Broadband Dielectric Spectroscopy and its Relationship to Other Spectroscopic Techniques

A. Schnhals
BAM Federal Institute for Materials Research and Testing, Unter den Eichen 87, 12205 Berlin

6th International Conference on Broadband Dielectric Spectroscopy and its Applications Satellite Courses, 6.09.2010 Madrid, Spain

Content
Introduction, Dielectric Spectroscopy Basics of Relaxation Spectroscopy Examples of Relaxation Spectroscopy Thermal spectroscopy Neutron spectroscopy (Scattering)

Application of Relaxation Spectroscopy

Dielectric Relaxation Spectroscopy

Maxwells Equations:
r r rot E = B t
Electric field Magnetic induction

r div B = 0

r r r rot H = j + D t
Magnetic field Dielectric displacement

r div D =

Density of charges

Current density

Material Equation:
Small electrical field strengths: 0 permittivity of vacuum Complex Dielectric Function * is time dependent if time dependent processes taking place within the sample

r r D = * 0 E

r r r r P = D D 0 = ( * 1) 0 E

Polarization

Dielectric Relaxation Spectroscopy A Special Case of Linear Response Theory

Input E(t)
Simplest Case : Step-like Input

System under investigation (t)

Output P(t)

The polarization measured as response to a step-like disturbance

P( t ) P ( t ) = E
P(t); Output
E(t); Input
E

PS

Relaxational Contribution
P

Instantaneous response

Time

Time

Dielectric Relaxation Spectroscopy A Special Case of Linear Response Theory

Input E(t)
Arbitrary input

System under investigation (t)

Approximation of the Input by step-like changes

Output P(t)
E * t t

E ( t ) E ( 0) +
E(t); Input

dx * dt dt
P( t ) = P + 0

E * t t

( t t ' )

d E( t ' ) dt ' dt '

Time

Linearity Basics of Linear Response Theory Causality

Dielectric Relaxation Spectroscopy A Special Case of Linear Response Theory

Special input Periodical input

E ( t ) = E 0 exp( it ) = E 0 sin(t )
- angular frequency

Phase shift

P( t ) = P0 sin(t + )
Complex Numbers

E(t) ; P(t)

P() = 0 [( i)1] E()

Time

In-Phase with E(t)

90-shifted to E(t)

Complex Dielectric Function Complex Compliance

* () = ' () i ' ' ()

Dielectric Relaxation Spectroscopy A Special Case of Linear Response Theory

Complex Compliance

* () = ' () i ' ' ()

Real Part Related to the energy stored reversibly during one cycle J

Imaginary or Loss Part Related to the energy dissipated during one cycle

* J*
Complex Plane

tan =

' ' '

Phase shift

Dielectric Relaxation Spectroscopy A Special Case of Linear Response Theory

Real Part Related to the energy stored reversibly during one cycle

Law of energy conservation

Loss Part

Related to the energy dissipated during one cycle Relationship between both quantities

Kramers Kronig Relationships

1 ' ' ( ) d ' () = ' ' () = 1 ' ( ) d

Dielectric Relaxation Spectroscopy A Special Case of Linear Response Theory

P( t ) = P + 0
t

( t t ' )

d E( t ' ) dt ' dt '

Linear Equation

Can be inverted

Output

(t) System under investigation

Input

E(t) M(t)
Electrical Modulus

P(t)

Relationship between (t) and M(t)

(t) Dirac function

( t t ' ) M( t ' ) dt ' = (t )

Fourier Transformation

M * () * () = 1

Dielectric Relaxation Spectroscopy A Special Case of Linear Response Theory

Thermodynamic quantities are average values. Because of the thermal movement of the molecules these quantities fluctuate around their mean values

Correlation function of Polarization Fluctuations

< P() P(0) > ( ) = < P 2 >

Spectral Density < P 2 > 2 (P ) = () exp (i) d 2 Fluctuation Dissipation Theorem

r 1 r P = i V

< (0) () > + 2 < (0) () > ( ) = < ( ) >

i i i i i< j 2 i j i i

Measure for the frequency distribution of the fluctuations Links microscopic fluctuations and macroscopic reactions For a small (linear) disturbance a system reacts only in the way as it fluctuates

( ) =
(P 2 ) =

1 ( ) 1 k T
1 ' ' () 1 kT

Dielectric Spectroscopy..

