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Competence in Physics key to your success BASF Aktiengesellschaft Polymer Physics Ludwigshafen, Germany Nikolaus Nestle Diffusion Fundamentals II 27.08.07 L'Aquila, Abruzzi, Italia Diffusion challenges in (chemical) industries

Diffusion challenges in (chemical) industries

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Page 1: Diffusion challenges in (chemical) industries

Competence in Physicskey to your success

BASF AktiengesellschaftPolymer Physics

Ludwigshafen, Germany

Nikolaus Nestle

Diffusion Fundamentals II27.08.07

L'Aquila, Abruzzi, Italia

Diffusion challenges

in (chemical) industries

Page 2: Diffusion challenges in (chemical) industries

GKP 000-0000 (2) (Januar 2005)

Competence in Physicskey to your successThe many contexts of

diffusion...

...@ DiffuFu-II:

•Talks Cavalli-Sforza, Vogl

•Poster B9 (Fujie, Odagaki)

...@ in economic life: ...

Page 3: Diffusion challenges in (chemical) industries

GKP 000-0000 (3) (Januar 2005)

Competence in Physicskey to your successLimiting the topic a bit...

... Fickian and near-Fickian diffusionof molecules and/or energy

Page 4: Diffusion challenges in (chemical) industries

GKP 000-0000 (4) (Januar 2005)

Competence in Physicskey to your successOutline

• Scaling behaviour of diffusion effects

• Diffusion as a challenge:• Diffusion of heat • Diffusion of reactants • Diffusion in multicomponent materials and finished goods

• Diffusion as a friend: controlled release

• Going micro and nano: approaching the apparent dwarf

Page 5: Diffusion challenges in (chemical) industries

GKP 000-0000 (5) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsMacroworld experience:Diffusion is slow.

Typical example:a real Saxonian„Semester-uhr“(„term clock“)

Page 6: Diffusion challenges in (chemical) industries

GKP 000-0000 (6) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsMacroworld experience:Diffusion is slow.

Typical example:a real Saxonian„Semester-uhr“(„term clock“)

Nevertheless:sufficient changeto observe during first hour of the experiment.

Page 7: Diffusion challenges in (chemical) industries

GKP 000-0000 (7) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsMacroworld experience:Diffusion is slow.

Typical example:a real Saxonian„Semester-uhr“(„term clock“)

Nevertheless:sufficient changeto observe during first hour of the experiment.

Non-linear time behaviour of diffusion

... taking a closer look at the short-time behaviour...

Page 8: Diffusion challenges in (chemical) industries

GKP 000-0000 (8) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsDissolution of coloured ions: KMnO4 and eosin

Page 9: Diffusion challenges in (chemical) industries

GKP 000-0000 (9) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsDissolution of coloured ions: KMnO4 and eosin

KMnO4

Page 10: Diffusion challenges in (chemical) industries

GKP 000-0000 (10) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsDissolution of coloured ions: KMnO4 and eosin

Dominating effect: density-driven flow

KMnO4

Page 11: Diffusion challenges in (chemical) industries

GKP 000-0000 (11) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsDissolution of coloured ions: KMnO4 and eosin

Dominating effect: Suppression of convection density-driven flow by xanthan

KMnO4

Water

Xanthan gum, 0,5 % w/vdissolved in water(no major effect on diffusion)

Page 12: Diffusion challenges in (chemical) industries

GKP 000-0000 (12) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsDissolution of coloured ions: KMnO4 and eosin

Dominating effect: Suppression of convection density-driven flow by xanthan

KMnO4

Page 13: Diffusion challenges in (chemical) industries

GKP 000-0000 (13) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsDissolution of coloured ions: KMnO4 and eosin

Dominating effect: Suppression of convection density-driven flow by xanthan

KMnO4

Convection cells,„interference“

Page 14: Diffusion challenges in (chemical) industries

GKP 000-0000 (14) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsDissolution of coloured ions: KMnO4 and eosin

Dominating effect: Suppression of convection density-driven flow by xanthan

KMnO4

Page 15: Diffusion challenges in (chemical) industries

GKP 000-0000 (15) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsDissolution of coloured ions: KMnO4 and eosin

Dominating effect: Suppression of convection density-driven flow by xanthan

KMnO4

Diffuse concentration profiles, no „interference“

Page 16: Diffusion challenges in (chemical) industries

GKP 000-0000 (16) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsDissolution of coloured ions: KMnO4 and eosin

Dominating effect: Suppression of convection density-driven flow by xanthan

KMnO4

Diffuse concentration profiles, no „interference“

Seemingly constantsupply of dissolvedKMnO4

Propagationof eosin slows down withtime

Page 17: Diffusion challenges in (chemical) industries

GKP 000-0000 (17) (Januar 2005)

Competence in Physicskey to your success

Diffusion: really slow?

