fundamentals of rheology
DESCRIPTION
literatura reologíaTRANSCRIPT
FUNDAMENTALS of RHEOLOGY- From Deformation to Flow of Materials -
Abel Gaspar-RosasTA Instruments, Inc. – USA
2003 Sales MeetingMarbella, Spain
• Review of fundamental concepts of rheology
• Practical issues
• Advances in rheometry
• Advanced evaluation methods
ObjectiveObjectives
Key points
• Deformation
• Flow
• Practical view
• Rheology equipment
• Evaluation methods
Definition of Rheology
• Rheology is the science of flow and deformation of matter.
?
“” (everything flows)
- Heraclitus de Samos (500 B.C.)
Time scale in rheology
Deborah Number De = / texp
Judges 5:5
material texp us (you and me)
Flow and Deformation???
Interest: Rheological PropertiesClassical Extremes
Ideal Solid -- [External Force] -- Ideal Fluid
STEEL WATER Strong structure Weak structure Rigidity Fluidity Deform Flow Retain/recover shape Lose shape Store Energy Dissipate Energy (purely Elastic – R. Hooke, 1678) [Energy] (purely Viscous – I. Newton, 1687)
ELASTICITY VISCOSITY Storage Modulus Loss Modulus
REAL Behavior Apparent Solid [Energy + time] Apparente Fluid
- viscoelastic materials -
Flow and Deformation Parameters:[Shear Stress, Shear Strain, Shear Rate]
Stress: Force per unit area.
Symbol: Units: Pa (SI) or dynes/cm² (cgs)
Shear Strain: Relative deformation in shear.Symbol: Units: None
Shear Rate: Change of shear strain per unit time.Symbol: Units: [1/s] = s-1
Simple Shear Deformation and Flow
= FA
h
x(t)
1 x(t)
h t
Strain =
x(t)h
Strain Rate = . Vh
Rigidity G =
V
y
x
Az
Shear Deformation
Viscosity =.
=
Shear Flow
Summary of Types of ‘Flow’
Newtonian
Bingham Plastic(shear-thinning with yield stress)
Shear Thickening (Dilatant)
Shear Thinning (Pseudoplastic)
Bingham (Newtonian with yield stress)
Shea
r St
ress
,
Shear Rate,
y
deformation
flow
Model Fitting - Shear Stress vs. Shear Rate
K
K
K
n
n
y
n
c
y
n
n
n
( )
( )
1
1
12
0
Newtonian
Pseudoplastic
Dilatant
Bingham
Casson
Herschel-Bulkley
Summary of Viscosity Models
12
12
12
The Idealized Flow Curve
1
1) Sedimentation2) Leveling, Sagging3) Draining under gravity4) Chewing and swallowing5) Dip coating6) Mixing and stirring7) Pipe flow8) Spraying and brushing9) Rubbing10) Milling pigments in fluid base11) High Speed coating
2 3
6
5
8 9
1.001.00E-5 1.00E-4 1.00E-3 0.0100 0.100
shear rate (1/s)
10.00 100.00 1000.00 1.00E4 1.00E5
log
1.00E6
117
4
10
Models Fit to log-log Plots
0 =(K--
)m
= K 1n 1
= + K1n-1
= - Ko 1n 1
Predicts the shape of the complete Flow Curve
Cross
Sub-sets of the Cross Equation which predict portions of the complete Flow Curve
Power Law
Sisko
Williamson
Rotational Testing Deformation and Flow
upper plate‘moving’
lower plate‘fixed’
sample
Newtonian and Non-Newtonian Behavior of Fluids
Newtonian Region Independent of
Non-Newtonian Region
= f()
1.0001.000E-5 1.000E-4 1.000E-3 0.01000 0.1000
shear rate (1/s)
1.000E5
10000
(P
a.s)
1.000E5
1.000
10.00
100.0
1000
10000
(P
a)
Flow dependence
CMT - Stress Ramp Test - Continuous Ramp
Stress is applied to material at a constant rate. Resultant strain is monitored with time.