PPG, Mw= 4000 g/mol

Dynamic Glass Transition, relaxation

0.5
204.5 K

332.8 K

233.7 K

253.3 K 303.3 K 273.2 K

0.0 Normal Mode Relaxation -0.5

log ''

-1.0

-1.5 -4 -2 0 2 4 6 8
Coaxial Reflectometer

10

Time Domain Spectrometer

log ( f [Hz])
Frequency Response Analysis

Dielectric Spectroscopy ..

PMPS, Mw= 1000 g/mol

-1.0
8

-1.5 6
4

log ''

log(fp [Hz])

-2.0

VFT- equation:
2 0

log f p = log f p

A T T0

-2.5
-2

-3.0 -4 3.0 -4

* HN () = +
-2
3.5 0

24.0
-1

4.5 6

85.0

10

(1 + (iHN ) )

1000 /T ] log (f[K [Hz])

HP4191A Alpha-Analyzer

Mean Relaxation Rate fp Dielectric Strength

Linear Response Theory

Molecular Motions Input System under Investigation Disturbance x(t) Reaction y(t) Output

Material function

Electric field E Shear tension Magnetic field H Temperature T

Polarization P Shear angle Magnetization M Entropy S

Basics of Relaxation Spectroscopy

Molecular Motions Input System under Investigation Disturbance x(t) Disturbance
Intensive - independent of V

Output

Reaction y(t) Reaction

Extensive ~ V

Material function
Generalized Modulus G(t)

Relaxation
Tensile Strain
Extensive ~ V

Strain
Intensive - independent of V

Elastic Modulus
Generalized Compliance J(t)

Retardation
Strain Tensile Strain Elastic Compliance

Input System under Investigation x(t)

Type of Experiment Disturbance x(t) Response y(t) Compliance J(t) or J*()

Output y(t)
Modulus G(t) or G*()

Dielectric

Electric field E Shear tension Pressure p Magnetic field H Temperature T

Polarization P Shear angel Volume V Magnetization M Entropy S

Dielectric Susceptibility *()=(*()-1) Shear compliance J(t) Volume compliance B(t) V Magnetic susceptibility *()=(*()-1) Heat capacity cp(t)

Dielectric Modulus Shear Modulus G(t) Compression Modulus K(t) -

Mechanical Shear Isotropic Compression Magnetic

Heat

Temperature Modulus GT(t)

Specific Heat Spectroscopy

Input T(t)
Temperature Modulated DSC

A Special Case of Linear Response Theory

System under investigation cp(t) Output S(t)

The modulated temperature results in a modulated heat flow Thermocouples The heat flow is phase shifted if time dependent processes take place in the sample

Furnace
Temperature

& * t + A sin( * t ) T( t ) = T

C*p()= Cp() i Cp()

Time
Ch. Schick, Temperature Modulated Differential Scanning Calorimetry - Basics and Applications to Polymers in Handbook of Thermal Analysis and Calorimetry edited by S. Cheng (Elsevier, p 713. Vol. 3, 2002).

Specific Heat Spectroscopy

Example Temperature Modulated DSC Due to heating rate

A Special Case of Linear Response Theory

Polystyrene

2.00 Tg(q) 1.75 total cp 1.50 cp' T( ) 0.10 0.05 0.00 -0.05
Gaussfit

Specific Heat Capacity in J g

-1

-1

Due to modulation

cp''

340

360

380

400

Temperature in K
Hensel, A., and Schick, C.: J. Non-Cryst. Solids, 235-237 (1998) 510-516.