Scaling behaviour ofdiffusion effects

Dissolution of coloured ions: KMnO4 and eosin

Diffusion through thin stagnant layer at crystal- water interface allows fast mass transport into region of convective flow.

Fast convection on macroscaleis fed by fast diffusion on micro-scale.

Diffusion limited interface layer

Page 18: Diffusion challenges in (chemical) industries

GKP 000-0000 (18) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effects

T1 T2

T1 T2

c1 c2

c1 c2

j Q=−T 1−T 2

l

jQ=−dTdx

l l

Fick's first law Fourier's law Fouriersches Gesetz

j D=−Dc1−c2

l

jD=−D dcdx

„Large“ reservoirs

Stationary profile of c or T in wall

Diffusive current throughwall:

Page 19: Diffusion challenges in (chemical) industries

GKP 000-0000 (19) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effects

T1 T2

T1 T2

c1 c2

c1 c2

j Q=−T 1−T 2

l

jQ=−dTdx

l l

Fick's first law Fourier's law Fouriersches Gesetz

j D=−Dc1−c2

l

jD=−D dcdx

„Large“ reservoirs

Stationary profile of c or T in wall

Diffusive current throughwall:

Everything still seems linear ...

... however: What happens for instationary situations?

Page 20: Diffusion challenges in (chemical) industries

GKP 000-0000 (20) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsExample: instationary heat diffusion:Heat current produces change in inner energy, i.e. heating of volumeelement:

dU = jQx− jQxdx Adt

dU =Cdm dTdt

dt=C dV dTdt

dt=C Adx dTdt

dt

Page 21: Diffusion challenges in (chemical) industries

GKP 000-0000 (21) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsExample: instationary heat diffusion:Heat current produces change in inner energy, i.e. heating of volumeelement:

Comparing the expressions leads to

dU = jQx− jQxdx Adt

dU =Cdm dTdt

dt=C dV dTdt

dt=C Adx dTdt

dt

C Adx dTdt

dt= jQx− jQxdx Adt

C dTdt

dx= jQx − jQ xdx =−djQ x

Page 22: Diffusion challenges in (chemical) industries

GKP 000-0000 (22) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsExample: instationary heat diffusion:Heat current produces change in inner energy, i.e. heating of volumeelement:

Comparing the expressions leads to

dU = jQx− jQxdx Adt

dU =Cdm dTdt

dt=C dV dTdt

dt=C Adx dTdt

dt

C Adx dTdt

dt= jQx− jQxdx Adt

C dTdt

dx= jQx − jQ xdx =−djQ x

C dTdt

=−djQ x

dx= d 2 T

dx2

Fick's second law of heat diffusion

jQ=−dTdx

Page 23: Diffusion challenges in (chemical) industries

GKP 000-0000 (23) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsExample: instationary heat diffusion:Heat current produces change in inner energy, i.e. heating of volumeelement:

Comparing the expressions leads to

dU = jQx− jQxdx Adt

dU =Cdm dTdt

dt=C dV dTdt

dt=C Adx dTdt

dt

C Adx dTdt

dt= jQx− jQxdx Adt

C dTdt

dx= jQx − jQ xdx =−djQ x

C dTdt

=−djQ x

dx= d 2 T

dx2

Fick's second law of heat diffusion

jQ=−dTdx

dcdt=D d 2 c

dx2

Fick's second law of (matter) diffusion

Page 24: Diffusion challenges in (chemical) industries

GKP 000-0000 (24) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsSolution of diffusion equation for δ−shaped disturbance (1D):

c x , t =Co

2Dtexp−x2

4Dt Mean diffusive shift:

sD ,1 D= x2=2Dt

Page 25: Diffusion challenges in (chemical) industries

GKP 000-0000 (25) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsSolution of diffusion equation for δ−shaped disturbance (1D):

into a 3D medium

c x , t =Co

2Dtexp−x2

4Dt Mean diffusive shift:

sD ,1 D= x2=2Dt

Page 26: Diffusion challenges in (chemical) industries

GKP 000-0000 (26) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsSolution of diffusion equation for δ−shaped disturbance (1D):

