weight calculation

a. 9 moles, molecular weight (Mw) = 30,000

5 moles, molecular weight ( Mw) = 50,000

Mn =

(9 mol x 30,000 g/mol) + (5 mol x 50,000 g/mol)

9 mol + 5 mol
9 mol(30,000 g/mol)2 + 5 mol(50,000 g/mol)2

Mw =

9 mol(30,000 g/mol) + 5 mol(50,000 g/mol)

= 37,000 g/mol

= 40,000 g/mol

Example of molecular weight calculation

b. 9 grams, molecular weight ( Mw ) = 30,000

5 grams, molecular weight ( Mw ) = 50,000
Mn =

Mw =

9g+5g
(9 g/30,000 g/mol) + (5 g/50,000 g/mol)
(9 g/30,000 g/mol) + (5 g/50,000 g/mol)
9g+5g

= 35,000 g/mol

= 37,000 g/mol

Polymer Solutions
A. Process of polymer dissolution : two step
first step : the solvent diffuses into polymer masses to make
a swollen polymer gel

second step : swollen polymer gel breaks up to solution

Polymer Solutions
Thermodynamics of solubility :
Gibb's free energy relationship
G = H
S
- T
G < 0 : spontaneously dissolve
T and S are always positive for dissolving process.
Conditions to be negative G,
H must be negative or smaller than TS.

C. Solubility parameter :

Hmix=Vmix

E1

E2

[( V ) -( V ) ]
1/2

1/2

1, 2 = volume fraction
E1/V1, E2/V2 = cohesive energy densities
1, 2 = solubility parameter

1, 2 =

1/2

Hmix= Vmix(
1 2)212
E = Hvap- RT
1 =

H vap - RT
V

1/2

if 1= 2, then Hmix= 0

1 2

Small's and Hoy's G parameter

a. Small(designated G derived from Heat of vaporization, Table 2.1)

dG
= MM
( d : density , M : molecular weight of unit )
ex) polystyrene 1.05(133+28+735)
=
104

= 9.0

b. Hoy(designated G based on vapor pressure measurement, Table 2.1)

dG
= MM
ex) polystyrene :

= 1.05[131.5+85.99+6(117.1)]
104

= 9.3

Hydrodynamic volume of polymer molecules in solution.

to be depended on followings
a. polymer-polymer interaction
b. solvent-solvent interaction
c. polymer-solvent interaction
d. polymer structure ( branched or not )
e. brownian motion
r = end-to-end distance
s = radius of gyration
Figure : Coil molecular shape

r 2 = ro22
s2= so22
2)1/2
(r
=
(ro2)1/2

The greater the value of , the better

the solvent
= 1, 'ideal' statistical coil.

Polymer Solutions
Mark-Howink-Sakurada equation
: The relationship between intrinsic viscosity and molecular weight
[
] =

KMa

[
] : intrinsic viscosity
K , a : constant for specific polymer and solvent
M : average molecular weight

Important properties of polymer solution : solution viscosity

a. paint spraying and brushing
b. fiber spinning

Polymer Solutions
F. theta(
) temperature and theta(
) solvent
The lowest temperature at which =1 : theta() temperature blink
The solvent satisfied this condition : theta() solvent point

G. Flory-Fox equation :
The relationship among hydrodynamic volumes,
intrinsic viscosity and molecular weight

[] =

(r2)3/2
M

[] : intrinsic viscosity
M : average molecular weight
: Flory constant (31024/mol)
r : end-to-end distance

Viscomerts

Ostwald

Ubbelohde

Capillary viscometers : (A) Ubbelohde, and (B) Cannon-Fenske.

Dissolution of polymer chains

Data from capillary viscometer

Measurement of Number Average Molecular Weight

End-group Analysis

Molecular weight limitation up to 50,000

End-group must have detectable species
a. vinyl polymer : -CH=CH2
b. ester polymer : -COOH, -OH
c. amide and urethane polymer : -NH2, -NCO
d. radioactive isotopes or UV, IR, NMR detectable function

Measurement of Number Average Molecular Weight

Mn =

2 x 1000 x sample wt
meq COOH + meq OH

Requirement for end group analysis

1. The method cannot be applied to branched polymers.
2. In a linear polymer there are twice as many end of the chain
and groups as polymer molecules.
3. If having different end group, the number of detected end group
is average molecular weight.
4. End group analysis could be applied for
polymerization mechanism identified
E. High solution viscosity and low solubility : Mn = 5,000 10,000

Another important characteristics of polymer solutions which

can be determined from the value of [ ] is the
overlap
concentration of polymer coils c*

c < c*

c = c*

c > c*

Dilute polymer
solutions

Overlap
concentration

Semidilute
polymer solutions

The average polymer concentration in the

solution is equal to that inside one polymer
coil at the overlap concentration c*. Thus,
c

3
R

= 1

1
3

1 2

[ ]

Since c* N/R3 , and [] R3/N , we have

[]c* 1.

Schematic representation of a membrane osmometer.

Membrane Osmometry
According to van't Hoff equation

)C=0 =

RT
+ A2C
Mn

limitation of : 50,0002,000,000
The major error arises from low-molecular-weight species diffusing
through the membrane.
FIGURE 3 Automatic membrane osmometer [Courtesy of Wescan Instruments, Inc.]

Plot of reduced osmotic pressure (/c) versus concentration (c).

