biofoambark bark valorization into insulating foams and ......net project woodwisdom-net 2. the...

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BIOFOAMBARKBark Valorization into Insulating Foams and Bioenergy

Curing Kinetics of Spruce Bark Tannin-Based Foams

Milan Šernek&

Matjaž Čop, Graduate student

University of Ljubljana, Slovenia

SWST 2014 International Convention

Technical University in Zvolen, Slovakia

June 23-27, 2014

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BIOFOAMBARK – Research Collaboration

2

WP4: TECHNOLOGY OF TANNIN FOAMS (U. Ljubljana, Šernek)

WP

2: IN

VE

NT

OR

Y &

S

UP

PLY

CH

AIN

(U

. Fre

ibur

g, B

ecke

r)

WP6: CONVERSION IN SYNGAS (Fraunhofer Inst., Aicher) WP

5: S

US

TA

IN

AB

IL

IT

Y

(U. S

anti

ago,

Mo

reir

a)

WP

1: P

RO

JE

CT

M

AN

AG

EM

EN

T (U

. Fre

ibur

g, L

abor

ie) WP3: TANNIN EXTRACTION (VTT, Mikkonen)

Design of tannin

foams / including nanocellulosemodification

Kinetic modeling of

tannin foam formation

Characterization of tannin

foam chemistry, morphology & performance as insulating

material

U. Freiburg and U. Nancy I

U. Ljubljana

Establishment of Structure

/Processing /Performancerelationships

Freiburg and U. Nancy I U. Ljubljana

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Spruce Bark Tannin-Based Foams

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The objectives

1. To assess the impact of tannin-based foam

formulation on its cure kinetics using AMFK

2. To study the influence of the content of the

catalyst, glycerol, and tannin in the foam

formulations on the kinetics

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Materials

NAME Furfuryl alcohol (g) Glycerol (g) Tannin (g) Catalyst – pTSA (g) Set of measurements

5:2:5:3 5 2 5 3 Reference

5:0:5:3 5 0 5 3

Variation of the glycerol5:1:5:3 5 1 5 3

5:3:5:3 5 3 5 3

5:2:3:3 5 2 3 3

Variation of the tannin5:2:4:3 5 2 4 3

5:2:6:3 5 2 6 3

5:2:5:2 5 2 5 2

Variation of the catalyst5:2:5:4 5 2 5 4

5:2:5:5 5 2 5 5

Tannin-based foams are networked structures that are obtained by polycondensation of polyflavonoid

tannins and furfuryl alcohol

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Differential scanning calorimetry (DSC)

p = 20 bar

Different temperature programs (combination of dynamic and isothermal), with heating rates similar to real conditions found during the formation of foam.

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Temperature programs / AMFK procedure

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DSC thermograms

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Curing Kinetics

tot

t

H

H

dt

dH

Hdt

d t

tot

1

)()(

fTkdt

d

RT

EATk exp)(

dttRT

EtTEJ

i

a

t

t

ia

)(

exp)(,

Vir: Vyazovkin, 2008

This algorithm is integrated using the Mettler Toledo STAR V10.0 software, with the function “Advanced Model Free Kinetics (AMFK)”

111

)(ln)(ln)/ln(

T

f

T

Tk

T

dtd

R

E

T

dtd a

1

)/ln(

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Heat of reaction during isothermal DSC

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Activation energy vs. Conversion

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Prediction of conversion by AMFK

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Prediction of conversion by AMFK

• Depending on the amount of glycerol

• Two isothermal temperatures (50 °C & 80 °C)

Type of composition

5:0:5:3 5:1:5:3 5:2:5:3 5:3:5:3

50 °C 80 °C 50 °C 80 °C 50 °C 80 °C 50 °C 80 °C

Co

nve

rsio

n

0.10 15.0 1.7 18.0 1.5 26.4 2.8 33.0 3.8

0.20 27.6 3.2 36.0 3.9 48.6 6.6 59.4 9.6

0.30 41.4 5.8 52.2 7.8 71.4 10.2 86.4 15.0

0.40 54.6 9.0 70.2 12.6 100.2 14.4 120.6 21.0

0.50 70.8 13.2 94.2 17.4 139.2 19.8 165.6 28.8

0.60 94.8 17.4 127.8 24.6 195.6 28.2 232.2 40.2

0.70 132.0 24.6 177.6 35.4 282.0 43.2 345.0 60.6

0.80 196.8 40.2 269.4 57.0 440.4 76.8 576.6 103.8

0.90 337.2 85.8 498.0 114.6 819.6 195.6 1205.4 236.4

0.99 883.8 287.4 1533.6 391.2 2411.4 723.6 4341.6 958.8

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Conclusions

1. It was demonstrated for the first time that the cure kinetics of tannin foams can be monitored by differential scanning calorimetry (DSC) and modelled using the Vyazovkin advanced isoconversional method.

2. The results show that the curing process is delayed when the proportion of glycerol or tannin in the mixture is increased. However, for the catalyst, it was observed that an optimum amount exists.

3. The optimal proportion of the components used depends on the temperature conditions.

Čop et al. (2014). “Curing spruce tannin-based foams,” BioResources 9(3), 4643-4655

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Current Research Work: Foam Rheology

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Current Research Work: Foam Morphology

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Current Research Work: Compression Strength

0 20 40 60 80

0.0

0.5

1.0

1.5

2.0

Deformation in %

Str

ess in M

Pa

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Future plans

• To finalize work on AMFK

• Thermal conductivity

• Resistance against fire

• Resistance against fungi

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Acknowledgement

The study was funded by the WoodWisdom-ERA Net Research Program, which is a trans-national R&D program jointly funded by national funding organisations within the framework of the ERA-

NET project WoodWisdom-Net 2.

The research was also funded by the Slovenian Ministry of Education, Science, and Sport.

Thank you for your attention!