Diffusion from a line source

into a 3D medium

c x , t =Co

2Dtexp−x2

4Dt Mean diffusive shift:

sD ,1 D= x2=2Dt

c x , t =M o

4Dtexp−x2

4Dt

Page 27: Diffusion challenges in (chemical) industries

GKP 000-0000 (27) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsSolution of diffusion equation for δ−shaped disturbance (1D):

Diffusion from a line source

or a point source

into a 3D medium

c x , t =Co

2Dtexp−x2

4Dt Mean diffusive shift:

sD ,1 D= x2=2Dt

c x , t =M o

8Dt 3exp−x2

4Dt

c x , t =M o

4Dtexp−x2

4Dt

Page 28: Diffusion challenges in (chemical) industries

GKP 000-0000 (28) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effectsSolution of diffusion equation for δ−shaped disturbance (1D):

Diffusion from a line source

or a point source

into a 3D medium

c x , t =Co

2Dtexp−x2

4Dt Mean diffusive shift:

sD ,1 D= x2=2Dt

c x , t =M o

8Dt 3exp−x2

4Dt

c x , t =M o

4Dtexp−x2

4Dt

Different normalizationfactors due to geometry:Faster depletion of con-centration in center dueto growing volume elements for cyclindricaland spherical geometry.

Page 29: Diffusion challenges in (chemical) industries

GKP 000-0000 (29) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effects

l l

dTdt

=

C d 2Tdx2 = d 2T

dx2=

C Heat diffusion coefficient

More realistic scenarioes: semiinfinite media and finite sheets

Page 30: Diffusion challenges in (chemical) industries

GKP 000-0000 (30) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effects

l l

dTdt

=

C d 2Tdx2 = d 2T

dx2=

C Heat diffusion coefficient

More realistic scenarioes: semiinfinite media and finite sheets

T x , t =12

T o erfc x2 t

T(x,0) T(x,t)

Page 31: Diffusion challenges in (chemical) industries

GKP 000-0000 (31) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effects

l l

dTdt

=

C d 2Tdx2 = d 2T

dx2=

C Heat diffusion coefficient

More realistic scenarioes: semiinfinite media and finite sheets

T(x,0) T(x,t) T x , t =12

T o erfc x2 t

T(x,0) T(x,t) T x , t =12

T o[erf h− x2 t

−erf hx2 t

]

-h h

Page 32: Diffusion challenges in (chemical) industries

GKP 000-0000 (32) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effects

l l

dTdt

=

C d 2Tdx2 = d 2T

dx2=

C

l∝ tHeat diffusion coefficient

More realistic scenarioes: semiinfinite media and finite sheets

T(x,0) T(x,t)

T(x,0) T(x,t)

-h h

Relevant charac- teristic lenght scale for all diffusion processes

T x , t =12

T o erfc x2 t

T x , t =12

T o[erf h− x2 t

−erf hx2 t

]

Page 33: Diffusion challenges in (chemical) industries

GKP 000-0000 (33) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effects„Velocity“ of diffusive transport processes:

Inversely proportional to diffusion length!

v D=sD

t s=

sD

sD2

2D

=2DsD

Page 34: Diffusion challenges in (chemical) industries

GKP 000-0000 (34) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effects„Velocity“ of diffusive transport processes:

Inversely proportional to diffusion length!

Ratio of diffusive velocity to characteristic velocity in system:

Péclet number

v D=sD

t s=

sD

sD2

2D

=2DsD

Pe=LChar vChar

D

vChar

vD=

sD vChar

2D

Page 35: Diffusion challenges in (chemical) industries

GKP 000-0000 (35) (Januar 2005)

Competence in Physicskey to your successScaling behaviour of

diffusion effects„Velocity“ of diffusive transport processes:

Inversely proportional to diffusion length!

