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Gelatine liquid-solid transition

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0.5μm Gelatin : liquid for Tm>32°C solid for Tg< 28°C For T<Tg gelatin presents : aging and memory effects at 10%wt concentration after a cooling at 26°C it takes ~2h to solidify In our experiment we use 10%wt concentration in water Gelatin liquid-solid transition mercredi 20 mars 2013
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Page 1: Gelatine liquid-solid transition

0.5µm

Gelatin :

liquid for Tm>32°C

solid for Tg< 28°C

For T<Tg gelatin presents : aging and memory effects

at 10%wt concentration after a cooling at 26°C it takes ~2h to solidify

In our experiment we use

10%wt concentration in water

Gelatin liquid-solid transition

mercredi 20 mars 2013

Page 2: Gelatine liquid-solid transition

Gelatin Gelatin : liquid for Tm>32°C solid for Tg< 28°C 38°C

Trapping laser

Trapped glass particle R=1µm

For T<Tg gelatin presents : aging and memory effects

at 10%wt concentration after a cooling at 26°C it takes ~2h to solidify

Liquid

Gelatin liquid-solid transition

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Page 3: Gelatine liquid-solid transition

Gelatin Gelatin : liquid for Tm>32°C solid for Tg< 28°C 26°C

Trapping laser

Trapped glass particle R=1µm

For T<Tg gelatin presents : aging and memory effects

at 10%wt concentration after a cooling at 26°C it takes ~2h to solidify

solid

Gelatin liquid-solid transition

mercredi 20 mars 2013

Page 4: Gelatine liquid-solid transition

Gelatin 26°C

Trapping laser

Trapped glass particle R=1µm

Gelatin : liquid for Tm>32°C solid for Tg< 28°C

Infrared Laser switched on for a few minutes

Gelatin liquid-solid transition (heating)

mercredi 20 mars 2013

Page 5: Gelatine liquid-solid transition

RL

A drop of liquid of radius RL=5 µm is formed

Gelatin 26°C The temperature around the focus grows till 38°C and the gel melts

Infrared Laser switched on for a few minutes

Gelatin liquid-solid transition (heating)

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Page 6: Gelatine liquid-solid transition

RL

Gelatin 26°C

At t=1ms after the switch off we obtain:

A drop of an unstable liquid at 26°C inside a stable solid

The infrared laser is switched off and the liquid drop cools very fast

Trapped glass particle R=1µm

Gelatin liquid-solid transition(quench)

mercredi 20 mars 2013

Page 7: Gelatine liquid-solid transition

RL

Gelatin 26°C Drop of an unstable liquid at 26°C inside a stable solid

What happens ?

How long does it take to solidify ?

Does the transition start from the frontier ?

What is the nature of the bead fluctuations inside the drop ?

Gelatin liquid-solid transition(quench)

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Page 8: Gelatine liquid-solid transition

RL

Gelatin 26°C

Drop of the unstable liquid at 26°C inside the stable solid

Dynamics of the bead

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Page 9: Gelatine liquid-solid transition

Dynamics of the bead

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Page 10: Gelatine liquid-solid transition

From equipartition

Time evolution of the variance

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Page 11: Gelatine liquid-solid transition

From equipartition

Time evolution of the variance

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Page 12: Gelatine liquid-solid transition

The applied oscillating force

The linear response

Motion of a Brownian particle trapped by a laser Beam

Viscoelastic Langevin dynamics

Elastic modulus

Viscosity

Active microrheology

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Page 13: Gelatine liquid-solid transition

The gel forms in about 30 min

Time evolution of the viscous and elastic modulusI. Pure viscousII. Negligible elasticityIII. Logarithmic growth of G’ etG’’

Gelatine liquid-solid transition

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Page 14: Gelatine liquid-solid transition

Heat Fluctuations

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Page 15: Gelatine liquid-solid transition

Gel elasticity

Heat Fluctuations

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Page 16: Gelatine liquid-solid transition

Gel elasticity

Heat Fluctuations

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Page 17: Gelatine liquid-solid transition

Gel elasticity

Heat Fluctuations

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Page 18: Gelatine liquid-solid transition

glicerol

gelatin

Energy PDF

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Page 19: Gelatine liquid-solid transition

Mean heat

Energy PDF and mean heat

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Page 20: Gelatine liquid-solid transition

FT fixes the symmetries of the PDF

Fluctuation theorem

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Page 21: Gelatine liquid-solid transition

FT fixes the symmetries of the PDF

What is the value ?

