Download - EXPERIMENTAL PLANNING & DATA ANALYSIS
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P A G E 0 P A G E 0
O U T L I N E
• Experimental tips and tricks
• Experimental planning
• Cleaning of surfaces
• Samples
• Instrument
• Data analysis
• Modelling fundamentals
• Advanced modelling
EXPERIMENTAL PLANNING
& DATA ANALYSIS
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P A G E 1 P A G E 1
EXPERIMENTAL TIPS AND
TRICKS
GENERATING QUALITY DATA
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P A G E 2 P A G E 2
QCM-D Experiment Planning
Surface
What type of surface?
How will I clean/prepare the surface?
What buffer (solvent)?
Which concentration(s)?
What Temperature?
Do I need to degas my samples?
Samples
How do I clean/prepare the instrument?
What liquid path am I going to use?
What about solvent compatibility?
Flow rate/Batch mode?
Instrument 1
2
3
4
parallel
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P A G E 3 P A G E 3
Methods & Protocols
Collection of preparation and cleaning
methods for surfaces and instrument
Cleaning Au Cleaning SiO2 Instrument cleaning
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P A G E 4 P A G E 4
Surfaces in Gas & Liquid Environment Deposits in ambient air:
• hydrocarbons
• dust
• oxidation
• water
Deposits in liquid environment:
• solvent residues (organic, salt)
• detergents
• dissolution of surface components and deposits
Consequences of deposits:
• changes in chemical composition
• change in wetability
• decrease in reproducibility
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P A G E 5 P A G E 5
Contamination - 3D vs. 2D
small effect in 3D large effect in 2D
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P A G E 6 P A G E 6
Cleaning Q-Sense sensors
• Q-Sense sensors have been exposed to
ambient air for a considerable amount of
time (weeks) when they reach the
customer.
What are the practical implications of contamination?
• For most applications relevant cleaning is
necessary before use in order to get
reproducible results!
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P A G E 7 P A G E 7
Reusing Surfaces
sensors are disposable, but can
in some cases be reused
materials:
• quartz
• gold
• chromium
resistance to:
• many organic solvents, acids, bases
• temperatures up to 100ºC (and more)
reusing application-dependent
active side
contact side
Sensor
active
electrode
counter
electrode
quartz disc
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P A G E 8 P A G E 8
Clean Sensor (and tweezers)
+
Gold
Ammonia, Peroxide Mix (TL1) UV/Ozone
SiO2
SDS Thick films/
Heavy contaminated + UV/Ozone
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P A G E 9 P A G E 9
Equipment
Cleaning Holder
• holds up to 5 sensors
• made of Teflon
• prevents wear of sensors
• with removable grip for easy transfer
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P A G E 10 P A G E 10
Chemical Treatment, TL1
• Surface: Gold
• Removes: Lipids, thiols, proteins in
molecular layers
W. Kern et al., RCA Review 31 (1970) 187
Method:
• UVO-treatment (10 min)
• Heat 5:1:1-mixture of MQ-water,
ammonia (25%) and hydrogen peroxide
(30%) to 75C
• Immerse the sensors in the solution
using a cleaning holder (5 min)
• Clean tweezer
• Rinse in MQ-water, dry with N2
• UVO-treatment (10 min)
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P A G E 11 P A G E 11
Surfactant treatment
• Surface: Any metal and oxide surface (standard for SiO2)
• Much milder than TL1
• Removes: most biologic substances, like proteins and lipids
Method:
• UVO-treatment (10 min) (Not for Ag!)
• Prepare a solution of 2% Sodium
Dodecyl Sulfate (SDS) in milliQ water.
• Immerse the sensors in the solution in
room temperature for 30 min
• Rinse in mQ-water, dry with N2
• UVO-treatment (10 min) (Not for Ag!)