Ratio of diffusive velocity to characteristic velocity in system:

Péclet number

axial and radial

v D=sD

t s=

sD

sD2

2D

=2DsD

Pe=LChar vChar

D

vChar

vD=

sD vChar

2D

Page 36: Diffusion challenges in (chemical) industries

GKP 000-0000 (36) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge:

HeatHeating extended objects

e.g. baking

Chapatialmost homogeneousbaking time < 1min

European-style breadobviously inhomogeneousbaking time> 1 h

Page 37: Diffusion challenges in (chemical) industries

GKP 000-0000 (37) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge:

HeatHeating extended objects

e.g. baking

Chapatialmost homogeneousbaking time < 1min

European-style breadobviously inhomogeneousbaking time> 1 h

Heating up extended objects: intrinsically slow(time- and energy consuming)

Speeding up:•Increased temperature gradient •Optimized heat transfer (convection)

•Better alternative: avoid (i.e. reduce object size)

Benefits of slow heat transfer:•No thermal damage to interior in short high-temperature treatment of outer surfaces (e.g. „Baked Alaska“)

Page 38: Diffusion challenges in (chemical) industries

GKP 000-0000 (38) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge:

HeatSelf-heating systems

Page 39: Diffusion challenges in (chemical) industries

GKP 000-0000 (39) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge:

HeatSelf-heating systems •Substantially higher temperatures

in extended objects (e.g. over 80 °C in massive concrete structures vs. almost neglegible heating in slender structures)

Page 40: Diffusion challenges in (chemical) industries

GKP 000-0000 (40) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge:

HeatSelf-heating systems •Substantially higher temperatures

in extended objects (e.g. over 80 °C in massive concrete structures vs. almost neglegible heating in slender structures)

•Especially problematic for reactions with positive temperature coefficient

•Major danger in scale-up of reactions (power excursions!)•Countermeasures: keep S/V constant, increase stirring to achieve better heat exchange, active cooling

Page 41: Diffusion challenges in (chemical) industries

GKP 000-0000 (41) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge:

HeatHeat-diffusion in buildings

Nordic Alpine Similar static heat conduction through walls

Low heat capacity High heat capacity

Page 42: Diffusion challenges in (chemical) industries

GKP 000-0000 (42) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge:

HeatC

alde

rone

Gla

cier

@ G

ran

Sas

so25

/08/

07

Page 43: Diffusion challenges in (chemical) industries

GKP 000-0000 (43) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

reactants

Traditional tanks and reactors:

Large Péclet numbers

Exceptions: •Heat exchangers•Intraparticle processes

Page 44: Diffusion challenges in (chemical) industries

GKP 000-0000 (44) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

reactants

Traditional tanks and reactors:

Large Péclet numbers Active mixing processes needed•In low viscosity systems: induce turbulence

•Shorter length scales for diffusive mixing•Smaller Pe

Page 45: Diffusion challenges in (chemical) industries

GKP 000-0000 (45) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

reactants

Traditional tanks and reactors:

Large Péclet numbers

Exceptions: •Heat exchangers•Intraparticle processes

Active mixing processes needed•In low viscosity systems: induce turbulence

•Shorter length scales for diffusive mixing•Smaller Pe

•High viscosity systems•Thorough mixing increasingly difficult•Typically lower D, too

Page 46: Diffusion challenges in (chemical) industries

GKP 000-0000 (46) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

reactantsPolymerization reactions: especially strong increase in viscositydue to entanglement effects.

•Degree of polymerization•Polymer concentration (solution processes) yield!•Branching and crosslinks

Page 47: Diffusion challenges in (chemical) industries

GKP 000-0000 (47) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

reactantsPolymerization reactions: especially strong increase in viscositydue to entanglement effects.

•Degree of polymerization•Polymer concentration (solution processes) yield!•Branching and crosslinks

•Residual monomers•Plasticizers

Page 48: Diffusion challenges in (chemical) industries

GKP 000-0000 (48) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

reactantsPolymerization reactions: especially strong increase in viscositydue to entanglement effects.

•Degree of polymerization•Polymer concentration (solution processes) yield!•Branching and crosslinks

•Temperature heating energy! decomposition!•Residual monomers•Plasticizers

Page 49: Diffusion challenges in (chemical) industries

GKP 000-0000 (49) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

reactantsPolymerization reactions: especially strong increase in viscositydue to entanglement effects.

