Progress in Regenerated

Cellulose Fiber Production

Workshop on Cellulose Dissolution and regeneration,
Göteborg, December 3rd, 2013
Herbert Sixta
Department of Forest Products Technology, Aalto University, Finland.
 Research team

AALTO University Helsinki University

Senior scientist: Professor
– Dr. Michael Hummel – Ilkka Kilpelainen
PhD students: Senior scientist:
– Lauru Hauru – Dr. Alistair King
– Anne Michud PhD students:
– Shirin Asaadi – Arno Parviainen
Textile design – Ashley Holding
– Marjaana Tanttu – Tia Kakko
 Outline
Background
Regenerated Cellulose
Processes
Cellulose dissolution and
regeneration
Spinning at AALTO

Structure Formation

Composites
 Market of Cellulose Products
Global textile market
10 MMC staple fiber, Mio t/a - Cotton stagnant at 26-28 Mio t/a
- High cotton prices
8 9% - 33-37% minimum share of
cellulosics in textiles
6 - GAP of 15 Mio t/a of cellulosic
fibers in 2030
4
6%
Growth rates
2
- Viscose, Lyocell > 9%/a
- Acetate 1.5%/a
0
1940 1960 1980 2000 2020

The Fiber Year 2013: World Survey on Textiles`& Nonwovens, April 2013
 Textile Fibers Overview

FIBERS

Man-made fibers
Natural fibers
From natural Synthetic Inorganic
polymers polymers compounds

Protein- Cellulose Cellulose

based Protein- Polyester
based based (MMC) based Polyamide
Carbon
Elastan
Wool Cotton Viscose Ceramics
Casein PP
Silk Flax Modal Glass
Collagen PU
Angora Jute Lyocell Metal
Ardein Acryl
Cashmere Hemp Cupro
Zein PET
others Others Acetate
Eichinger, Lenzing AG, 2012
 Textiles value chain

Fiber Knitting& Dyeing & Garment

Spinning Yarn Retail Customer
Producer Weaving Finishing Manufact

Apparel Hometextiles:
– Silkiness – Mattresses
– Soft drape – Mattress pads
– Good moisture absorption – Upholstery
– skin sensory – Carpets
characteristics
– Lingerie

Lenzing AG, 2013

 Nonwovens

Private
Fiber Roll-good Conv
label or Retailer Customer
Producer producer erter
brand
Wipes
Hygiene
– Tampon fibers
Medical
– Plasters
– Wound pads
– Surgical swabs, drapes and gowns
Technical
– Filtration
– Papers (short cut fibers)
– Battery separators
– Precursor fibers (carbon, graphite ,..fibers)
Lenzing AG, 2013
 Outline
Background
Regenerated Cellulose
Processes
Cellulose dissolution and
regeneration
Spinning at AALTO

Structure Formation

Composites
 Michelin BoCell DuPont
Formate/air Superphosphoric acid Acetate in
gap/saponified Air gap / acetone regen TFA/HCOOH/steamdr
awn/saponified

Fortisan
LYOCELL Acetate/acetone
(a) NMMO.MH spun, saponified
(b) Ionic liquids

Carbamate
NaOH/urea in o-
xylene *
Cupro
[Cu(NH3)4](OH)2
Viscose BioCelsol
CS2/NaOH Enzyme/NaOH/ZnO
(urea/thiourea)

*CarbaCell®
Commercial, now or in former times
Non-commercial
 Viscose vs. Lyocell

NaOH / CS2 wood pulp

Viscose Lyocell
derivatization direct dissolution

wet spinning dry-jet wet spinning

10
Andrzej Ziabicki, Fundamentals of fiber spinning, John Wiley & Sons Ltd, (ISBN: 0-471-98220-2).
 Viscose, Lyocell
Global production, 2012: 3.7 Mio t
Global capacity, 2012: 5.2 Mio t

Cotton Modal Viscose Lyocell

Cellulose is converted to a cellulose xanthate which is then
dissolved in diluted caustic.
o CV: Regular Viscose
o CMD: Modal Fibres are high wet modulus fibres produced by a
modified viscose process: Bisfa wet modulus > 5 cN/tex/5%
o CLY: Lyocell, Tencel®: air-gap spun from solution in direct solvent
Untersberger, CEO Lenzing AG, 2013
 Historic viscose fiber developments