/c

RT
Mn
Slope = A2

Cryoscopy and Ebulliometry

Freezing-point depression (Cryoscopy)
RT2
+ A2C
(
)C=0 =
Hf Mn
C

Tf

Tf : freezing-point depression,
C : the concentration in grams per cubic centimeter
R : gas constant
T : freezing point
Hf: the latent heats of fusion
A2 : second virial coefficient

Cryoscopy and Ebulliometry

Boiling-point elevation (Ebulliometry)

RT2
+ A2C
(
)C=0 =
C
HvMn

Tb

Tb : boiling point elevation

H v : the latent heats of vaporization
We use thermistor to major temperature. (1
10-4
)
limitation of Mn : below 20,000

Vapor Pressure Osmometry

The measuring vapor pressure difference of solvent and solution drops.

T =

RT2
100

)m

: the heat of vaporization per gram of solvent

m : molality

limitation of Mn : below 25,000

Calibration curve is needed to obtain molecular weight of polymer sample
Standard material : Benzil

Refractive Index Measurement

A. The linear relationship between refractive index and 1/Mn .
B. The measurement of solution refractive index by refractometer.
C. This method is for low molecular weight polymers.
D. The advantage of the method is simplicity.

Let us assume that the incident beam of light (wavelength

0 , intensity J0 ) passes through a dilute polymer solution.

Light Scattering

Schematic of a laser
light-scattering photometer.

Light source
High pressure mercury lamp and laser light.
Limitation of molecular weight( ) : 104
107

Measurement of Weight Average Molecular Weight

Light Scattering
. The intensity of scattered light or turbidity() is depend on following factors
a. size
b. concentration
c. polarizability
d. refractive index
e. angle
f. solvent and solute interaction
g. wavelength of the incident light

wavelength of the incident light :

= HcMW
32
H= 3
Hc =

No2(dn/dc)2
4No

1
+ 2A2C
MP()

C : concentration
no: refractive index of the solvent
: wavelength of the incident light
No : Avogadro's number
dn/dc : specific refractive increment
P() : function of the angle,
A2 : second virial coefficient
Zimm plot (after Bruno Zimm) : double extrapolation of concentration
and angle to zero (Fig 6)

Zimm plot of light-scattering data.

Hc

1
Mw

C=0

Experimental
Extrapolated

sin2/2 + kc

Ultracentrifugation

This technique is used

for protein rather than synthetic polymers.
for determination of Mz

Principles : under the centrifugal field, size of molecules are

distributed perpendicularly axis of rotation.
Distribution process is called sedimentation.

Viscometry
A. IUPAC suggested the terminology of solution viscosities as following.
Relative viscosity :

t
rel = =
: solution viscosity
to
o
o: solvent viscosity
t : flow time of solution
t o: flow time of solvent
Specific viscosity :

- o
o

sp =

sp

Reduced viscosity :

rel =

Inherent viscosity :

inh =

Intrinsic viscosity :

[] = (

t - to
to

rel - 1
c

In rel
c

sp
c

)c=o=(
inh)C = 0

= rel - 1

Mark-Houwink-Sakurada equation

[] = KMa
log[] = logK + alogMv
(K, a : viscosity-Molecular weight constant, table2.3)
Mw > Mv > Mn
Mv

is closer to Mw

than Mn

Representative Viscosity-Molecular Weight Constantsa

Polymer

Solvent

Polystyrene
(atactic)c

Cyclohexane
Cyclihexane
Benzene
Decalin

Temperature, Molecular Weight

oC
Range 10-4
8-42e
35 d
50
4-137e
25
3-61f
3-100e
135

Benzyl alcohol
Cyclohexanone

155.4d
20

4-35e
7-13f

156
13.7

0.50
1.0

Toluene
Toluene
DMFg
DMF

30
30
25
25

5-50f
5-16f
5-27e
3-100f

30.5
29.4
16.6
39.2

0.725
0.753
0.81
0.75

1-Chlorobutane
1-Chlorobutane
M-Cresol
M-Cresol

30
30
25
25

5-55e
4.18-81e
0.04-1.2f
1.4-5f

Polyethylene
(low pressure)
Poly(vinyl chloride)
Polybutadiene
98% cis-1,4, 2% 1,2
97% trans-1,4, 3% 1,2
Polyacrylonitrile
Poly(methyl methacrylate-costyrene)
30-70 mol%
71-29 mol%
Poly(ethylene terephthalate)
Nylon 66

aValue

taken from Ref. 4e.

bSee text for explanation of these constants.
cAtactic defined in Chapter 3.
d temperature.
eWeight average.
fNumber average.
gN,N-dimethylformamide.

Kb 103
80
26.9
9.52
67.7

17.6
24.9
0.77
240

ab
0.50
0.599
0.74
0.67

0.67
0.63
0.95
0.61

Mechaical and dynamic properties

Chain breakup

Rate of disengagement

Some Mechanical properties

Mechanical strength of some plastics

Oxidation

Chain scission

Spring and dashpot

Maxwell and Kelvin elements

Dynamic behavior of springs and dashpots

Maxwell:

Kelvin:

Dynamic mechanical spectroscopy on polystyrene crosslinked with 2% divinyl benzene. Data taken with a Rheovibron
at 110 Hz. Note that the tan d peak occurs at a slightly higher
temperature than the E peak

Typical polymer behavior

The retardation time

Relationship among macromolecular

parameters
Polymer density

Diameter between
Entangled tube

Mw between
entanglement
End-to end distance

Flory Rehner theory

Gel formation