•Degree of polymerization•Polymer concentration (solution processes) yield!•Branching and crosslinks

•Temperature heating energy! decomposition!•Residual monomers•Plasticizers

More polymer dynamicstomorrow: Talks Richterand Sarti

Page 50: Diffusion challenges in (chemical) industries

GKP 000-0000 (50) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

reactantsAlternative approach to polymerizations: emulsion polymerization

•Especially attractive for production of cross-linked polymers•Diffusive transport only at length scale of droplets or micelles•Low-viscosity convection in conti- nous liquid phase

Page 51: Diffusion challenges in (chemical) industries

GKP 000-0000 (51) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

reactantsAlternative approach to polymerizations: emulsion polymerization

•Especially attractive for production of cross-linked polymers•Diffusive transport only at length scale of droplets or micelles•Low-viscosity convection in conti- nous liquid phase

•Different modes of operation depending on distribution of monomers and starters•Surfactant material needed•Most typical case: oil-in water emulsions•Monodisperse particles from ordered micellar phases

Page 52: Diffusion challenges in (chemical) industries

GKP 000-0000 (52) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

reactantsCement hydration:Dissolution of suspended clinker grains Repreciptation of CSH phases

Dissolution of unreactedcement clinker increasinglyimpeded by CSH diffusion barrier

•Delayed hydration •poor use of clinker

Page 53: Diffusion challenges in (chemical) industries

GKP 000-0000 (53) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

reactantsCement hydration:Dissolution of suspended clinker grains Repreciptation of CSH phases

Dissolution of unreactedcement clinker increasinglyimpeded by CSH diffusion barrier

•Delayed hydration •poor use of clinker

Poster C03 Bordallo et al. :water in CSH phases

Page 54: Diffusion challenges in (chemical) industries

GKP 000-0000 (54) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

reactants

0

50

100

150

0 10 20 30 40thyd [h]

1/T 1

[1/s

]

native10 % MCC10 % PTFE powder10 % carbon black

Enhanced hydration in the presence of microfillers

Cement hydration kinetics studied by TD-NMR1/T1 essentially proportional to S/V inside cement stone matrix

Inert microfillers

Page 55: Diffusion challenges in (chemical) industries

GKP 000-0000 (55) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

reactants

0

50

100

150

0 10 20 30 40thyd [h]

1/T 1

[1/s

]

native10 % MCC10 % PTFE powder10 % carbon black

Enhanced hydration in the presence of microfillers

Cement hydration kinetics studied by TD-NMR1/T1 essentially proportional to S/V inside cement stone matrix

0

50

100

150

200

250

0 5 10 15 20 25 30 35thyd [h]

1/T 1

[1/s

]

nativAnatas µRutil µAnatas P25

TiO2

Page 56: Diffusion challenges in (chemical) industries

GKP 000-0000 (56) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

reactants

0

50

100

150

0 10 20 30 40thyd [h]

1/T 1

[1/s

]

native10 % MCC10 % PTFE powder10 % carbon black

Enhanced hydration in the presence of microfillers

Cement hydration kinetics studied by TD-NMR1/T1 essentially proportional to S/V inside cement stone matrix

0

50

100

150

200

250

0 5 10 15 20 25 30 35thyd [h]

1/T 1

[1/s

]

nativAnatas µRutil µAnatas P25

TiO2

Accelerated hydration desirable for enabling faster construction.

Favourable permeability propertiesdue to denser pore system.

Page 57: Diffusion challenges in (chemical) industries

GKP 000-0000 (57) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

composite products

Polymer 1 w/o plasticizer

Polymer 2 w plasticizer

T

Page 58: Diffusion challenges in (chemical) industries

GKP 000-0000 (58) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

composite products

Polymer 1 w/o plasticizer

Polymer 2 w plasticizer

T

Possible adverseeffects of plasticizer

Page 59: Diffusion challenges in (chemical) industries

GKP 000-0000 (59) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

composite products

Polymer 1 w/o plasticizer

Polymer 2 w plasticizer

T

Degradadion due to loss of pasticizer

Possible adverseeffects of plasticizer

Page 60: Diffusion challenges in (chemical) industries

GKP 000-0000 (60) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

composite products

Polymer 1 w/o plasticizer

Polymer 2 w plasticizer

T

Degradadion due to loss of pasticizer

Possible adverseeffects of plasticizer

Risk of delamination

Page 61: Diffusion challenges in (chemical) industries

GKP 000-0000 (61) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

composite products

Polymer 1 w/o plasticizer

Polymer 2 w plasticizer

T

Degradadion due to loss of pasticizer

Possible adverseeffects of plasticizer

Parameters affecting diffusion effects in composite materials

•Distribution coefficient between two layers•Miscibility (possibly temperature effects)•Diffusion coefficient