Fluctuation theorem

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Page 22: Gelatine liquid-solid transition

Using the experimental observation that P(x) are GaussianOne gets from a simple model in the limit of large τ :

Data analysis

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Page 23: Gelatine liquid-solid transition

Using the experimental observation that P(x) are GaussianOne gets from a simple model in the limit of large τ :

Data analysis

mercredi 20 mars 2013

Page 24: Gelatine liquid-solid transition

Using the experimental observation that P(x) are GaussianOne gets from a simple model in the limit of large τ :

from which

Data analysis

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Page 25: Gelatine liquid-solid transition

glicerol

gelatin

Energy PDF

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Page 26: Gelatine liquid-solid transition

Similar relations have been theoretically derived :

Comparisons with other results

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Page 27: Gelatine liquid-solid transition

Similar relations have been theoretically derived :

A) In the stationary case for the heat flux between two reservoirs at different temperatures

TH TC

heat flux

Comparisons with other results

mercredi 20 mars 2013

Page 28: Gelatine liquid-solid transition

Similar relations have been theoretically derived :

A) In the stationary case for the heat flux between two reservoirs at different temperatures

TH TC

heat flux

B) In the non-stationary case during the aging of spin glasses

Comparisons with other results

mercredi 20 mars 2013

Page 29: Gelatine liquid-solid transition

From Fluctuation Theorem

is the entropy production rate of the relaxation process

Comparing this result with numerical data of aging spin-glasses

Aging can be interpreted as an heat transfer (cooling) of the slow modes towards the heat bath

What this is useful for ?

mercredi 20 mars 2013

Page 30: Gelatine liquid-solid transition

The liquid-solid transition is studied inside a drop of liquid after a very fast quench.

Conclusions

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Page 31: Gelatine liquid-solid transition

The liquid-solid transition is studied inside a drop of liquid after a very fast quench.

a) The fluctuations of heat are asymmetric, i.e. the dynamics transfer heat towards the bath

b) The Fluctuation Theorem is satisfied in a non-stationary regime

Conclusions

mercredi 20 mars 2013

Page 32: Gelatine liquid-solid transition

The liquid-solid transition is studied inside a drop of liquid after a very fast quench.

a) The fluctuations of heat are asymmetric, i.e. the dynamics transfer heat towards the bath

b) The Fluctuation Theorem is satisfied in a non-stationary regime

c) The Fluctuation Dissipation Theorem is violated

Conclusions

mercredi 20 mars 2013

Page 33: Gelatine liquid-solid transition

Fluctuations and Linear response

0<t<15s 75<t<90s

S(f, t)

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Page 34: Gelatine liquid-solid transition

Fluctuations and Linear response

0<t<15s 75<t<90s

S(f, t)

S(f, t) =2kB T

πfIm[R(f, t)] in equilibrium

FDT

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Page 35: Gelatine liquid-solid transition

Fluctuations and Linear response

0<t<15s 75<t<90s

S(f, t)

S(f, t) �= 2kB T

πfIm[R(f, t)] out of equilibrium

FDT is violated in our experiment

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Page 36: Gelatine liquid-solid transition

� ∞

0

�S(f, t)− 2kB T

πfIm{R(f, t)}

�df =

2Qt,∆t

k

Fluctuations and Linear response

0<t<15s 75<t<90s

S(f, t)

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Page 37: Gelatine liquid-solid transition

� ∞

0

�S(f, t)− 2kB T

πfIm{R(f, t)}

�df =

2Qt,∆t

k

Fluctuations and Linear response

0<t<15s 75<t<90s

S(f, t)

heat dissipated in the time interval [t,t+Δt]

mercredi 20 mars 2013

Page 38: Gelatine liquid-solid transition

� ∞

0

�S(f, t)− 2kB T

πfIm{R(f, t)}

�df =

2Qt,∆t

k

Fluctuations and Linear response

0<t<15s 75<t<90s

S(f, t)

heat dissipated in the time interval [t,t+Δt]

As in the generalized FDT for NESS the extra additive term is related to the heat flux. (Chetrite, Gawedzki, Seifert Speck, Maes, Lipiello, Corberi)

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Page 39: Gelatine liquid-solid transition

The liquid-solid transition is studied inside a drop of liquid after a very fast quench.