Str
ess
(P
a)
time (min.)
m = Stress rate (Pa/min)
USES Yield stress ‘Scouting’ Viscosity Run
Str
ess
(P
a)
Shear Rate,
y
deformation
flow
300.00 50.00 100.0 150.0 200.0 250.0
Shear Stress (Pa)
10000
0.01000
0.1000
1.000
10.00
100.0
1000
Vis
cosi
ty (
Pa.
s)
SMT Samplea: yield stress: 6.582 Pab: viscosity: 0.3777 Pa.sc: rate index: 0.8319
LMT Samplea: yield stress: 5.207 Pab: viscosity: 0.2909 Pa.sc: rate index: 0.8426
Short milling timeLong milling time
Automotive Paint Samples: Data fit to Herschel-Bulkley Model
10001.000 10.00 100.0Shear Stress (Pa)
10000
0.01000
0.1000
1.000
10.00
100.0
1000
Vis
cosi
ty (
Pa.
s)
Short milling timeLong milling time
Automotive Paint Samples: Viscosity vs. Shear Stress
SMT Technology - Step Rate
Select the step rate test to measure the transient viscosity or normal stress difference
In a step rate test (stress growth), a step strain rate is applied to the material and the stress and normal force is recorded over time.
The strain rate ramp is ideal for a fast viscosity scan as a function of shear rate for lower to medium viscosity fluids
In a thixotropy experiment, the strain rate is varied linear with time up and down and the stress is recorded over time.
SMT Technology - Thixotropy
In a steady rate experiment the equilibrium stress upon application of a step strain rate is measured. The equilibrium stress or viscosity is recorded as a function of the strain rate.
In a steady experiment, only the equilibrium value is measured over a manual selected time period
SMT Technology - Steady Rate Sweep Test
Creep Recovery Experiment
Response of Classical Extremes
– Strain for t>t1 is constant– Strain for t >t2 is 0
time
Str
ain
time
Str
ain
time
– Stain rate for t>t1 is constant– Strain for t>t1 increase with time– Strain rate for t >t2 is 0
t2
Str
ess
t1
t1 t2t2t1
6000.0 global time (s)
80.0
0
10.0
20.0
30.0
40.0
50.0
60.0
70.0
% s
trai
n
Creep Long milling time Short milling time
Automotive Paint Samples: Creep / Recovery Test
Recovery
Recovery
?1
?2
?2
10.001.000E-3 0.01000 0.1000 1.000
time (s)
30.0
0
5.00
10.0
15.0
20.0
25.0
% s
trai
n
Elastic Ringing
Long milling timeShort milling time
Automotive Paint Samples:
Creep Recovery Test
insidethe ?1
SMT Technology - Creep Test
In a creep test, a step stress is applied to the material and the deformation is recorded over time. If the stress is removed after a time t1 the recoverable deformation (recoil) is obtained.
The recoil test is the most sensitive test to determine aq material’s elasticity
Oscillatory Testing Deformation and Flow
upper plate‘moving’
lower plate‘fixed’
sample
Dynamic Flow Testing
Deformation
Response
Phase angle
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 control andthe response is measured.
Fundamentals of Rheology The fundamental definition of rheology indicates that for a material to flow its original structural composition must first exceed a critical limited deformation.
Rheology, the science of deformation and flow of materials characterizes materials through parameters such as;
• storage modulus (G’) loss modulus (G”)• loss factor (Tan ) critical deformation c
• viscosity () yield point (y)• characteristic times () flow index (n)• ...
With exquisite presicion, rheology describes the behavior of materials as viscoelastic fluids (G”>G’ and -> 90°) to viscoelastic solids (G’>G” and -> 0°)
Information commonly used to improve formulations optimize processes, select aplication conditiosn, evaluate product performance, determine shelf life, evaluate product economy, and more.