Process DP pulp Cellulose CS2 Spinbath Stretch- Modifiers X-ray Accessi Td, Tw,
conc, % charge, % ability, crystal- bility, % cN/tex cN/tex
% linity, % (H/D)

Standard 350-450 8-9 26-32 High acidity, high 50-70 No or low amount of 28-35 65 25 12
Na2SO4, modifiers
moderate ZnSO4
High-wet 500-550 6 35-40 Moderate acidity 80-150 Organic modifiers 35-40 50 35 20
modulus and Na2SO4, high (amines, PEOs)
ZnSO4
Polynosic 600-650 6 38-42 Weakly acidic, 200-300 Addition of 40-47 45 35-55 25-35
strongly (max formaldehyde to
coagulating salt 600) form methylol
bath. groups, which are
Second, more split off in the
acidic bath second bath
 Outline
Background
Regenerated Cellulose
Processes
Cellulose dissolution and
regeneration
Spinning at AALTO

Structure Formation

Composites
 Cellulose dissolution

Cellulose is amphiphilic (structural anisotropy): contains

polar in equatorial and nonpolar groups in axial directions
->electrostatic repulsion between charged backbones prevents re-association (Zn[OH] 42-]

Thermodynamic aspects: hydrophobic interactions, 2.0 kcal/

mol/residue, H-bonding, effect of charges

Kinetic aspects: removal of primary cell wall structure facilitates

the penetration of the solvent molecules into internal cellulose
structure->ballooning phenomena avoided

• Martin Kihlman et al. Braz. Chem. Soc., Vol. 24, No. 2, 295-303, 2013
• Medronoh, B.; A. Romano; M.G. Miguel; L. Stigsson; B. Lindman. Cellulose (2012), 19, 581-587
• Bergenstråhle,M.; J.Wohlert, ME Himmel, JW Brady. Carbohydr Res (2010), 14, 2060-2066
• Le Moigne, N.; Navard, P. ACS Symposium Series (2010), 1033 (Cellulose Solvents), 137-148.
Dissolution of Cellulose in ILs

+
O3-H-O5 intrachain
O2-H-O6 intrachain
+ O6-H-O3 interchain
 O3-H-O5 intrachain
O2-H-O6 intrachain
Intersheet bonds O6-H-O3 interchain
intersheet H-bond
 O3-H-O5 intrachain
Solvation of nonpolar cellulose surface O2-H-O6 intrachain
+ O6-H-O3 interchain
by the cation intersheet H-bond

Cho, H.M.; Gross, A; Chu J.-W. J. Am. Chem. Soc. 2011, doi 10.1021/ja2046155.
Regeneration of cellulose

O3-H-O5 intrachain
Re-formation of intersheet and intrachain O2-H-O6 intrachain
+ HO intersheet H-bond
bonds 2

Liu, H.; Sale, K.L.; Simmons, B.A.; Singh, S. Phys. Chem. B 2011, 115, 10251–10258.
 Cellulose dissolution in a vertical kneader

Temperature, C
150 600

Torque, Nm
dissolved

100 400

50 200
Wood pulp
0 0
0 30 60 90 120
Time, min

IL / H2O

Solubility up to 20 wt%
PHK-Pulp, [ ] = 424 mL/g

Final dope has to be filtrated and degassed

19
 Dissolution mechanism
In Cupri ethylendiamine
Euca Sulfite DWP Swelling & Dissolution mechanisms:
1. Dissolution by fragmentation
2. Dissolution by ballooning
3. Swelling by balloning
4. Homogeneous swelling

Influence of Cell Wall Structure

Complete dissolution by left handed 1. Solvent penetrates inside the fiber
untwisting of cellulose fibrils 2. The S2 layer dissolved by fragmentation
Euca Kraft-CCE100 3. The S1 layer swells under pressure
4. The primary wall breaks to form collars