Specific Heat Spectroscopy

Example Temperature Modulated DSC

A Special Case of Linear Response Theory

Glass forming liquid crystal E7
Mixture of different LCs

Real Part Frequency

4
1.6

Loss factor

Phase Transition: Frequency Glass Transition:

TN/I = 333 K Tg = 211 K

Phase Transition
3

0.20 1.66 mHz 3.33 mHz 6.66 mHz 13.3 mHz 26.6 mHz 53.2 mHz

Heat Flow [mW]

Glass Transition
1.66 mHz 3.33 mHz 6.66 mHz 13.3 mHz 26.6 mHz 53.2 mHz

corrected phase angle / rad

0.16

1.4

0.12

cp [Jg K ]

-1

-1

0.08

1.2

0.04

0.00

-0.04

1.0 200

205

210

215

220

200

205

210 T [K]

215

220

1 -100

T [K]

-50

FrequencyT range : [C]

10-3 Hz

. 5

50

*10-2

Hz

100

Heating and cooling rates must be adjusted to meet stationary conditions !

Specific Heat Spectroscopy

Input T(t) AC Chip calorimetry

A Special Case of Linear Response Theory

System under investigation cp(t) Output S(t) Pressure gauge, Xsensor Integration

10 mm

2 mm Fast heating and cooling

0.1 mm

Differential setup

Increase of sensitivity

H. Huth, A. Minakov, Ch. Schick, Polym. Sci. B Polym. Phys. 44, 2996 (2006).

Specific Heat Spectroscopy

Example AC calorimetry

A Special Case of Linear Response Theory

PMPS, Mw= 1000 g/mol

95

1.5

90 1.0 85
Corr [deg]

C' [au]

80

f=240 Hz

0.5

75 0.0 70 180 200 220 240 260 280 300

T [K]

Frequency range : 10 Hz . 5000 Hz

A. Schnhals et al. J. Non-Cryst. Solids 353 (2007) 3853

Combination of Dielectric Spectroscopy ..

PMPS, Mw= 1000 g/mol

and Specific Heat Spectroscopy

8 6 4

Specific Heat
AC Chip Calorimetry

log (fp [Hz])

2 0

Dielectric
TMDSC

-2 -4 3.0

3.5

4.0

4.5
-1

5.0

1000 / T [K ]

Both methods measure the same process. Glassy dynamics of PMPS A. Schnhals et al. J. Non-Cryst. Solids 353 (2007) 3853

Combination of Dielectric Spectroscopy ..

Nematic Isotropic Glass forming liquid crystal E7

Questions:
0

log ''

Temperature dependence of both modes?

-relaxation

-1

Which mode corresponds to glassy dynamics?

-2 -2

Tumbling-mode
0 2 4 6 8 10

log (f [Hz])

A.R. Bras et al. Phys Rev. E 75 (2007) 61708

Combination of Dielectric Spectroscopy ..

Glass forming liquid crystal E7

10 8 6 log (fp [Hz]) p 4 2 0 -2 2.5

TI/N

Tumbling-mode
The temperature dependence of the relaxation rates of both the - and the tumbling mode is curved vs. 1/T.

Tg

Close to Tg the temperature dependencies of both mode seems to collapse.

-relaxation
3.0 3.5 4.0
-1

4.5

5.0

-1 1000 / T [K ]

Derivative analysis
A.R. Bras et al. Phys Rev. E 75 (2007) 61708

Combination of Dielectric Spectroscopy ..

Glass forming liquid crystal E7
The temperature dependence of the relaxation rates of both the - and the tumbling mode follow the VFT-equation.
10

Similar to the decoupling of VFTequation:

rotational and translation diffusion in glass-forming liquids Similar to the decoupling of segmental and chain dynamics in polymers
1 / 2

A log f p = log f p T T0

8 {d log (fp [Hz]) / dT [K] }

Tumblingmode
Difference in T0 = 30 K !!!!

Derivative

-1/2

d log f p 1 (T T0 ) = 1/ 2 d T A be explained Can by different

averaging of modes with different length scales

T0,

T0,Tumb

-relaxation Which mode is responsible Straight Line for glassy dynamics?

0 160 180 200 220 240 260 280 300 320

T [K]

A.R. Bras et al. Phys Rev. E 75 (2007) 61708

Combination of Dielectric Spectroscopy ..