Linear and Non-Linear Stress-Strain Behavior of Solids
Non-Linear Region
G = f()Linear Region G is constant
G
1000.00.010000 0.10000 1.0000 10.000 100.00% strain
1000
1.000
10.00
100.0
G' (
Pa
)
100.0
0.01000
os
c. s
tres
s (
Pa
)
Deformation Flow
10001.000E-3 0.01000 0.1000 1.000 10.00 100.0
osc. stress (Pa)
100.0
1.000E-3
0.01000
0.1000
1.000
10.00
G' (
Pa)
Frequency = 6.28 rad/s
Short milling timeLong milling time
Automotive Paint Samples: Stress Sweep after Time Sweep
Elastic Component
Yield Stress y
SMT Technology - Strain Sweep Test
In a strain sweep, the strain is varied linear or logarithmic over the selected range. Strain, stress amplitude and phase shift are recorded.
The non-linear monitor (NLM) senses the end of the linear viscoelastic range
Frequency Sweep: Material Response
Terminal Region
Rubbery PlateauRegion
TransitionRegion
Glassy Region
12
Storage Modulus (E' or G')
Loss Modulus (E" or G")
log Frequency (rad/s or Hz)
log
G'a
nd G
"
Dynamic Moduli of a Polymer Melt vs. Frequency
10001.000E-4 1.000E-3 0.01000 0.1000 1.000 10.00 100.0
ang. frequency (rad/sec)
1000000
0.1000
1.000
10.00
100.0
1000
10000
100000
G' (
Pa)
1000000
0.1000
1.000
10.00
100.0
1000
10000
100000
G''
(Pa)
1.00E7
100.0
1000
10000
100000
1000000
* (
Pa
.s)
G"
G'
*
PDMS at 20°C
SMT Technology - Temperature Sweep Test
In a temperature sweep, the temperature is varied continuously or discrete over the selected range. Strain, stress amplitude and phase shift are recorded.
In all temperature dependent test, the AutoTension function is available
Practical Issues
• Sample handling• Sample handling• Sample handling
Non-Newtonian, Time Dependent Fluids
Thixotropy A decrease in apparent viscosity with time under
constant shear rate or shear stress, followed by a gradual recovery, when the stress or shear rate is removed.
Rheopexy An increase in apparent viscosity with time under
constant shear rate or shear stress, followed by a gradual recovery when the stress or shear rate is removed. Also called Anti-thixotropy or negative thixotropy.
Reference:Barnes, H.A., Hutton, J.F., and Walters, K., An Introduction to Rheology, Elsevier Science B.V., 1989. ISBN 0-444-87469-0
Non-Newtonian, Time Dependent Fluids
time
Vis
cosi
ty
Thixotropic
Rheopectic
Shear Rate = Constant
10000 100.0 200.0 300.0 400.0 500.0 600.0 700.0 800.0 900.0
time (s)
100.0
0.1000
1.000
10.00
G' (
Pa)
Pre_shear: 1000 1/s for 60 secStress = 0.1 PaFrequency = 6.28 rad/s
Short milling timeLong milling time
Automotive Paint Samples: Structural Change – Structure Rebuild (Thixotropy)
Elasticidad
Osc. –> Rotat. -> osc
No-Newtonian rheological behavior (shear-thinning) must produce a balance of properties during the formation of the coating film.
• formulation, estability, aplication
• satisfactory leveling
• uniform thickness
• resistance to sag/drainage
ADDITIVES - can cause non desired effects.