0s

45 s
Increased swelling, no dissolution
Ballooning, formation of collars
Cuissinat, C.; Navard, P. Macromol Symp (2006), 244, 1-18
Gehmayr, V., Potthast, A., H. Sixta, Cellulose (2012) Le Moignet, N.; Navard, P. ACS Symposium Series 1033 (2010), 137 20
 Cellulose Aggregate Solution
0.2-0.3 wt% Pulp dissolved in NMMO.MH
Molecules laterally aligned,
800 250 core surrounded by
*MW/162 DP

Rg, radius of gyration, nm

disordered regions;
aggregate number*

200
600 aggregate size not affected
150
400
100
200
50

0 0
no wat2e0r % NaOidHammonia
liqu
pre-treatment Interpenetrated network
solution
Static light scattering measurements (Guinier-Zimm)
21
T. Röder, B. Morgenstern, Polymer 40 (1999) 4143 - 4147
Cellulose Dissolution&Regeneration in Water

Dissolution of Euca-PHK in:

– [EMIM]OAc
– [TMGH]OAc
– [TMGH]EtCOO
– NMMO H2O

• Regeneration by addition of water and mixing

• On completion of regeneration, turbidity appears

over a range

Hauru, L.K.J.; Hummel, M.; King, A.W.T.; Kilpeläinen, I.; Sixta, H. Biomacromolecules 2012, 13, 2896-2905..
 Empirical Kamlet Taft solvent descriptors
predict cellulose solubility
Effects on the UV–VIS spectra of dyes
Dissolution window to probe particular solvent properties
• Correlation of KT-parameter *
with cellulose solubility
• Concept of net-basicity, , to take N+

into account
O-

Reichardt's dye
[emim]OAc green-blue in methanol

1,0 [TMGH]EtCO2
… hydrogen bond acidity (donor)
[TMGH]OAc
20 … hydrogen bond basicity (acceptor)
0,5 NMMO H2O
*…dipolarity/polarizability (ability of a solvent to
NMMO 2H2O 100
[Pnnnn] stabilize a charge or a dipole)
0,0 LiCl/DMAc
[Rmim]MeOHPO2
[eimH]EtCOO Empirical solvent descriptors are very
-0,5 [DMAPH]EtCOO
[HOC2mim] helpful in the development of novel
[emim]
-1,0 [bmim] solvents for the dissolution of
individual lignocellulosic components
0,0 0,3 0,6 0,9 1,2 1,5
M.J. Kamlet and R.W. Taft: JACS, 98:2, 377-383 (1976)
Hauru, L.K.J.; Hummel, M.; King, A.W.T.; Kilpeläinen, I.; Sixta, H. R.W. Taft and M.J. Kamlet: JACS, 98:10, 2886-2894 (1976)
Biomacromolecules 2012, 13, 2896-2905. 23 M.J. Kamlet, J-L.M. Abboud, MH: Abraham, R.W.Taft, JOGS, 48, 23
2877-2887 (1983)
 Effect of Water
ET(30) decreases almost
54
1.2 * linearly.
1.1
51
1.0 Deviation of linearity
48 0.9 due to water activity
45 0.8 (non-linear).
0 2 4 0 2 4 6
0.8 1.2
[TMGH]EtCOO Similar slope for
[TMGH]OAc
0.6 1.0 [emim]OAc different Ils.
NMMO
0.4 0.8 LiCl/DMAc
values of NMMO
0.2 hydrates more sensitive
0.6
0.0
0 2 4 0 2 4 6
to water (high enthalpy
Stoichiometry, (n H2O) Stoichiometry, (n H2O) of hydration of NMMO).

Hauru, L.K.J.; Hummel, M.; King, A.W.T.; Kilpeläinen, I.; Sixta, H.

Biomacromolecules 2012, 13, 2896-2905.
 Cellulose Regeneration in Water

400 • Noticeable turbidity

Turbidity (NTU)

[EMIM]OAc
[TMGH]EtCOO appears only when
300 [TMGH]OAc 2 mol H2O/ mol IL are
NMMO
reached or exceeded.
200
• Slope of turbidity rise
100 slower for [TMGH]-ILs
than for the reference
0 solvents.
0 2 4 6 8 10
Stoichiometry (n H2O)

Hauru, L.K.J.; Hummel, M.; King, A.W.T.; Kilpeläinen, I.; Sixta, H.

