Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
and
Polymer Characterization
Asst Prof Anongnat Somwangthanaroj
Anongnat.s@chula.ac.th 20 Sep 2010
http://pioneer.netserv.chula.ac.th/~sanongn1/course.html
Fundamentals:
Why Rheology ? Fundamental Rheology Concepts and Parameters Fundamental Rheometry Concepts Viscosity, Viscoelasticiy and the Storage Modulus The Linear Viscoelastic Region (LVR)
AGENDA
Why Rheology ? Fundamental Rheology Concepts and Parameters Fundamental Rheometry Concepts Viscosity, Viscoelasticiy and the Storage Modulus The Linear Viscoelastic Region (LVR)
A Rheological Paradox
BECAUSE
If a material is pumped, sprayed, extended, extruded, molded, coated, mixed, chewed, swallowed, rubbed, transported, stored, heated, cooled, aged RHEOLOGY is important .!!
AGENDA
Why Rheology ? Fundamental Rheology Concepts and Parameters Fundamental Rheometry Concepts Viscosity, Viscoelasticiy and the Storage Modulus The Linear Viscoelastic Region (LVR)
(everything flows )
Heraclito de Samos (500 A.C.)
De = / texp
Judges 5:5
Definition of Rheology
Rheology is the science of ____?____ and ____?___ of matter under controlled testing conditions .
flow deformation
Definition of Rheology
Rheology is the science of deformation and flow of matter under controlled testing conditions .
x(t)
y0
A
x
. = t
Rheology: The study of deformation and flow of matter at specified conditions. Range of material behavior
Solid Like
(Ideal Solid
---------------------
Liquid Like
Ideal Fluid)
Classical Extremes
=G
or
(Stress = G x Strain)
Non-Linear Region
100.0
G = f()
osc. stress (Pa)
100.0
G' (Pa)
10.00
Newtons Law: =
where is the Coefficient of Viscosity
Non-Newtonian Region
1.000E5
= f()
10000
1000
(Pa.s)
100.0
10.00
0.1000
1.000 1.000
(Pa)
-- [External Force] --
Ideal Fluid
WATER Weak Structure Fluidity Flow Losses form Dissipates Energy
(Purely Viscous I. Newton, 1687)
Apparent Fluid
- viscoelastic materials -
Deformation rate dependent viscosity Yield Stress (plasticity) Elasticity Thixotropy Transient behaviour
AGENDA
Why Rheology ? Fundamental Rheology Concepts and Parameters Fundamental Rheometry Concepts Viscosity, Viscoelasticiy and the Storage Modulus The Linear Viscoelastic Region (LVR)
Frame of Reference Recognize that a rheometer is a highly sensitive device used to quantify viscoelastic properties of the molecular structure of materials. A rheometer can not always mimic the conditions of a process, application or use. Rheometers determine apparent properties under a wide range of testing conditions.
The apparent behavior can be used as a finger print or benchmark of the material.
Constitutive Relations
Decane
Water
Steel
AGENDA
Why Rheology ? Fundamental Rheology Concepts and Parameters Fundamental Rheometry Concepts Viscosity, Viscoelasticiy and the Storage Modulus The Linear Viscoelastic Region (LVR)
Dynamic Testing
Deformation
An oscillatory (sinusoidal) deformation (stress or strain) is applied to a sample. The material response (strain or stress) is measured. The phase angle , or phase shift, between the deformation and response is measured.
Response
Phase angle
0 < < 90
Strain
Viscoelastic Parameters
The Complex Modulus: Measure of materials overall resistance to deformation. The Elastic (Storage) Modulus: Measure of elasticity of material. The ability of the material to store energy. The Viscous (loss) Modulus: The ability of the material to dissipate energy. Energy lost as heat. Tan Delta: Measure of material damping - such as vibration or sound damping.
Tan = G"/G'
Deformation
Time
USES Time dependent Thixotropy Cure Studies Stability against thermal degradation Solvent evaporation/drying
AGENDA
Why Rheology ? Fundamental Rheology Concepts and Parameters Fundamental Rheometry Concepts Viscosity, Viscoelasticiy and the Storage Modulus The Linear Viscoelastic Region (LVR)
Deformation
Time
The material response to increasing deformation amplitude (stress or strain) is monitored at a constant frequency and temperature.