• too much elasticity (rapid contraction of structure)
• extreme shear-thinning
• flocculation of pigment
Response for a Viscoelastic Material
At short times (high frequencies) the response is solid-like
At long times (low frequencies) the response is liquid-like
THE HISTORY OF LOADING IS CRUCIAL
Exponential Close
Gap
Time
~ 1000 - 2000 micronsfrom final gap
Squeeze Flow effectis less pronounced
Rapid Close
Controlled Close
Comparison of Standard and Exponential Sample Gap Close on Paint
0 200 400 600 800 10000
50
100
150
200
250
Time (s)
G' (
Pa)
Fast Linear Close
Exponential Close
• Reduces errors due to solvent evaporation• Available for cones, plates, and concentric cylinders [cover only]
Solvent Trap System
Shear Rate
Time
(ddt)
Visual confirmation of Material’s Response
Steady State Rotational Flow
Steady State Oscillatory Flow
Advances
in Rheology Equipment
Interest: Rheological PropertiesClassical Extremes
Ideal Solid -- [External Force] -- Ideal Fluid
STEEL WATER Strong structure Weak structure Rigidity Fluidity Deform Flow Retain/recover shape Lose shape Store Energy Dissipate Energy (purely Elastic – R. Hooke, 1678) [Energy] (purely Viscous – I. Newton, 1687)
ELASTICITY VISCOSITY Storage Modulus Loss Modulus
REAL Behavior Apparent Solid [Energy + time] Apparente Fluid
- viscoelastic materials -
TA’s New Concept - “SMT” and “CMT” TechnologyThe Rheometric Series
• Historically - Controlled Stress or Controlled Strain rheometers• Today - Instruments can do both - to a greater or lesser degree
• TA’s Rheometry Technology Concept
• SMT - Separate Motor & Transducer - Controlled Strain
• CMT - Combined Motor & Transducer - Controlled Stress
SMT‘ARES’5 models
CMT‘AR’
5 models
SMT RHEOMETRY - The ARES“from water to steel and everything in between!”
• Independent measure of Torque & Strain• System inertia has no effect on Measurement • Force Rebalance transducer (spring for RDA)• Controlled Strain• Oscillatory testing on low viscosity fluids• Simultaneous measurements
• Rheo-Optical • System Optimized for Application• Best Normal Force • LCD display for status information• ARES – a highly recognized name• Powerful Software and Analysis• Powerful, $$$
CMT RHEOMETRY - The AR2000“from water to steel and everything in between!”
• Controlled Stress• Creep / Recovery test• High Angular Resolution• Advanced Electronics• Mobius Drive – Strain• Smart Swap technology• Very low Shear Rate FC• Signals for each point• Status window• Powerful Software & Analysis• Easy Manual measurements• Versatile, Powerful, great $$$
Rheometrics Series - Labels
TA is the ONLY company that offers SMT & CTM technology with the best technical support
The AR2000
• Advanced design !!!– Mobius™ Drive– Smart Swap™ -
Interchangeable Peltier Plate, Peltier Concentric Cylinder, and ETC
– Air bearing drive– Normal force sensor– Optical encoder resolution– Casting– Fast Electronics
AR2000 Smart Swap™
• Push button to release and attach temperature systems
• Firmware automatically senses type of system and configures software accordingly
• All connectors are on front of unit
• Takes less than 30s to exchange temperature systems
• All systems are powered and controlled from the main electronics
Smart Swap - RemovalPress ‘Release’ button
Press ‘Release’ button again
Continuous green status light indicates attachment can be removed
Flashing green status light indicates it is safe to unplug
• Torque range CS: 0.1N.m to 200mN.m
• Torque range CR: 0.03N.m to 200mN.m
• Speed range CS: 1E-8 to 300rad/s
• Speed range CR: 1E-4 to 300rad/s
• Inertia: ~15N.m2
• Frequency range: 1.2 E-7 to 100Hz
• Step change in speed: < 30ms
• Step change in strain: < 60ms
• Step change in stress: <1ms
and much more…
: Specifications
AR2000: Angular Resolution - 40nRad
1.00E60.10 1.00 10.00 100.00 1000.00 10000.00 1.00E5osc. torque (micro N.m)
0.1000
1.00E-9
1.00E-8
1.00E-7
1.00E-6
1.00E-5
1.00E-4
1.00E-3
0.0100
dis
pla
cem
ent
(rad)
resolution check-0002oresolution limit
Oscillation – Amp. Sweep
1.00E-7 1.00E-6 1.00E-5 1.00E-4 1.00E-3 0.0100displacement (rad)
0
2.500
5.000
7.500
10.00
12.50
15.00
17.50
20.00|n
*| (
Pa.