Relaxation Map
10 8
8 {d log (fp [Hz]) / dT [K] }
-1/2

Glass forming liquid crystal E7

and Specific Heat Spectroscopy

Derivative Plot
10 Stars Thermal data

TI/N

Tumbling-mode -relaxation

6 log (fp [Hz]) 4 2 0

Tg

-relaxation
-2

Tumbling-mode
-4 2.5 3.0 3.5 4.0
-1

Thermal data
0 160

4.5 180

200

5.0

220

240

260

280

300

320

1000 / T [K ]

T [K]

The thermal data agree perfectly with that of the tumbling with regard to the absolute values and its temperature dependence
A.R. Bras et al. Phys Rev. E 75 (2007) 61708

Tumbling mode is responsible for glassy dynamics!

Neutron Scattering

Neutrons are parts of the atomic nuclei Isotopes: Elements with the same number of protone but with a different number of neutrons. Examples: Hydrogen, Deuterium, Tritium

Neutrons Have the same mass than protons Electrically neutral Have a spin

Neutrons can be obtained by nuclear fission processes Atomic reactor, Neutron spallation source

Neutron Scattering
Theoretical Consideration Neutron Cross Sections, Correlation Functions
ki Nuclei

ki wave vector of the incoming neutron kf wave vector of the scattered neutron
kf

q Scattering vector: Momentum transfer: q = kf - ki

q

= ( kf ki) = 2 ( kf2 ki2)

2 - scattering angle

Energy transfer: | kf | | ki | | kf | | ki |

Elastic scattering: Inelastic scattering:

r 4 q = | q | = sin 0
Time dependence

Time and spatial information

Comparison of Scattering Vector and Energy Ranges of Different Inelastic Scattering Methods
r/
10 10 10
4 2 0

10

10

10

10

10

-1

10
inelastic

-3 -1 1 3

10 10 10
NMR

Raman Brilloui n scatt.

X-R

E /meV

10 10 10 10 10 10

-2 -4 -6 -8

t / ps

10 10

5 7 9 11

-10 -12

Laser PCS

10
X-R PCS

10 10
-1

10

-3

10

-2

Q /

-1

10

10

10

Neutron Scattering
Theoretical Consideration Neutron Cross Sections, Correlation Functions
The intensity of the scattered neutrons is described by a double differential cross section:
N 1 kf 2 rr r { [ = dt exp( i t ) b b exp i q r ( t ) rk (0)]} j k j j , k h 2h k i

Solid angle

Energy change

Position of atom j at time t Scattering lengths

Position of atom k at time t =0

k 2 = f N b2 b h hk i
Self Correlation Pair Correlation

{[

]S

r r 2 ( q , ) + b S ( q , ) inc

N 1 r r r -12 = dt exp( i t ) exp[ i q r ( 0 )] exp[ i q rj ( t )] ( q , ) = -0.374 * 10 cm Hydrogen bHS inc j j 2N N 1 r r r Deuterium bD S =(0.667 * 10-12 cm dt exp( i t ) exp[iqrj ( t )] exp[iqrk (0)] q, ) = j, k 2N

Scattering lenght:

Time Domain, Incoherent scattering

r 1 N q r 2 Sinc (q, t ) = exp [rj ( t ) rj (0)] N j 6

Neutron Scattering
Input

A Special Case of Linear Response Theory ?

Output y(t)=?
J(t)=?

System under Investigation x(t)=?

r r 1 N q Sinc (q, t ) = exp r j ( t ) r j ( 0) 2 N j 6

r r r Sinc (q, t ) =< (q, t )(q ) >

Density correlation function

van Hove Correlation function

Correlation function

Fluctuation Dissipation Theorem

Modulus, Compliance ?

Thermodynamics (t=0):

(q ) =

S(q) kTN

Isothermal compressibility

S(q,t) is related to a q-dependent Compression Modulus

W. Gtze in Hansen et al. "Liquids, Freezing and the Glass Transition", North Holland 1990

Neutron Scattering

IN 6 IN 16

Time of Flight - IN 6 / ILL Energy scale: meV Time scale: 0.2 .. 20 ps

Backscattering - IN 16 / ILL and BSS Jlich Energy scale: eV Time scale: 0.1 .. 4 ns

Neutron Scattering.. Examples

IN6
1.0 0.10
1.0

IN 6
PMPS - Bulk

IN 16

Resolution of the spectrometer

T=120 K

Broadband Neutron Spectroscopy Quasielastic

Scattering

0.9 0.08
0.8 SInc(, 54) [a.u.] 0.06 0.8 0.6 0.04 0.7 0.4 0.02 0.2 0.6 0.00 0.0 0.5