K. Harewood et al, Anal. Biochem. 55 (1973) 573
J. Penfold et al, Langmuir 18 (2002)
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P A G E 12 P A G E 12
Cleaning Surfaces–UVO-Treatment
sensor surface
• effective in air
• exposure time: 5-10 min
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P A G E 13 P A G E 13
does:
• volatilize thin films of organic contaminants
• oxidize the surface
does not:
• remove thick films of contaminants (risk of incrustation)
• remove inorganic contaminants (dust, salt)
Plasma cleaning – an alternative ?
• common cleaning method
• UVO-treatment cheaper
• risk of contamination in contaminated chamber
Cleaning Surfaces – UVO-Treatment
references:
J.R. Vig, J. Vac. Sci. Technol. A 3 (1985) 1027
Krozer et al, J. Vac. Sci. Technol. A 15 (1997) 1704
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P A G E 14 P A G E 14
Be careful with polymer surfaces!
• Surfactants like SDS and Hellmanex may increase
the surface roughness of the polymer coating, or
remove parts of it
• SDS particles may also get stuck in the polymer
• UVO-treatment may destroy a polymer surface
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P A G E 15 P A G E 15
Sensors Dry and Dust Free
Rinse washing solution off Dry with a clean gas
N2
Ar2
CO2
Never use compressed air!
Keep tweezer below sensor
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P A G E 16 P A G E 16
Surfaces – Spin-Coating
• Thickness of the deposited film can be roughly determined with
QCM-D by measuring f and D before and after coating
• Excess polymer solution can travel over sensor edge and cover
backside electrodes – clean with solvent on cotton stick
References on spin-coating:
• Meyerhofer et al., J. Appl. Phys. 49 (1978) 3993
• Bornside et al., J. Imaging Technology 13 (1987) 122
sensor
cotton stick
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P A G E 17 P A G E 17
QCM-D Experiment Planning
Surface
What type of surface?
How will I clean it?
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P A G E 18 P A G E 18
Pure samples
Water:
18,3 MΩ MilliQ
Buffers:
Prepare your own
buffers, do not trust
the ”kitchen”!
Water
PBS
HEPES
MES
ACETAT
.....
sterile≠clean
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P A G E 19 P A G E 19
Concentrations
low high
No/slow response
Diffusion / Depletion
Bulk effect, aggregation
Too rapid kinetics
Costly
Typical Concentrations
Protein 0.1-100 μg/ml
Antibody 0.01-10 μg/ml
Cells 104 - 106 CFU/ml
DNA pmol-nmol
0.1-100 µg/ml
Optimal concentration region
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P A G E 20 P A G E 20
-10
-5
0
5
10
-3
-2
-1
0
1
2
0 5 10 15 20
f3 (Hz)f5 (Hz)f7 (Hz)
D3 (1E-6)D5 (1E-6)D7 (1E-6)
f (H
z)
D
(10
-6)
time (min)
Bulk effects – “Buffer step”
Effect:
offset in baseline of f and D
when changing solution
Cause:
bulk properties
- density & viscosity -
influence f and D
D
off
f o
ff
buffer 1 buffer 2
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P A G E 21 P A G E 21
Avoid Temperature changes
Sun light
Draught
Air condition
Fume Hood
General recommendation
• Constant ambient
temperature
• Ensure good heat transport
from chamber base
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P A G E 22 P A G E 22
Degas samples
Origin: Buffer
Hydrophobic
surfaces more
problematic!
Degassing samples
• Sonicator + vacuum
• Heat (Tsample>Tinstrument)
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P A G E 23 P A G E 23
QCM-D Experiment Planning
Surface
What type of surface?
How will I clean it?
What buffer (solvent)?
Which concentration(s)?
Temperature?
Degassing
Samples
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P A G E 24 P A G E 24
Instrument cleaning
Cleaning solutions:
Hellmanex 2% in mQ (ca 10 ml)
SDS 2% in mQ (ca 10 ml)
Always end with a water
rinse and store chamber
dry!
Replace rubber parts when
worn out or every year.