Measures against diffusion•Reduction of diffusion coefficient •Introduction of barriers

Page 62: Diffusion challenges in (chemical) industries

GKP 000-0000 (62) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

composite products

Polymer 1 w/o plasticizer

Polymer 2 w plasticizer

T

Degradadion due to loss of pasticizer

Possible adverseeffects of plasticizer

Risk of delamination

Parameters affecting diffusion effects in composite materials

•Distribution coefficient between two layers•Miscibility (possibly temperature effects)•Diffusion coefficient

Measures against diffusion•Reduction of diffusion coefficient •Introduction of barriers

Polymer 1 w/o plasticizer

Polymer 2 w plasticizer

Page 63: Diffusion challenges in (chemical) industries

GKP 000-0000 (63) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

food•Natural diffusion barriers

•Outer skins: essential self-protection systems of organisms against loss of moisture and oxydation

Fresh

Page 64: Diffusion challenges in (chemical) industries

GKP 000-0000 (64) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

food•Natural diffusion barriers

•Outer skins: essential self-protection systems of organisms against loss of moisture and oxydation

Fresh

5 days later

Shelf-life

Page 65: Diffusion challenges in (chemical) industries

GKP 000-0000 (65) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

food•Natural diffusion barriers

•Outer skins: essential self-protection systems of organisms against loss of moisture and oxydation•Internal barriers: helping to maintain local concentration gradients

Shelf-life

Page 66: Diffusion challenges in (chemical) industries

GKP 000-0000 (66) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

food•Natural diffusion barriers

•Outer skins: essential self-protection systems of organisms against loss of moisture and oxydation•Internal barriers: helping to maintain local concentration gradients

•Inside „homogeneous“ tissues:•Almost free diffusion (water and/or vapour phase) in extracellular media•Possibly even faster transport pathways due to capillary effects•Barrier action of cell walls much weaker than outer barriers

Shelf-life

Page 67: Diffusion challenges in (chemical) industries

GKP 000-0000 (67) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

food•Natural diffusion barriers

•Outer skins: essential self-protection systems of organisms against loss of moisture and oxydation•Internal barriers: helping to maintain local concentration gradients

•Inside „homogeneous“ tissues:•Almost free diffusion (water and/or vapour phase) in extracellular media•Possibly even faster transport pathways due to capillary effects•Barrier action of cell walls much weaker than outer barriers

Shelf-life

Drying

Page 68: Diffusion challenges in (chemical) industries

GKP 000-0000 (68) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

foodProcessing and spicing

marinated and pickledfoods

•In absence of outer barriers: 1 cm/day•Whole fruit with intact skin (e.g. olives): months

•Natural diffusion barriers•Outer skins: essential self-protection systems of organisms against loss of moisture and oxydation•Internal barriers: helping to maintain local concentration gradients

•Inside „homogeneous“ tissues:•Almost free diffusion (water and/or vapour phase) in extracellular media•Possibly even faster transport pathways due to capillary effects•Barrier action of cell walls much weaker than outer barriers

Page 69: Diffusion challenges in (chemical) industries

GKP 000-0000 (69) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

foodProcessing and spicing

marinated and pickledfoods

•In absence of outer barriers: 1 cm/day•Whole fruit with intact skin (e.g. olives): months

Mechanical or osmotic disruption of barriers before frying

•Natural diffusion barriers•Outer skins: essential self-protection systems of organisms against loss of moisture and oxydation•Internal barriers: helping to maintain local concentration gradients

•Inside „homogeneous“ tissues:•Almost free diffusion (water and/or vapour phase) in extracellular media•Possibly even faster transport pathways due to capillary effects•Barrier action of cell walls much weaker than outer barriers

Page 70: Diffusion challenges in (chemical) industries

GKP 000-0000 (70) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

food composites(Organic) chocolate aftera few weeks with occasionalheating episodes up to 30 °C (i.e. in a kitchen without airconditioning)

Macroscale demixing of solid and liquid fat components and diffusion to the surface

Similar effect in a Bacio with internal (macroscopic) fat-fat interfaces

Page 71: Diffusion challenges in (chemical) industries

GKP 000-0000 (71) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

food composites(Organic) chocolate aftera few weeks with occasionalheating episodes up to 30 °C (i.e. in a kitchen without airconditioning)

Macroscale demixing of solid and liquid fat components and diffusion to the surface

Similar effect in a Bacio with internal (macroscopic) fat-fat interfaces

Not just limited to food:

Similar high-temperature effects in steel.

