solid state properties chapter 4. amorphous glassy semi-crystalline elastomeric polyisoprene t g =...
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Solid State Properties
Chapter 4
AmorphousGlassy
Semi-CrystallineElastomericPolyisoprene Tg = -73 °CPolybutadiene, Tg = -85 °CPolychloroprene, Tg = -50 °CPolyisobutylene, Tg = -70 °C
Viscous Liquid
Polymer Phases
Polystyrene Tg = 100 °CPolymethyl methacrylate, Tg = 105 °C
Nylon 6,6, Tg = 50 °C; Tm = 265 °CPoly ethylene terephthalate, Tg = 65 °C; Tm =270 °C
Polydimethylsiloxane Tg = -123°C; Tm = -40 °C
Glass-rubber-liquid
• Amorphous plastics have a complex thermal profile with 3 typical states:
Log(stiffness)Pa
Temperature
3
9
6
7
8
4
5
Glass phase (hard plastic)
Rubber phase (elastomer)
Liquid
Leathery phase
Polystyrene
Tg
Tygon (plasticized PVC)
PDMS
polyisobutylene
Phase diagram for semi-crystalline polymer
Temperature
Tg Tm Tb
Vol
ume
Glassy Solid
Crystalline Solid
Glassy SolidsPolystyrene Tg 100 °CPMMA Tg 105 °CPolycarbonate Tg 145 °CRubber Tg -73 °C
Crystalline SolidsPolyethylene Tm 140 °CPolypropylene Tm 160 °CNylon 6,6 Tm 270 °C
Polymers don’t exist in gas state; RT for boiling is higher than bond energies
Liquid
LiquidsInjection molding & extrusionPolydimethylsiloxane Tm -40 °C
Polymer Phases
Differential Scanning Calorimetry (DSC)
Modulus versus temperature
Viscous Response of Newtonian Liquids
AF
s =σ
A
A
y
Fx
tx
v
=
There is a velocity gradient (v/y) normal to the area. The viscosity relates the shear stress, σs, to the velocity gradient.
ytx
yv
s
σ ==
The viscosity can thus be seen to relate the shear stress to the shear rate:
γγ
σ &====tty
xyt
xs
ΔΔΔ
The top plane moves at a constant velocity, v, in response to a shear stress:
v
has S.I. units of Pa s.
The shear strain increases by a constant amount over a time interval, allowing us to define a strain rate:
tγ
γ =& Units of s-1
Measuring viscosities
Requires standards10-100,000 cP
1 pascal second = 10 poise = 1,000 millipascal second
Viscosity of Polymer Melts
Poly(butylene terephthalate) at 285 ºC
For comparison: for water is 10-3 Pa s at room temperature.
Shear thinning behaviour
Scaling of Viscosity: ~ N3.4
~ TGP
~ N3.4 N0 ~ N3.4
Universal behaviour for linear polymer melts
Applies for higher N: N>NC
Why?Data shifted
for clarity!
G.Strobl, The Physics of Polymers, p. 221
3.4
Viscosity is shear-strain rate dependent. Usually measure in the limit of a low shear rate: o
Concept of “Chain” Entanglements If the molecules are sufficient long (N >100 - corresponding to the entanglement mol. wt., Me), they will entangle with each other.
Each molecule is confined within a dynamic “tube”.
Tube G.Strobl, The Physics of Polymers, p. 283
Network of Entanglements
There is a direct analogy between chemical crosslinks in rubbers and “physical” crosslinks that are created by the entanglements.
The physical entanglements can support stress (for short periods up to a time T), creating a “transient” network.
An Analogy!
There are obvious similarities between a collection of snakes and the entangled polymer chains in a melt.
The source of continual motion on the molecular level is thermal energy, of course.
“Memory” of Previous State
Poly(styrene)
Tg ~ 100 °C
Development of Reptation Scaling Theory
Sir Sam Edwards (Cambridge) devised tube models and predictions of the shear relaxation modulus.
In 1991, de Gennes was awarded the Nobel Prize for Physics.
Pierre de Gennes (Paris) developed the concept of polymer reptation and derived scaling relationships.
There once was a theorist from Francewho wondered how molecules dance.“They’re like snakes,” he observed, “As they follow a curve, the large onesCan hardly advance.”
D ~ M -2
P.G. de GennesScaling Concepts in Polymer Physics
Cornell University Press, 1979
de Gennes
Entanglement Molecular Weights, Me, for Various Polymers
Poly(ethylene) 1,250
Poly(butadiene) 1,700
Poly(vinyl acetate) 6,900
Poly(dimethyl siloxane) 8,100
Poly(styrene) 19,000
Me (g/mole)
Amorphous Glasses (< Tg)
Tg: 40 carbons in backboneStarting moving in concert
Glass transition temperature
Rate of cooling affects Tg
Polymer Tg ( °C)
Polymer Tg ( °C)
Factors that affect Tg
Polar groups increase packing density; more thermal energy is needed to created volume
Factors that affect Tg
**
OHn
**
CNn
**
FnOther polar vinyl polymer:
Factors that affect Tg
Factors that affect Tg
Main chain stiffness: reduced flexibility
N
O
O
*
O
NH
H2C
npolyamide imide (Torlon)
Tg = 550-600 °C
O
*NH
n
polybenzamide
Tg = 500+ °C
N
NH
*
N
HN
n
polybenzimidazole (PBI)
Tg = 700-775 °C
Polyarylenes
Nylon-3Tg = 110-200 °C
* NH
*
O
n
Nylon-6Tg = 52 °C
*
HN *
O
n * NH
*
O
n
Nylon-11Tg = 42 °C
O
*NH
n
polybenzamide
Tg = 500+ °C
Nylons or polyamides
Side Chain Rigidity
Long chains plasticize
Factors that affect Tg
Anchors to movement
Long chains plasticize movements
Factors that affect Tg
OOMe
n
poly(methyl methacrylate)
Me
OMeO
OMeOO
MeOOMeOO
MeO
Tg = 47 °C (isotactic)
OMeO
OMeOO
MeOOMeOO
MeO
Tg = 120-140 °C (syndiotactic)
Tg = 110 °C (atactic > 50 % syndiotactic)
poly(methyl methacrylate)
Factors that affect Tg
Tacticity
Factors that affect Tg
Symmetry of substituents
**
Fn
**
Fn
F
Tg = -39 °CTg = -20 °C
**
Cln
**
Cln
Cl
Tg = -17 °CTg = 87 °C
asymmetric symmetric
Asymmetric have higher Tg’s
Factors that affect Tg: Mw
Factors that affect Tg: Crosslinking
Factors that affect Tg: Plasticizer
Phthalates
O
O
O
O
Immiscible (Two phase) and miscible (blends) polymers
Tg as a function of film thickness
Glass Transition
• Rigid group in backbone
• Flexible polymer backbone
• Steric Hinderance
• Long plasticizing side groups
• Symmetrical substituents
• Polar functionalities
• Plasticizers
O*O
O
*
n
polyether ketone (PEEK)Tg = 119 °C
O*O
O
*
n
polyether ketone (PEEK)Tg = 225 °C
Additional Kinds of Transitions
Amorphous Polymers Thermo-mechanical properties