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P A G E 25 P A G E 25
Handling of the system
Flow modules can be disassembled and cleaned
Tubing and other consumables need exchanging
High chemical compatibility (Teflon, titanium, o-
ring and gasket polymer material)
Cleaning protocols, chemical compatibility charts
and consumable guides available
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P A G E 26 P A G E 26
Solvent compatibility
E4/E1 systems
Liquid interfacing materials
(standard configuration)
• Module: Titanium, grade 2
• Inlet/outlet tubing: Teflon
• O-rings and gaskets: Viton
• Pump tubing: Viton
Check Chemical Compatibility Chart!
Highly resistant tubings and O-rings/sealings (Kalrez)
available
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P A G E 27 P A G E 27
Summary
Surface
What type of surface?
How will I clean it?
What buffer (solvent)?
Which concentration(s)?
Temperature?
Degassing
Samples
Cleaning
Liquid path
Solvent compatibility
Flow rate
Instrument 1
2
3
4
parallel
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P A G E 28 P A G E 28
Tech tips
• Ensure to have a clean surface
• Always start in reference solvent (buffer, water etc)
• Avoid difference in bulk properties
• Bubble = trouble
• Do your own sample preparation!
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P A G E 29 P A G E 29
DATA ANALYSIS
h
r
h m
Δ
D
time
Δf Δf ΔD ΔD
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P A G E 30 P A G E 30
O U T L I N E
• Different types of data evaluation
– Qualitative vs Quantitative analysis
• Quantitative analysis (modeling)
– Sauerbrey vs Viscoelastic modeling (Qtools)
1. What is the difference?
2. When to use what model
3. What happens if I use the wrong model?
• Viscoelastic modeling in Qtools
1. Procedure step by step
2. How do I know I have a good fit?
3. How do I improve the fit?
• Advanced modelling options
Δ
D
time
Δf Δf ΔD ΔD
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P A G E 31 P A G E 31
Q U A L I T A T I V E
A N A L Y S I S
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P A G E 32 P A G E 32
QCM-D data analysis
Qualitative :
– raw data plot
relative comparison of responses, shifts, rates, etc
– f –D plot reveals for example phase transitions
ΔD
time
Δf
Δf ΔD
ΔD
Frequency [Hz]
Phase 1
Phase 2
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P A G E 33 P A G E 33
Q U A N T I T A T I V E
A N A L Y S I S
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P A G E 34 P A G E 34
QCM-D data analysis
Quantitative (modeling): – rigid film: Sauerbrey m = -17.7 * f/n
– soft film: Viscoelastic modeling of f:s and D:s
Δ
D
time
Δf Δf ΔD
ΔD
•m (r, h)
•m
•h
?
h
r
h m
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P A G E 35 P A G E 35
From raw data extract numbers that
describe our system in a quantitative way
1. RIGID FILM
2. SOFT FILM
Viscoelastic model
Output:
ρ: density (kg/m3)
η: viscosity (G’’/ω), (kg/ms)
μ: elasticity (G’), (Pa)
d: thickness (m)
Input:
∆f:s
∆D:s
Output:
m: mass (ng/cm2)
Input:
∆f Sauerbrey relation
Quantitative Analysis:
h
r
h m
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P A G E 36 P A G E 36
The Sauerbrey equation
- input and Output
m = -17.7 * f/n
G. Sauerbrey in 1959
Sauerbrey
m = areal mass density (ng/cm2)
Thin and rigid homogeneous films Laterally heterogeneous films (“discrete particles”) with little energy dissipation
includes hydrodynamically coupled solvent
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P A G E 37 P A G E 37
Mucin adsorption onto Au