Posters B1, B2 Evteev et al.

Page 72: Diffusion challenges in (chemical) industries

GKP 000-0000 (72) (Januar 2005)

Competence in Physicskey to your successDiffusion as a challenge

food compositesA sweets manu-facturers' crunchy trick to control diffusive transport between different fat phases

Insert a hydrophiliccracknelcapillary barrier between the two fatty layers

Page 73: Diffusion challenges in (chemical) industries

GKP 000-0000 (73) (Januar 2005)

Competence in Physicskey to your successDiffusion as a friend:

controlled release

Active agent

Substrate Target

Page 74: Diffusion challenges in (chemical) industries

GKP 000-0000 (74) (Januar 2005)

Competence in Physicskey to your successDiffusion as a friend:

controlled release

Active agent dissolved in high concentration•Concentration difficult to maintain (e.g. washout, degradation)•Side effects

Substrate Target

Page 75: Diffusion challenges in (chemical) industries

GKP 000-0000 (75) (Januar 2005)

Competence in Physicskey to your successDiffusion as a friend:

controlled release

Active agent dissolved in low concentration•Concentration difficult to maintain (e.g. washout, degradation)•Less side effects

Substrate Target

Page 76: Diffusion challenges in (chemical) industries

GKP 000-0000 (76) (Januar 2005)

Competence in Physicskey to your successDiffusion as a friend:

controlled release

Constant supply of agent for dissolution:•Desired effect: maintainance of a low and effectiveagent concentration for a long time

Substrate Target

Page 77: Diffusion challenges in (chemical) industries

GKP 000-0000 (77) (Januar 2005)

Competence in Physicskey to your successDiffusion as a friend:

controlled release

Constant supply of agent for dissolution:•Desired effect: maintainance of a low and effectiveagent concentration for a long time

Substrate Target

Page 78: Diffusion challenges in (chemical) industries

GKP 000-0000 (78) (Januar 2005)

Competence in Physicskey to your successDiffusion as a friend:

controlled release

Constant supply of agent for dissolution:•Desired effect: maintainance of a low and effectiveagent concentration for a long time

Substrate Target

Page 79: Diffusion challenges in (chemical) industries

GKP 000-0000 (79) (Januar 2005)

Competence in Physicskey to your successDiffusion as a friend:

controlled release

Constant supply of agent for dissolution:•Desired effect: maintainance of a low and effectiveagent concentration for a long time

Substrate Target

Remainingchallenges:•Time profile of release•Delayed onset of action•Combination of several agents

Page 80: Diffusion challenges in (chemical) industries

GKP 000-0000 (80) (Januar 2005)

Competence in Physicskey to your successDiffusion as a friend:

controlled release

Constant supply of agent for dissolution:•Desired effect: maintainance of a low and effectiveagent concentration for a long time

Substrate Target

Remainingchallenges:•Time profile of release•Delayed onset of action•Combination of several agents

Related topic:poster D3Pilar et al.

Page 81: Diffusion challenges in (chemical) industries

GKP 000-0000 (81) (Januar 2005)

Competence in Physicskey to your successGoing micro and nano:

approaching the apparent dwarf

10 mm

Washing out a blue colourtracer (C.I. Basic Violet 3) from a circular flat cell

Page 82: Diffusion challenges in (chemical) industries

GKP 000-0000 (82) (Januar 2005)

Competence in Physicskey to your successGoing micro and nano:

approaching the apparent dwarf

10 mm

Washing out a blue colourtracer (C.I. Basic Violet 3) from a circular flat cell

•Context: Interplay between diffusion and relaxation in thin excited slices (A. Gädke and N.N., Diffusion Fundamentals 3 38.1-38.12)

Page 83: Diffusion challenges in (chemical) industries

GKP 000-0000 (83) (Januar 2005)

Competence in Physicskey to your successGoing micro and nano:

approaching the apparent dwarf

10 mm

After 4.5 s of 10 ml/minwater flow.

Page 84: Diffusion challenges in (chemical) industries

GKP 000-0000 (84) (Januar 2005)

Competence in Physicskey to your successGoing micro and nano:

approaching the apparent dwarf

10 mm

After 4.5 s of 10 ml/minwater flow.

