Viscoelastic behavior of polymer

Elastic

Viscoelastic

Viscoelastic behavior: depends on time and temperature

Viscous

Stress relaxation test:

to o and hold.
-- observe decrease in stress
with time.tensile test
-- strain

strain
(t)
time

Relaxation modulus:

E r (t )

(t )
o

Relaxation Modulus is the time dependent

change in stress w.r.t maintained constant strain.

Crystalline isotactic PS

Lightly x-linked atactic PS

decompose

Amorphous PS

f08_14_pg498

Plastic Recycling Symbols

In 1988 the Society of the Plastics Industry
developed a numeric code to provide a uniform
convention for different types of plastic containers.
These numbers can be found on the underside of
containers.
1.

6.

PET; PETE (polyethylene terephthalate): plastic water and

soda bottles.
HDPE (high density polyethylene): laundry/dish detergent
V (Vinyl) or PVC: Pipes, shower curtains
LDPE (low density polyethylene): grocery bags, sandwich
bags
PP (polypropylene): Tupperware, syrup bottles, yogurt
cups,
PS (polystyrene): Coffee cups, disposable cutlery

7.

Miscellaneous: any combination of 1-6 plastics

2.
3.
4.
5.

Group Problem 4 (03/02/2016): Marks 2. Each group 2

Please mention the following point in your answer sheet
Name
ID
group problem number
Date
Derive the following relation

c s a
Wt (%)crystallinity
100
s c a
s = overall density of the sample
c = density of the crystalline part
a = density of the amorphous part

X-Ray Diffraction

X-Ray Diffraction

Diffraction gratings must have spacings comparable

to the wavelength of diffracted radiation.
Cant resolve spacings
Spacing is the distance between parallel planes of
atoms.
9

X-Rays to Determine Crystal Structure

d

g
ut

ng
i
o

For constructive
interference, reflected light
must be in phase

ay
r
X-

ec
to
r

1
g
in 2
m
co ys
in -ra
X

extra
distance
travelled
by wave 2

et
Incoming X-rays diffract from crystal planes.

Adapted from Fig. 3.20,

Callister & Rethwisch
8e.

spacing
d between
planes

X-ray
intensity
(from
detector)

Path difference (2dsin) is

a multiple of the
wavelength
Measurement
of critical angle, c, allows
computation of planar spacing, d.

reflections must
be in phase for
a detectable signal

n
d
2 sinc

c
10

X-Ray
Diffraction
Pattern
z
z
z
Intensity (relative)

y (110)

c
y

b
(211)

(200)

Diffraction angle
2
Diffraction pattern for polycrystalline
-iron (BCC)
Adapted from Fig. 3.22, Callister 8e.
12

Phase detection (Composition, Ratio)

Peak Position: Lattice Parameters

XRD Line Broadening

Instrumental Unresolved 1 , 2 peaks
Bi

Non-monochromaticity of the source (finite width of p

Imperfect focusing

Crystallite size In the vicinity of B the ve of Braggs equation not bei

Bc

Strain
Bs

Residual Strain arising from dislocations, coherent

precipitates etc. leading to broadening

Stacking fault
In principle every defect contributes to some
Other defects broadening

B ( FWHM ) Bi Bc Bs BSF ...

B ( FWHM ) Bi Bc Bs BSF ...

Scattering by the Unit cell (uc)

Coherent Scattering
Unit Cell (uc) representative of the crystal structure
Scattered waves from various atoms in the uc interfere to create the
diffraction pattern

The wave scattered from the middle plane is out of phase with the
ones scattered from top and bottom planes

Selection / Extinction Rules

Bravais
Lattice
SC
BCC
FCC
DC

Allowed Reflections
All
(h + k + l) even
h, k and l unmixed
h, k and l are all odd
Or
all are even

THE POWDER METHOD

2dSin

Cubic crystald Cubic

a
h2 k 2 l 2

2
2
4
a
sin

2
2
h k2 l2

2
4
a
(h 2 k 2 l 2 ) 2 sin 2

2
2
2
a2
(
h

l
)
2
4 sin

(h 2 k 2 l 2 ) sin 2

h2 + k2 + l2

SC

100

110

111

111

200

200

Bravai
s
Lattic
e

Allowed
Reflections

SC

All

210

BCC

(h + k + l) even

211

FCC

h, k and l unmixed

DC

h, k and l are all

odd
Or
all are even

FCC

BCC

DC

110
111
200
211

7
8

220

220

300, 221

10

310

11

311

311

12

222

222

13

320

14

321

220

220

310
311
222
321

15
16

400

17

410, 322

18

411, 330

19

331

400

400

400

411, 330
331

331

The ratio of (h2 + K2 + l2) derived from extinction rules

SC

BCC

FCC

11

12

DC

11

16

 For electromagnetic radiation to be diffracted the

spacing
in the grating should be of the same order as the
wavelength
In crystals the typical interatomic spacing ~ 2-3 so the
suitable radiation is X-rays
Hence, X-rays can be used for the study of crystal
structures

Beam of electrons

Target

X-rays

An accelerating (/decelerating) charge radiates electromagnetic radiation

Mo Target impacted by electrons accelerated by a 35 kV potential

Intensity

K
White
radiation

0.2

Characteristic radiation
due to energy transitions
in the atom

0.6

1.0

Wavelength ()

1.4

Target Metal

Of K radiation ()

Mo

0.71

Cu

1.54

Co

1.79

Fe

1.94

Cr

2.29

Incident X-rays
SPECIMEN

Fluorescent X-rays

Heat

Electrons

Scattered X-rays

Compton recoil Photoelectrons

Coherent
Incoherent (Compton modified)
From bound charges From loosely bound charges

Transmitted beam
X-rays can also be refracted (refractive index slightly less than
1) and reflected (at very small angles)
Refraction of X-rays is neglected for now.