Biomacromolecules 2012, 13, 2896-2905.
 Regeneration
1,0
Dissolution vs Regeneration
--
• decreases upon water addition.
--
-- • [emim][OAc] water-tolerant ~ 16 w/w%
0,5 -- --
-- -- --
--
-- ---- • [TMGH]-ILs water-intolerant 1-4 w/w%
----
-- -- LiCl/DMAc
-- -- • [TMGH]+ hydrotrope, bulky, hydrophobic
-- [TMGH]EtCO2
0,0 -- -- [TMGH]OAc
-- NMMO
• Order of water tolerance: [TMGH][OAc]
lit. [emim]OAc
< [TMGH][EtCO2] << [emim]OAc
0,6 0,8 1,0 1,2

Hauru, L.K.J.; Hummel, M.; King, A.W.T.; Kilpeläinen, I.; Sixta, H. Biomacromolecules
26 2012, 13, 26
2896-2905. DOI:10.1021/bm300912y.
Structure formation

In a dry-jet wet fiber spinning

process the fluid filament is
drawn in the air gap

Take-up velocity Extrusion

velocity

27
 Structure formation

• Orientation of cellulose
polymers due to
extensional stress

Irregular molecules
• Solvent exchange arrangement

Crystallites

• Formation of fiber’s Laminas

microstructure

Draw
Fourné, Synthetic Fibers; Carl Hanser Verlag, Munich 1999.
28
Experimental details
dissolution
Cotton linters: DP 1975 (729 ml/g)
DP 2640 (909 ml/g)
Eucalyptus urograndis pulp
DP 1100 (468 ml/g)
water
addition
H2O

H2O

29
Nephelometry

Turbidity measured by 350 100

quantifying back-scattered 300
light: Nephelometer

Complex viscosity [Pa·s]

250
10

Turbidity (NTU)
200

150

100 1

50
Turbidity
0 Complex viscosity
0.1
not sensitive enough! 0 10 20 30 40 50
water (%)

Mazza et al. Cellulose, 2009, 16, 207-215 (DOI: 10.1007/s10570-008-9257-x).

30
 Steady shear measurements

5% cotton linters (DP 1975) in

[emim][OAc]
10000 0.0 %
5.0 %
• Solution is diluted upon 7.3 %
9.7 %
water addition 10.4 %

Dynamic viscosity [Pa·s]

1000
15.0 %

100

10

1
0.1 1 10 100
-1
Shear rate [s ]

31
 Steady shear measurements

5% cotton linters (DP 1975) in

[emim][OAc]
10000 15.3 %
17.3 %
• Solution is diluted upon 19.2 %
24.9 %
water addition

Dynamic viscosity [Pa·s]

1000

• Gel formation, i.e. formation

of a supramolecular network
100
structure
• Structure collapses, phase
10
separation

1
0.1 1 10 100
-1
Shear rate [s ]

32
Rheological sample analysis

Rheological key 3% cotton linters (DP 1975) in [emim] OAc

parameter as function of
1000
water content Complex viscosity
Storage modulus 4
Loss modulus
Damping factor
Viscosity decreases

Complex viscosity [Pa·s]

Dynamic moduli [Pa]
100
before a steep rise is

Damping factor
observed
G’, G’’ depict similar 2

behavior 10

Damping factor ( ) most

1 0
sensitive parameter 0 10 20 30 40 50
Water (w/w-%)

33
 Outline
Background
Regenerated Cellulose
Processes
Cellulose dissolution and
regeneration
Spinning at AALTO

Structure Formation

Composites
Spinning at Aalto
IONCELL-F
Dry-wet jet spinning - preliminary tests

UNSTRETCHED STRETCHED

NMMO/H2O/E-PHK 13 wt-%

• Textr. = 100ºC
• Vextr. = 0.8 cm3/min

[EMIM][OAc]/E-PHK 20 wt-%

• Textr. = 95ºC
• Vextr. = 0.8 cm3/min

36
 Fiber properties
20 wt% Eu-PHK in
[emim][OAc] at 95°C
• Despite comparable rheology,
Dynamic Moduli, Pa
1E+04
[emim][OAc] dopes are much more
difficult to spin than NMMO dopes
1E+03 13 wt% Eu-PHK in
NMMOxH2O at 100°C
• Structure formation in spinbath
1E+02
delayed. Weak filament breaks
when certain draw is exceeded.
1E+01 • Slight increase in orientation with
0,01 0,1 1 10 100
Angular frequency, 1/s increasing dope concentration.
NMMO (multi 18/100) 1,0
tenacity [cN/tex]