s)
0.01
0.10
1.00
10.00
100.00
1000.00
10000.00
osc. torque (micro N
.m)
0.03 Nm
Performance on ~1Pa.s Oil
[rad/s]
Time to 10% [s]
Time to 1% [s]
0.1 0.015 0.018
1.0 0.014 0.022
10 0.017 0.025
100 NA NA100.01.000E-3 0.01000 0.1000 1.000 10.00
time (s)
1000
1.000E-4
1.000E-3
0.01000
0.1000
1.000
10.00
100.0
vel
ocity
(ra
d/s)
1Pa.s oil [ 0.1 rad per sec1Pa.s oil [1.0 rad per sec1Pa.s oil [10 rad per sec
Real Rheological Data
100.01.000E-3 0.01000 0.1000 1.000 10.00
time (s)
1000
1.000E-4
1.000E-3
0.01000
0.1000
1.000
10.00
100.0
ve
loci
ty (
rad
/s)
1.000E5
1.000
10.00
100.0
1000
10000
vi
sco
sity
(P
a.s)
1Pa.s oil 0.1 rad per sec1Pa.s oil 1.0 rad per sec
1Pa.s oil 10 rad per sec
Certified value 1.43Pa.s
Stress Relaxation on PDMS
• Within 1% of set value in 30ms
• Within 1% of set value in 30ms
• Within 1% of set value in 30ms
0
0.2
0.4
0.6
0.8
1
1.2
0.001 0.01 0.1 1 10 100
time [s]
% s
tra
in
0
1
2
3
4
5
6
0.001 0.01 0.1 1 10 100
time [s]
% s
trai
n
0
2
4
6
8
10
12
0.001 0.01 0.1 1 10 100
time [s]
% s
tra
in
Shear Rate
Time
(ddt)
Visual confirmation of Material’s Response
Steady State Rotational Flow
Steady State Oscillatory Flow
time
str
ain
time
str
ain
time
str
ain
1.0001.000E-7 1.000E-6 1.000E-5 1.000E-4 1.000E-3 0.01000 0.1000shear rate (1/s)
1.000E8
10000
1.000E5
1.000E6
1.000E7
visc
osi
t y (
Pa.
s)
Carreaua: zero-rate viscosity: 4.982E7 Pa.sb: infinite-rate viscosity: 0.4928 Pa.s
c: consistency: 2.007E5 sd: rate index: 0.5756 standard error: 7.506
Visual confirmation of Steady State Flow
Visual Confirmation - Oscillation Frequency Sweep
100.01.000E-5 1.000E-4 1.000E-3 0.01000 0.1000 1.000 10.00frequency (Hz)
1.000E6
0.01000
0.1000
1.000
10.00
100.0
1000
10000
1.000E5
G' (
Pa
)
1.000E6
0.01000
0.1000
1.000
10.00
100.0
1000
10000
1.000E5
G'' (P
a)
1.000E5
100.0
1000
10000
|n*|
(P
a.s
)
PDMS
PDMS Extended frequency sweep-0001o, Frequency sweep step
Evaluation MethodsViscoelastic Transformations
•Each material has a unique set of viscoelastic properties
investigated by oscillatory flow, creep/recovery test, or stress relaxation test.
• If each test is performed within the linear viscoelastic region of the material, the information should be the same even though each test provides different sections of the total rheological characterization profile.