PMPS PMPS212 212K K

Sinc(Q,t)
1.81 -1 1.64 -1 1.42 -1 1.16 -1 0.87 -1 0.54
-4 -4 0 -2 -2
-1

Sinc(Q,t)

incoherent intermediate scattering function

0 0

2 2

4 3 4

Energy EnergyTransfer Transfer [meV] [meV] log(t [ps])

Spectral Shape of IN16 data similar but energy resolution eV

Fourier Transformation of each data set Comparison in time domain

Overview of the molecular Dynamics of PMPS by elastics Scans

Elastic scans on a backscattering instrument give an efficient overview over the temperature dependent dynamics.
Mean square displacement ueff:
3
0.5

Q < u > eff I el / I 0 = exp 3

2 2
Iel elastically scattered intensity I0 totally scattered intensity

0.4

Increase of Mobility

<u >eff [ ]

0.3

<u >eff [ ]

Glass Transition
1

0.2

Methyl Groups Methyl Groups Harmonic Vibrations

Analysis Methyl group rotation Analysis Glass transition

0.1

0.0

0
00 50

100 100

150 200

200

300

T [K]T [K]

Data Analysis Methyl Groups PMPS

3 protons in the CH3 -group 8 protons 5 protons in the phenyl ring Analysis of the CH3 group rotation !

3/8 of the scattering is due to localized rotation of the CH3 -group

IN 6
1.0

IN 16
PMPS - Bulk
T=120 K

Debye-Waller-factor Elastic incoherent structure factor (EISF)

0.9

0.8

Sinc(Q,t)

0.7

0.6

1.81 -1 1.64 -1 1.42 -1 1.16 -1 0.87 -1 0.54 0 1 2 3 4

-1

CH 3 t SInc (Q, t ) = DWF * (1 A) exp A + CH3

KWW-function

0.5

=0.7 !
log(t [ps])

Data Analysis Segmental Relaxation PMPS

From CH3-Analysis Above T results from the g the scattering

CH 3 seg t t CH3 group rotation + SInc (Q, t ) = DWF * (1 A) exp A exp seg CH3 Segmental relaxation
1.0 DWF 0.8 CH3 0.6 PMPS Bulk T=250 K -1 Q=1.16

Fast Processes (DWF)

From Dielectric

< >=
Segmental

Sinc (Q,t)

KWW 1

0.4
Contribution segmental

Comparison with other experiments

0.2
Contribution CH3 -group

0.0 -1 0 1 2 3 4

log (t [ps])

Overall Molecular Dynamics PMPS

Precise determination of glassy dynamics in a wide temperature range using different probes

Neutrons

12 10 8
Q

CH3-Rotation

log(fp [Hz])

6 4 2 0 -2
Segmental

Dielectric

Thermal

-4 2 3 4 5 6
-1

1000 / T [K ]

Analysis of the Temperature dependence

Dielectric data cannot be described by the VFTequation in the whole temperature range VFT- equation:
log f p = log f p A T T0

10 8 6 log (fp [Hz]) 4 2 0 -2 -4 3.4

3.6

Derivative
d log f p dT
1 / 2

1 A1 / 2

(T T0 )

3.8

4.0

4.2
-1

4.4

4.6

4.8

1000 / T [K ]

Straight Line, T0>0

Analysis of the Temperature dependence

Derivative-Plot
8

low and high temperature regime

TB
{ log (fp [Hz]) / dT [K] }
-1/2

two VFT - dependencies

T0,high

Crossover temperature TB = 250 K Thermal and dielectric data have the same temperature dependence

T0,Low
2

0 160 180 200 220 240 260 280 300

T [K]

red : dielectric data blue: thermal data

Temperature dependence of the dielectric relaxation strength

Dipole moment Debye Theory

2 N 1 = g 3 0 kB T V
Interaction parameter
80

TB

Temperature dependence of is much stronger than predicted Cooperative effects

T*

60

40

Change of the temperature dependence of at TB

20

3.2

3.6

4.0

4.4
-1

4.8

1000 / T [K ]