40 13 wt% E-PHK Tw/Td

30 0,8

20 0,6

10 [emim][OAc] (mono)
6% 15% 0,4
9% 20%
0
2 4 6 8 10 5 10 15 20
DR Dope conc, wt%
 Tailored ionic liquids for air-gap spinning

A series of novel ILs has been synthesized and

characterized.
All have high and net-basicity values ( - ) excellent
cellulose solvents.

RTIL ET(30)(a) *[b] [b] [b]

-
[emim][OAc] 50.1 1.01 0.50 1.09 0.59
[emim][O2CEt] 50.3 0.96 0.54 1.09 0.56
IL-1 51.3 1.02 0.56 1.08 0.52
IL-2 52.6 1.04 0.64 1.11 0.47
IL-3 53.2 1.00 0.71 1.16 0.46

[a] Dimroth-Reichardt polarity scale, [b] Kamlet Taft parameters

A. Michud, A. Parviainen et al. FIBIC poster, Aug 20-21, 2013
 Pulp Dope Fiber
Fiber analysis
dissolution characterization spinning

pre-mixing kneading/dissolution filtration

 Pulp Dope Fiber
Fiber analysis
dissolution characterization spinning

shear-rheological characterization extensional-rheological characterization

(to determine spinnability) (to determine filament stability in air gap)
10 wt% BahiaPulp, 60ºC

Complex viscosity [Pa.s]

5 IL2

Dynamic moduli [Pa]

5
10 3.4x10

4
10 5.6x10
4

IONCELL
3 8.1x10
2
10

2
10
G'
G''
1 *
10
0,1 1 10 100
Angular Frequency [1/s]

visdiameter (mm)
13 wt% E-PHK in IONCELL co
1,0 -c
Dope characteristics Value ap
illa elasto-
= 1 6 nm ry
22.1 re capillary
gi
= nm on
54.1
0,5 0,1 elasto-capillary
10.0 region
0,02
= 0.33 wt%
150 160 170
time (sec)
( ) 6.9 0,0
=2 0.01 3.8 wt% 0 50 100 150 200
time (sec)
 Pulp Dope Fiber
Fiber analysis
dissolution characterization spinning

41
 Pulp Dope Fiber
Fiber analysis
dissolution characterization spinning

Standard fiber Polarized light SEM Mechanical stress

analysis microscope
• Titer (linear density) • Birefringence • Morphology • Fibrillation
• Tenacity • orientation • Structure- tendency
• Elongation at break property relations
• Modulus

42
 Dope preparation

UNSTRETCHED STRETCHED

NMMO/H2O/E-PHK
13 wt-%
• Textr. = 100ºC

IONCELL*/ E-PHK
13 wt-%
• Textr. = 65-70ºC

Good spinnability

* Developed by Professor Ilkka Kilpelainen and Dr. Alistair King

Adapted from A. Michud et al. ACS conference, New Orleans, 2013
 °
Rheological characterization
13 wt% Euca-PHK 75000 13 wt% Euca-PHK
NMMOxH2O

[ ]0*, Pa.s
' 60000
G
[ ]0*

Complex viscosity, Pas

45000
Dynamic moduli, Pa

1E+04 1E+04
30000
''
G
15000 IONCELL

1E+03 1E+03
3

at cross-over
s-1
2
1
1E+02 1E+02 0
0,01 0,1 1 10 100 70 75 80 85 90 95 100
Angular frequency, 1/s Temperature, C

Dope from novel cellulose solvent shows stable

spinning conditions at much lower temperature than
dope from NMMO.
 Draw ratio vs Fiber properties
0,06 n

Tenacitycond [cN/tex]
50

Birefringence
40 0,04

IONCELL 30
13 wt% E-PHK 0,02
20 AALTO fiber
NMMO fiber (Mortimer, 1996)