Time (h:m:s)1:20:001:10:001:00:00
Th
ickn
ess (
nm
)
50
40
30
20
10
0
Mucin adsorption onto Au
Time (h:m:s)1:20:001:10:001:00:00
Vis
co
sity (
Pa
s)
0.0015
0.001
0.0005
0
Viscoelastic Model (QTools)
- input and Output
D_1:3gfedcb
D_1:5gfedcb
D_1:7gfedcb
D_1:9gfedcb
D_1:11gfedcb
F_1:3gfedcb
F_1:5gfedcb
F_1:7gfedcb
F_1:9gfedcb
F_1:11gfedcb
Mucin adsorption onto Au
Time (h:min:s)1:20:001:10:00
Fre
qu
en
cy s
hift
0
-10
-20
-30
-40
-50
-60
-70
-80
-90
Dis
sip
atio
n (E
-6)
15
14
13
12
11
10
9
8
7
6
5
4
3
2
1
0
-1
QTools
Input parameters
• Δf:s and ΔD:s
• Layer density
• Fluid density and viscosity
Mucin adsorption onto Au
Time (h:m:s)1:20:001:10:001:00:00
Sh
ea
r m
od
ulu
s (
Pa
)
1.5E4
1E4
5000
0
thickness
viscosity
Shear modulus
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P A G E 38 P A G E 38
Film is
• Rigidly attached
• Evenly distributed
• Homogeneous character ,
with certain properties
Thickness, h
Density, r
Viscosity,h
Elasticity, m
Our QCM-D response model
Assmptions:
homogeneous character, evenly distributed, rigidly attached
h
r
h m
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P A G E 39 P A G E 39
MODEL INPUT Δf1 , ΔD1
+
Δf2, ΔD2
+
ρ (or h)
Domack et al., Physical Review E 56 (1997);
Voinova et al., Physica Scripta 59 (1999)
ρ: density, (kg/m3)
η: viscosity (kg/m·s)
μ: elasticity (kg/m·s2)
h: thickness, (m)
Crystal
Film
(ρ, h, m) h
Fluid
(ρl, hl)
n=1 n=3
MODEL OUTPUT η, μ, m (=h· ρ)
Viscoelastic modelling - What exactly is it that we do?
h
r
h m
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P A G E 40 P A G E 40
Sauerbrey vs Viscoelastic modelling
When to use which model?
Sauerbrey Viscoelastic
• D = 0
• Responses overlapping
on all harmonics
• D > 0
• Responses NOT overlapping
on all harmonics
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P A G E 41 P A G E 41
Sauerbrey vs Viscoelastic modelling
What happens if I use the wrong model?
Sauerbrey when it should be
Viscoelastic
Viscoelastic
when it should be
Sauerbey
2. Mass will be
underestimated
1. Mass depends
on harmonic
Can be difficult to model
– not enough input
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P A G E 42 P A G E 42
Viscoelastic modelling in QTools
1. Procedure step by step
2. How do I know I have a good fit?
3. Improving the fit
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P A G E 43 P A G E 43
Grid Fit
max
Viscosity
Thickness
Shear
modulus min
max
max
• Three parameters
• From ”initial guess values” of
the wanted parametrs, the
model calculates the f and
D shift.
=> These shifts are
compared to the ”true”
experimental values for f and
D
• Backwards calculation
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P A G E 44 P A G E 44
The Viscoelastic Model- requirements
What needs to be fulfilled?
A laterally homogeneous and evenly distributed film
The bulk fluid is a Newtonian fluid
The adsorbed layer couples perfectly to the sensor (no slip) The observed signal is due only to the film
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P A G E 45 P A G E 45
Getting started
• Open a QSoft file in QTools
• Go to Modeling/New Model/Viscoel....
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P A G E 46 P A G E 46
Tab 1: ”Model Settings”
Choose the Voigt model
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P A G E 47 P A G E 47
Each harmonc is unique
in a viscoelastic system
Δf=function1(n,ηf,ρf,μf,δf)
ΔD=function2(n,ηf,ρf,μf,δf)
Tab 1, Model Settings:
How many overtones do I need to include?
Include as many
harmonics
as possible!