Temperature dependence of the dielectric relaxation strength

The change in the temperature dependence of is not much pronounced Plot of vs. log fp
0.40 0.35 0.30 0.25

Sharp transition fro a low temperature to a high temperature branch

TB

The crossover frequency coresponds to TB

0.20 0.15 0.10 0.05 -2 0 2 4 6 8 10 12

log (fp [Hz])

A. Schnhals Euro. Phys. Lett. 56 (2001) 815

Overall Molecular Dynamics PMPS

Neutrons

12 10 8
Q

CH3-Rotation

log(fp [Hz])

6 4 2 0 -2
Segmental

Dielectric

Thermal

-4 2 3 4 5 6
-1

1000 / T [K ]

Dynamics PMPS: Q-Dependence Segmental Relaxation

Bulk
4

2 / KWW

homogeneous

log (KWW [ps])

- Slope

2 T=250 K T=270 K T=300 K T=330 K -0.2 0.0 0.2

-1

heterogeneous

0 -0.4

0.4

1 240

260

280

300

320

340

360

log (Q [ ])

T [K]

t Sinc (Q, t ) = exp( Q 2 Dt ) = exp

~ Q 2

Theory :
t Sinc (Q, t ) = exp( Q At ) = exp
2

~ Q 2 /

Overall Molecular Dynamics PMPS

Neutrons CH3-Rotation

12 10 8
Q

log(fp [Hz])

6 4 2 0 -2
Segmental

Temperature dependence Arrhenius-like EA=8.3 kJ/mol In agreement with values found for other polymers

Dielectric

Thermal

-4 2 3 4 5 6
-1

1000 / T [K ]

Methyl Group Rotation in PMPS

Threefold Potential

1 sin( 3 Q r ) A 3 jump (Q) = 1 + 2 3 3Qr

1.0 1.0

A App (Q) = (1 c fix ) A(Q) + c fix

EISF EISF EISF Methyl groups Methyl groups Methyl groups

3/8 of the scattering is due to localized rotation of the CH3 -group

0.8 0.8 0.8

0.6 0.6

Structure:

cfix=5/8=0.624

Experiment: cfix=0.55

0.4 0.40.0 0.0 0.0

0.5 0.5 0.5

Q [ ] -1 -1 Q[ [ ]] Q

1.0 1.0-1 1.0

1.5 1.5 1.5

2.0 2.0 2.0

Methyl Group Rotation in PMPS Q - dependence of the Relaxation Time

2.4

T=120 K
2.0

Below Tg the relaxation times are independent of Q

log (CH3 [ps])

1.6

Slope: - 1.5

At Tg the relaxation times become Q dependent

1.2

T=212 K = Tg
-0.2 0.0 0.2
-1

Onset of segmental dynamics

0.4

-0.4

log(Q [ ])

Methyl Group Rotation in PMPS Temperature dependence of the EISF

1.0
0.8

0.9

0.7

120 K 170 K 212 K

< Tg = Tg

Additional mobility above Tg

EISFMethyl groups

0.8

0.6

EISF

Dynamical Heterogeneities
0.5

0.7

Islands of Mobility

0.6

0.4

Q=1.81 -1
0.5 0.3 0.4 100 0.6

Tg

TB

0.8150 1.0

1.2 200
-1

1.4 2501.6

Q [ ]T [K]

Higher quasielastic scattering Decrease of the EISF 1.8 300 2.0 350 above Tg Phenylring flip ???

Conclusion.
Precise Determination of the molecular dynamics of PMPS over 17 orders of magnitude in time
-Relaxation (glassy dynamics)
The temperature dependence of the relaxation times shows a crossover from a low to a high temperature range. Crossover temperature TB= 250K. In both ranges the temperature dependence of the relaxation rates is VFT-like with different Vogel temperatures Also the dielectric strength shows a crossover behavior at the same TB The dependence of the relaxation times on the momentum transfer indicates that the molecular dynamics is heterogeneous even above TB

Methyl group Rotation

The methyl group rotation can be described by jumps in a threefold potential considering the elastic scattering of the frozen chain. Above Tg the EISF becomes temperature dependent and the relaxation times depends on momentum transfer .
Thanks to the ILL and Research Center Jlich for enabling the neutron experiments.