0,00
0 2 4 6 8 10 12 14 16 18 0 5 10 15
Draw ratio Draw ratio [ ]

Fiber pick-up

Total draw ratio

Adapted from A. Michud et al. ACS conference, New Orleans, 2013
 Polymer stability under IONCELL
process conditions

kDa PULP DOPE FIBER

1,0 PULP
dw/d(logMM)

DOPE
Mw 240.4 216.0 207.5
FIBER Mn 72.2 76.8 774.6
PDI 3.3 2.8 2.8

0,5 Very little degradation,

which could be further
reduced by reduced
0,0
3 4 5 6 7 dissolution temperature
log(MM)
 IONCELL-F Demonstration Run
Parameter Unit Fiber tenacities Yarn tenacity
Cond Wet AALTO Viscose
Titer dtex 1.9±0.2 1.7±0.2
Tenacity cN/tex 46.9±3.0 43.5±4.2 34.4±4.7 17.3±1.6
Elongation % 10.0±0.8 11.8±1.2 7.4±0.6 18.2±1.2

Washed fibers Air-opened Brushed fibers 2nd carding

roving drafting
Yarn from
Rotor spinning 47 27 runs, 411 g
Feeding the roving
 Production of a Scarf from
IONCELL fibers

VIDEO: IONCELL-F - Cellulosic Fibers from Ionic Liquid Solution,

http://www.youtube.com/watch?v=5bhCbGmNfTQ&feature=youtu.be
 Outline
Background
Regenerated Cellulose
Processes
Cellulose dissolution and
regeneration
Spinning at AALTO

Structure Formation

Composites
 Tensile deformation of dry cellulose fibres

1000 stress-strain curve: Stage I:

Tensile strength, MPa

IONCELL
15 wt% Euca-PHK IONCELL Internal energy elasticity: Extension
800 of fibrillar&molecular structure without
III disrupting H-bonds between fibrils.
Plastic deformation due to disruption
600
of interfibrillar H-bonds close to PL

400 II Stage II:

PL
dry

Orientation of fibrils unhindered by

200 interconnecting H-bonds. Slower build-
up of stress
I
0
0 5 10 15 Stage III:
Elongation, % Chain slippage and chain rupture
 Stress-strain curves of Regenerated
Cellulose Fibers
1200
CMD IONCELL
Tenacitycond [MPa]

1000 CV NMMO
Cupro BOCELL

800

600

400

200

0
0 5 10 15 20 25
Elongationcond [%]
 Continuous chain model
Serial arrangment of small domains.
Elastic tensile deformation is due to the elongation of the polymer
chain and the shear deformation of the chain segment.
The shear deformation induces a rotation of the direction of the chain
segment towards the fiber axis
Fibers > Fibrils > Crystallites-> orientation distribution relative
1 1 to fiber axis: orientation parameter
= + , , elastic, chain, shear moduli
tensile stress

For small strains:

= + • elastic extension of the polymer chains
2 • Elastic shearing of the crystallites (row of book
when falling over)
3 Birefringence vs chain orientation in a fiber: Hermans,
=1 Elsevier, 1949
2
From (1) and (3): nmax is the value for perfectly
1+ oriented fibers for which E = ec

shear between adjacent chains

Northolt, M.G. et al. Polymer (2001), 42, 8249-8264; Northolt, M.G. Lenzinger Berichte, (1985), 59, 71-79
 Birefringence vs Compliance
0,07 1+
Linear part: = 90 ( )
birefringence, n

highly oriented fibers

0,05 =
1+
g = 3.7Gpa
nmax= 0.068
0,03 Ioncell, 17 wt% g = 2.5 GPa, dnmax = 0.0621
Bocell g = 3.6 Gpa, dnmax = 0.0812
Fortisan, EHM Non-linear part:
Viscose
Medium and low oriented fibers
0,01
0,02 0,03 0,04 0,07 0,14 (viscose): g is likely to be a
-9 2 function of the orientation:
1/E, 10 m /N
= 1.3 ln 0.81
For E = 10 ->g = 2.2