Almost no notabledecolouring of feedline

Page 85: Diffusion challenges in (chemical) industries

GKP 000-0000 (85) (Januar 2005)

Competence in Physicskey to your successGoing micro and nano:

approaching the apparent dwarf

10 mm

After 9 s of 10 ml/minwater flow.

Page 86: Diffusion challenges in (chemical) industries

GKP 000-0000 (86) (Januar 2005)

Competence in Physicskey to your successGoing micro and nano:

approaching the apparent dwarf

10 mm

After 13.5 s of 10 ml/minwater flow.

Page 87: Diffusion challenges in (chemical) industries

GKP 000-0000 (87) (Januar 2005)

Competence in Physicskey to your successGoing micro and nano:

approaching the apparent dwarf

10 mm

After 18 s of 10 ml/minwater flow.

Almost complete decolouringof feed line

Page 88: Diffusion challenges in (chemical) industries

GKP 000-0000 (88) (Januar 2005)

Competence in Physicskey to your successGoing micro and nano:

approaching the apparent dwarf

10 mm

After 22.5 s of 10 ml/minwater flow.

Page 89: Diffusion challenges in (chemical) industries

GKP 000-0000 (89) (Januar 2005)

Competence in Physicskey to your successGoing micro and nano:

approaching the apparent dwarf

10 mm

After 27 s of 10 ml/minwater flow.

Page 90: Diffusion challenges in (chemical) industries

GKP 000-0000 (90) (Januar 2005)

Competence in Physicskey to your successGoing micro and nano:

approaching the apparent dwarf

10 mm

After 31.5 s of 10 ml/minwater flow.

Page 91: Diffusion challenges in (chemical) industries

GKP 000-0000 (91) (Januar 2005)

Competence in Physicskey to your successGoing micro and nano:

approaching the apparent dwarf

10 mm

After 36 s of 10 ml/minwater flow.

Page 92: Diffusion challenges in (chemical) industries

GKP 000-0000 (92) (Januar 2005)

Competence in Physicskey to your successGoing micro and nano:

approaching the apparent dwarf

10 mm

After 40.5 s of 10 ml/minwater flow.

Page 93: Diffusion challenges in (chemical) industries

GKP 000-0000 (93) (Januar 2005)

Competence in Physicskey to your successGoing micro and nano:

approaching the apparent dwarf

10 mm

After 45 s of 10 ml/minwater flow.

Almost no wash-out in region outside of convection pathwaysneeds further flooding for severalminutes until substantial washoutoccurs.

Page 94: Diffusion challenges in (chemical) industries

GKP 000-0000 (94) (Januar 2005)

Competence in Physicskey to your successGoing micro and nano:

approaching the apparent dwarf

10 mm

After 45 s of 10 ml/minwater flow.

Almost no wash-out in region outside of convection pathwaysneeds further flooding for severalminutes until substantial washoutoccurs.

•Is continous flooding really necessary?

•Saving solvent•More sustainable process?

•Help by diffusion?

Page 95: Diffusion challenges in (chemical) industries

GKP 000-0000 (95) (Januar 2005)

Competence in Physicskey to your successGoing micro and nano:

approaching the apparent dwarf

10 mm

After waiting 3 min

Diffusive broadening of remaining(C.I. Basic Violet 3)

Page 96: Diffusion challenges in (chemical) industries

GKP 000-0000 (96) (Januar 2005)

Competence in Physicskey to your successGoing micro and nano:

approaching the apparent dwarf

10 mm

After 15 s of subsequent flooding

Page 97: Diffusion challenges in (chemical) industries

GKP 000-0000 (97) (Januar 2005)

Competence in Physicskey to your successGoing micro and nano:

approaching the apparent dwarf

Example shows: clever division of work between flow and diffusion helps saving resources

•Heterogeneous catalysis•Adsorption and ion exchange (Posters C4, C8,...)

•Environmental remediation (Talk Barker, Poster F4)

•Chromatography (Poster C11)•Lab on a chip

•Living organisms (Posters D6, D7)

Page 98: Diffusion challenges in (chemical) industries

Ringrazio tanto!Stefano BrandaniJörg KärgerRoberto VolpeChristian ChmelikAnna Cicolani

Walter Heckmann

Achim Gädke