• Polymer transformation software as a tool may inter-convert linear viscoelastic functions.
• It is now possible to easily transform data obtained from one technique into another.
Background
Interconversion routes
oscillationGG
creepcompliance
J(t)
stressrelaxation
G(t)
relaxationspectrum
H()
Stress Relaxation vs. FrequencySweepTransformed Data
• The black line on the plot was calculated by transforming a frequency sweep file through the discrete relaxation spectrum and then on to a stress relaxation file
100.00.01000 0.1000 1.000 10.00time (s)
1.00E5
1.000
10.000
100.000
1000.000
10000.000
Gt (
Pa)
Creep Test Data vs. Frequency SweepTransformed Data
1.0000 0.1000 0.2000 0.3000 0.4000 0.5000 0.6000 0.7000 0.8000 0.9000
time (s)
2.5000E-3
0
2.5000E-4
5.0000E-4
7.5000E-4
1.0000E-3
1.2500E-3
1.5000E-3
1.7500E-3
2.0000E-3
2.2500E-3
com
plia
nce
(m^2
/N)
Real data - shows creep ringingTransformed data – no ringing
Evaluation MethodsFrom H() MWD
oscillationGG
creepcompliance
J(t)
stressrelaxation
G(t)
relaxationspectrum
H()
MWD
10001.000E-5 1.000E-4 1.000E-3 0.01000 0.1000 1.000 10.00 100.0ang. frequency (rad/sec)
1.000E6
10.00
100.0
1000
10000
1.000E5
G' (
Pa)
1.000E6
10.00
100.0
1000
10000
1.000E5
G'' (P
a)
115k 1150k Blend
Blend of ‘Low’ and ‘High’ Mw
1.000E61.000E-41.000E-3 0.01000 0.1000 1.000 10.00 100.0 1000 10000 1.000E5Tau (s)
1.000E7
1.000
10.00
100.0
1000
10000
1.000E5
1.000E6
H (
Pa
)
Recipricol plus e^(PI/2)
Resultant Continuous Spectrum
74 5 6Log [Molar mass (g/Mol)]
0.3000
0
0.05000
0.1000
0.1500
0.2000
0.2500
w(M
)
Calculated Rouse subtraction
Resultant MWD
10001.000E-5 1.000E-4 1.000E-3 0.01000 0.1000 1.000 10.00 100.0ang. frequency (rad/sec)
1.000E9
1000
10000
1.000E5
1.000E6
1.000E7
1.000E8
|n*|
(P
a.s
)
115k1150k115k 1150k Blend
Molecular weight (WLF)n0: 1.691E5 Pa.sMw: 1.606E5 g/mol
Molecular weight (WLF)n0: 2.020E7 Pa.sMw: 6.613E5 g/mol
Molecular weight (WLF)n0: 1.365E8 Pa.sMw: 1.164E6 g/mol
* Comparison
Key Points - (review)
• Deformation
• Flow
• Practical view
• Advances in rheology equipment
• Advances in evaluation methods
- Rheology describes the structural behavior and physical properties of materials
- SMT and CMT technology provide the most complete rheological characterization of materials
- Rheological testing is a very practical and versatile tool
- Viscoelastic transformation add more power to rheology instrumentation
- TAI is the ONLY company that offers SMT & CMT technology with best technical support and service
CONCLUSIONS…..
next …
Interest: Rheological PropertiesClassical Extremes
Ideal Solid -- [External Force] -- Ideal Fluid
STEEL WATER Strong structure Weak structure Rigidity Fluidity Deform Flow Retain/recover shape Lose shape Store Energy Dissipate Energy (purely Elastic – R. Hooke, 1678) [Energy] (purely Viscous – I. Newton, 1687)
ELASTICITY VISCOSITY Storage Modulus Loss Modulus
REAL Behavior Apparent Solid [Energy + time] Apparente Fluid
- viscoelastic materials -
(Know)
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