1Northolt, M.G. et al. Polymer, (2001), 42, 8249

=
+ 2Kong, K.; Eichhorn, S.J. Polymer (2005), 46, 6380-6390
Structure formation vs mechanical properties
1000
Tensile stress, MPa
Polymer concentration vs.
800
orientation and tensile strength:
600 higher entanglement leads to
higher orientation, higher elasticity
400 and relaxation time?
IONCELL 13 wt% E-PHK
200 IONCELL 15 wt% E-PHK
IONCELL 17 wt% E-PHK
For IONCELL, biggest gap in n
0
NMMO 15 wt% HW-PHK and from 13 &15 wt% dope conc
0 5 10 15 20
0,06 Draw ratio
Birefringence and tensile stress
development clearly higher for
birefringence

0,04 IONCELL as compared to NMMO

0,02
IONCELL 13wt% E-PHK
IONCELL 17wt% E-PHK
NMMO 15wt% HW-PHK*
*Mortimer. Cell Chem Technol, 1996
0,00
0 5 10 15
Draw ratio
 Structure formation
1000
IONCELL 15 wt% E-PHK
Tensile stress, MPa

IONCELL 17 wt% E-PHK

NMMO 15 wt% HW-PHK
IONCELL: Elastic modulus, E, more
800 affected by polymer conc than tensile
stress.
600

NMMO: E levels off. Other results

400 show higher Es, but did not show the
E values of IONCELL
200
0 10 20 30 40
Initial modulus, GPa
relates to the extent of
1-Tw/Td
0,6
accessible material within the fiber
structure and thus to the
0,4
birefringence.
0,2
NMMO and IONCELL seem to have a
IONCELL 17 wt% E-PHK
NMMO 15 wt% HW-PHK
slightly different structure formation
0,0 Viscose regular
0,01 0,02 0,03 0,04 0,05 0,06
birefringence Bingham, B.E.M. Makromolekulare Chemie (1964), 77, 139-52
 Rheology of high concentration spinning
dopes
1E+05 According to the Cox-Merz rule,
(complex) viscosity, Pa.s

= 15.500 Pa.s
= 3.900 Pa.s the complex viscsoity, , is
equal to steady shear viscosity,
1E+04 when the angular frequency and
IONCELL
spinning dopes the shear rate approach zero.
13 wt% E-PHK: 70°C
oscillatory shear
1E+03 15 wt% E-PHK: 75°C
oscillatory shear
Cox-Merz rule works well at low
steady shear
17 wt% E-PHK: 85°C
conc., but the difference
oscillatory shear between and starts
steady shear
1E+02 getting higher with increasing
0,01 0,1 1 10 100 dope concentration1.
Angular frequency, 1/s
Shear rate Deviations from Cox-Merz:
destruction of strong intra- and
intermolecular bonds under
shear deformation (shear
1Kulicke, W.M.: Porter, R.S. Rheol. Acta (1980), 19 (5), 601-605 induced slippage)?2
2Song, H. et al. J. Phys. Chem B (2010), 114, 6006-6013
 Outline
Background
Regenerated Cellulose
Processes
Cellulose dissolution and
regeneration
Spinning at AALTO

Structure Formation

Composites
 Cellulose fibre-reinforced composites

Regenerated Cellulose has unlimited length, precise and predictable

geometry. IONCELL fiber is damage-free, has high strength&toughness.

1,0
L (wt%)
0
0,8 Tirecord
10

, GPa
0,6 20 15
10 OL
0,4 Lyocell
Modal
0,2 Viscose IONCELL-F
0,0
0 10 20 30 40
Young's modulus [GPa]
 Outlook ? !
Fundamental research on structure formation in air-gap
and regeneration bath(s).
Fundamental rheological studies of spinning solutions,
both shear and elongational.
Next stage of the technical development of the
IONCELL process with particular emphasis on the
solvent recovery.
Evaluation of fiber properties within the whole textile
chain. Tight collaboration with textile producers.

61
 Thank you for your attention!
Funding from Finnish Funding Agency for Technology and
Innovation (Tekes) and FiBiC as apart of the Future Biorefinery
programme is gratefully acknowledged

June, 2013

AALTO University, Biorefineries Research Group