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P A G E 48 P A G E 48
Fixed parameters
Tab 2: ”Parameters”
Parameters to fit
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P A G E 49 P A G E 49
”Estimate
all”
Tab 3: ”Measured data”
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P A G E 50 P A G E 50
Tab 4: ”Fit settings”
Limit x
Fit
direction
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P A G E 51 P A G E 51
Th
ickn
ess
Shear
modulus min
max
max
max
Grid
fit
Fitting routine SIMPLEX
Nelder, J. A., & Mead, R. 1965,Comp. J., 7, 308
Tab 4: ”Fit settings”
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P A G E 52 P A G E 52
1. Do the fitted and measured curves overlap well (i.e. is the ChiSquare low)?
2. Do the output parameters vary smoothly with time?
3. Does the output make physical sense?
Do I have a good fit?
Tab 5: ”Fit analysis”
2 = Σi [(Ytheory,i - Ymeas,i)/σi]2
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P A G E 53 P A G E 53
2 = Σi [(Ytheory,i - Ymeas,i)/σi]2
With a grid that is too rough, the deepest minimum might be overlooked Increase the number of steps or decrease the parameter range
How to improve the fit
(The best fit has the lowest chisquare 2)
10nm 100nm
e.g. thickness grid
2
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P A G E 54 P A G E 54
Summary Sauerbrey:
• ΔD is small / overtones are overlapping
• Rigid and thin film
Viscoelastic modeling:
• ΔD > 0 and spreading of overtones
• Soft (and laterally homogeneous) film
How to validate the fit?
• The fit should match the experimental data.
• Alter input parameter matrix (min, max and/or number of steps), and
check if the solution is unique
• Do the output parameters make sense physically?
• In time-resolved fitting, the output parameters (viscoelastic properties,
mass/thickness) should vary smoothly with time.
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P A G E 55 P A G E 55
ADVANCED MODELING OPTIONS
• Two layer modeling in QTools
• Frequency dependent viscoelasticity
(QTools Extended viscoelastic model)
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P A G E 56 P A G E 56
MODELING A TWO-STEP
ADSORPTION PROCESS
USING QTOOLS
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P A G E 57 P A G E 57
The experiment
Three approaches:
1. Model the layers one
by one (L1 + L2)
2. Model layer two as
L1(if first layer rigid)
3. Model L1 + L2
as one layer
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P A G E 58 P A G E 58
Approach 1: Model the two layers one by one
Step 1: Model Layer A as Layer 1 [L1]
– Parameters to fit: viscosity, shear modulus and thickness
– Limit x-values
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P A G E 59 P A G E 59
• Find the best solution
• Results in the parameters for L1, Layer A
Approach 1: Results step 1
Parameter Modeled data
L1 Viscosity 0,003 kg/ms
L1 Shear 22031 Pa
L1 Thickness 25 nm
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P A G E 60 P A G E 60
Approach 1
Step 2: Model Layer B as Layer 2 [L2]
– Fix the modeled parameters for layer 1
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P A G E 61 P A G E 61
Approach 1: Results step 2
• Limit the x-values to Layer B
Parameter Modeled data
L2 Viscosity 0,001 kg/ms
L2 Shear 55020 Pa
L2 Thickness 51 nm
Note: total thickness =
25 nm [L1] + 51 nm [L2] = 76 nm
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P A G E 62 P A G E 62
Approach 2: If Layer A is a rigid film
• Mark a data point before Layer B is added
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P A G E 63 P A G E 63
Approach 2
• Model Layer B as [L1] and limit x-values to this part
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P A G E 64 P A G E 64
Approach 2: Results
• Assumption: Layer A is perfectly rigid
• Advantage if you have 3 different layers to quantify
• If Layer A is not perfectly rigid it will affect the results of
Layer B
Parameter Modeled data
L1 Viscosity 0,001 kg/ms
L1 Shear 43421 Pa
L1 Thickness 59 nm
Parameter Modeled data
L2 Viscosity 0,001 kg/ms
L2 Shear 55020 Pa
L2 Thickness 51 nm
Approach 1
Layer B
Approach 2
Layer B
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P A G E 65 P A G E 65
Approach 3: Model all data as one layer
Parameter Modeled data
L1 Viscosity 0,002 kg/ms
L1 Shear 82964 Pa
L1 Thickness 56 nm
• Average density for both
layers
• Thickness includes both
layers
• Bad fit as layers are
different
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P A G E 66 P A G E 66
Conclusion
• L1: QTools treats the multilayer film as one homogenous
film to give an average value for the viscoelastic
parameters
• L1 and L2: QTools tries to find a solution with two
regions having different properties
• Recommended: model step-by-step according to
Approach 1
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P A G E 67 P A G E 67
FREQUENCY DEPENDENT
VISCOELASTICITY
the Extended viscoelastic model
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P A G E 68 P A G E 68
A Viscoelastic material can have different properties
depending on what frequency it is measured.