USES Identify Linear Viscoelastic Region Strength of dispersion structure - settling stability Resilience
Non-Linear Region
100.0
G = f()
10.00
Critical Strain c
1.0000 10.000 % strain 100.00 0.01000 1000.0
100.0
G' (Pa)
Frequency Sweep
Stress or Strain
Deformation
Time
The material response to increasing frequency (rate of deformation) is monitored at a constant amplitude (stress or strain) and temperature.
USES Viscosity Information - Zero Shear , shear thinning Elasticity (reversible deformation) in materials MW & MWD differences Polymer Melts and Polymer solutions. Finding Yield in gelled dispersions High and Low Rate (short and long time) modulus properties. Extend time or frequency range with TTS
80.00
G' (Pa)
60.00
40.00
20.00
0 0
25.00
50.00
75.00
100.0
125.0
150.0
175.0
200.0
225.0
time (s)
Non-Linear Region
100.0
G = f()
10.00
Critical Strain c
1.0000 10.000 % strain 100.00 0.01000 1000.0
100.0
G' (Pa)
TA Instruments
100.0 1000 100.0
G' (Pa)
n' (Pa.s)
G'' (Pa)
G'
Shear Rate Range 10-6 to 10-3 10-2 to 10-1 10-1 to 101 100 to 102 101 to 102 101 to 102 101 to 103 100 to 103 103 to 104 104 to 105 104 to 106 105 to 106 103 to 107
Examples
Medicines, Paints, Salad Dressing
Leveling due to surface tension Draining off surfaces under gravity Extruders Chewing and Swallowing Dip coating Mixing and stirring Pipe Flow Brushing Rubbing High-speed coating Spraying Lubrication
Paints, Printing inks Toilet bleaches, paints, coatings Polymers, foods Foods Confectionery, paints Liquids manufacturing Pumping liquids, blood flow Painting Skin creams, lotions Paper manufacture Atomization, spray drying Bearings, engines
time
Stress
Stress
0
time
time
Material
time
For small deformations (strains within the linear region) the ratio of stress to strain is a function of time only. This function is a material property known as the STRESS RELAXATION MODULUS, G(t) G(t) = s(t)/
Strain
Strain
Stain rate for t>t1 is constant Strain for t>t1 increase with time Strain rate for t >t2 is 0
t1
time t2
t1 time t2
/
Strain
Recoverable Strain
t2
time
Strain rate decreases with time in the creep zone, until finally reaching a steady state.
In the recovery zone, the viscoelastic fluid recoils, eventually reaching a equilibrium at some small total strain relative to the strain at unloading.
Reference: Mark, J., et.al., Physical Properties of Polymers ,American Chemical Society, 1984, p. 102.
HDPE
100000
viscosity (Pa.s)
LLDPE
10000
LDPE
1000 1.000E-4 1.00E-3 0.01000 0.1000 1.000 10.00
viscosity (Pa.s)
10000
. () = ()
PDMS.05F-Flow step PDMS.08F-Flow step
1000
Dynamic data gives high shear rates unattainable in flow
100.0 1.000E-5
1.000E-3
10.00
1000
Terminal Region
Temperature
Low MW
High Med. MW MW
Temperature
Tg melt
1.000E10
G
1.000E9 0.3000
- transition Tg = 88.0C
1.000E9
0.2500 tan(delta)
G' (Pa)
Cold Crystallization
G'' (Pa)
1.000E8
0.2000
1.000E8
0.1500
1.000E7
0.1000
- transition -56.62C
1.000E7
0.05000
tan
-150.0 -100.0 -50.0 0 50.0 100.0 150.0 200.0 1.000E6 250.0
1.000E6 0 -200.0
temperature (Deg C)
G
2.000 1.000E9 1.750
1.000E10
Melt Tm = 240C
1.000E9
1.000E8
1.500
G
tan(delta)
1.000E8
G'' (Pa)
1.000E7
1.000E6
0.7500
1.000E6
tan
- transition Tg = 103C
1.000E5
10000 0 -200.0
-150.0
-100.0
-50.0
50.0
100.0
150.0
200.0
10000 250.0
temperature (Deg C)
1.000E9
1.000E7
Cold Crystallization
150.0
200.0
250.0
Oxidation or Decomposition
Heat Flow
BECAUSE
Thermal Analysis describes thermal transitions
and because
Rheology
Shear Flexure
Tension
Compression
Creep
Creep
Stress relaxation
Creep
Stress relaxation
Creep
Stress relaxation
Acknowledgements
Abel Gaspar-Rosas, Ph.D.
TA Instruments Waters, Inc For graphs and figures