Conclusions

mercredi 20 mars 2013

Page 40: Gelatine liquid-solid transition

The liquid-solid transition is studied inside a drop of liquid after a very fast quench.

a) The fluctuations of heat are asymmetric, i.e. the dynamics transfer heat towards the bath

b) The Fluctuation Theorem is satisfied in a non-stationary regime

Conclusions

mercredi 20 mars 2013

Page 41: Gelatine liquid-solid transition

The liquid-solid transition is studied inside a drop of liquid after a very fast quench.

a) The fluctuations of heat are asymmetric, i.e. the dynamics transfer heat towards the bath

b) The Fluctuation Theorem is satisfied in a non-stationary regime

c) The Fluctuation Dissipation Theorem is violated. The amount of the violation is related to the heat flux as for the

Generalized FDT for NESS.

Conclusions

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Page 42: Gelatine liquid-solid transition

RL

t(s)

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Page 43: Gelatine liquid-solid transition

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Page 44: Gelatine liquid-solid transition

Experiment in gelatine at 10%wt sol-gel transition at 28°C

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Page 45: Gelatine liquid-solid transition

The stochastic resonance and Fluctuation Theorem

Brownian particle trapped by two laser beams P.Jop. A. Petrosian, S. Ciliberto, Eur. Phys. Lett. 81, 50005 (2008)

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Page 46: Gelatine liquid-solid transition

The stochastic resonance and Fluctuation Theorem

Brownian particle trapped by two laser beams P.Jop. A. Petrosian, S. Ciliberto, Eur. Phys. Lett. 81, 50005 (2008)

mercredi 20 mars 2013

Page 47: Gelatine liquid-solid transition

The stochastic resonance and Fluctuation Theorem

Brownian particle trapped by two laser beams P.Jop. A. Petrosian, S. Ciliberto, Eur. Phys. Lett. 81, 50005 (2008)

mercredi 20 mars 2013

Page 48: Gelatine liquid-solid transition

The stochastic resonance and Fluctuation Theorem

Brownian particle trapped by two laser beams P.Jop. A. Petrosian, S. Ciliberto, Eur. Phys. Lett. 81, 50005 (2008)

mercredi 20 mars 2013

Page 49: Gelatine liquid-solid transition

The stochastic resonance and Fluctuation Theorem

Brownian particle trapped by two laser beams P.Jop. A. Petrosian, S. Ciliberto, Eur. Phys. Lett. 81, 50005 (2008)

mercredi 20 mars 2013

Page 50: Gelatine liquid-solid transition

The non linear potential

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Page 51: Gelatine liquid-solid transition

The non linear potential

f=0.1Hz

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Page 52: Gelatine liquid-solid transition

Stochastic Resonance

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Page 53: Gelatine liquid-solid transition

Fluctuation Theorem for W

f=0.25Hz and τ= n / f

k BT

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Page 54: Gelatine liquid-solid transition

Fluctuation Theorem for Q

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Page 55: Gelatine liquid-solid transition

Theoretical comparison

A. Imparato, P. Jop, A. Petrosyan and S. Ciliberto, J. Stat. Mech. (2008) P10017

PDF of the heat computed on a single period : (initial phase=0) (averaged over different initial phases)

Experimental dataTheoretical prediction based on Fokker-Planck equation

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Page 56: Gelatine liquid-solid transition

Conclusions on FT (partial)

We have studied the energy fluctuations of a harmonic oscillator driven out of equilibrium by an external force.

We have measured the finite time corrections for SSFT and compared to the theoretical predictions. TFT is instead verifed for all times.

The ‘’ trajectory dependent entropy ‘’ has been measured and we checked that SSFT is verified for all times for the ‘’total

entropy’’.

We have shown that in this specific example the ‘’total entropy’’ takes into account only the entropy produced by the external driving, without the entropy fluctuations at equilibrium.

We have applied also SSFT to the strongly non-linear case of the stochastic resonance

mercredi 20 mars 2013


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