Example: Silly Putty
At short times, it bounces
like an elastic solid
t < 1ms
f >1kHz
At long times, it flows like
a viscous material
t > 1s
f <1Hz
Rheological properties depend on frequency
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P A G E 69 P A G E 69
www.wikipedia.com
Silly putty is a melt of entangled polymers
disentanglement
processes
segmental
relaxations
slow fast
Rheological properties of entangled polymers
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P A G E 70 P A G E 70
normalized frequency (Hz)
G’a
nd
G
’’ (P
a)
P. Oswald. 2009. Rheophysics
G* = G' + iG''
G* – complex shear modulus G’ – storage modulus G’’ – loss modulus
G’ >> G’’ – predominantly elastic G’ ≈ G’’ – viscoelastic G’ << G’’ – predominantly viscous
Rheological properties of polymers
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P A G E 71 P A G E 71
00 ffGG
V2 hfG
20
Shear elastic modulus:
00 ffGG 11
1
00V,V
hh ff
Shear loss modulus:
normalized frequency (Hz)
G’a
nd
G
’’ (P
a)
G = G' + jG''
’ and ” have different values in
different time zones
Frequency dependence of parameters
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P A G E 72 P A G E 72
www.wikipedia.com
• Viscoelastic properties can depend on the frequency
at which they are measured
• Viscoelastic properties of polymers are intimately
related to molecular-scale relaxation processes
• The viscoelastic parameters (G’ and G’’) of such
materials will vary as a function of frequency
Summary
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P A G E 73 P A G E 73
EXTENDED VISCOELASTIC
MODEL IN QTOOLS
Frequency dependent model
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P A G E 74 P A G E 74
Extended viscoelastic model in QTools
Same as the viscoelastic model in QTools but with
frequency dependence of storage modulus (shear)
and viscosity
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P A G E 75 P A G E 75
When to use the extended viscoelastic model in QTools
General criteria
• A laterally homogeneous and
evenly distributed film
• The bulk fluid is a Newtonian
fluid
• The adsorbed layer couples
perfectly to the sensor (no slip)
• The film is soft/viscoelastic
Additional reasons
• For films known to be
frequency dependent
• Can always be used
• When not finding a stable and
reasonable fit in the standard
model
Thickness will not be correctly modeled using the standard viscoelastic
model if the viscoelastic properties of the film are frequency dependent!
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P A G E 76 P A G E 76
Extended viscoelastic model
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P A G E 77 P A G E 77
Model settings – extended viscoelastic model
Frequency dependence
• Use the Voigt representation
• Include 1 layer only, to keep
the number of fit parameters
small
• Choose power-law frequency
dependence of viscosity and
shear
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P A G E 78 P A G E 78
h
hh 00 ffnn
hfG 2
00 ffGG nn
Storage modulus (shear):
00 ffGG nn
Loss modulus:
Parameters settings – extended equations
11
20
1 h
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P A G E 79 P A G E 79
Results
00 ffGG nn
h
hh 00 ffnn
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P A G E 80 P A G E 80
Summary – Extended viscoelastic model in QTools
• The extended viscoelastic model can be used if
the general criteria for modeling are fulfilled
• The extended viscoelastic model should be used
if viscoelastic properties of the film are frequency
dependent
• The model takes into account frequency
dependence of storage modulus (shear) and
viscosity
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P A G E 81 P A G E 81
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