Properties of regenerated fibres

CHEM-E2140 - Cellulose-Based Fibres

01.12.2015

Michael Hummel
Physical Properties of MMCFs
 Terms and Definitions
Linear Density (fiber fineness)
Mass per unit length (= titre)
1 dtex = g fibre / 10000 m
Circular cross section
Area A is related to diameter D:
Linear density c: 4

c... tex
D...mm 2

....g/cm3
Diameter of a 1.3 dtex fibre?
.
0.13 1 10
2 10.5 10 10.5
1000 1.53

11.3
Effect of Draw ratio on Fibre
Diameter
DR 3.0
40
19.5m -0.49
d = 33 (DR)

Diameter (m)
30

20

10
DR 0.7
0 2 4 6 8 10
Draw ratio
- Fibre diameter is strongly related to draw ratio
37.7m

Mortimer, S. A and Pguy, A. A. (1996), Cell. Chem. Technol, 30, 117

S. J. Eichhorn, K. Kong. 229th ACS National meeting March 13 17, 2005
4
 Adjustment of Linear Density (Titer)
Number of holes: n [] 1000
Diameter of holes: d [m] 85
Dope density: [kg/mL]
1.2
Cellulose content: C [wt%] 12
Draw ratio: DR [] 8
Extrusion velocity: v_0 [mL/min] 25
v_ex [m/min]
4.4
Takeup velocity: v_tu [m/min]
35.2
10 Titer T [dtex]
2 10
1.0

2 .
10 10

measured titer (dtex)

20

The measured titer is higher than the 15

8

calculated one due to contraction. 10

7
6
5
4

However, a clear relationship allows 5

3
2
1

the adjustment of the actual titer by 0

0 1 2 3 4 5 6 7 8

0
an empirical factor 0 5 10 15 20
calculated titer (dtex)
 Stress-Strain Curves

SI units of stress is Pa (Nm-2). In textile

technology the stress is related to the
linear density (mass per unit length)

Unit is Nm/kg or N/tex:

10 /

Stress f (GPa), specific stress (N/tex)

density (g/cm3)

Tenacity = Specific stress at break

 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

II
400
PL Stage II:
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
Initial Modulus
Specific strain

Initial modulus = tan

Slope in the energy elastic
region

Strain
Yield Point
Yield point as occuring at the
stress given by the
intersection of the tangent at
the origin with the tangent
having the least slope.

At the yield point, elastic

recovery becomes less
complete for higher strains.

Point at which permanent

deformation starts
 Tensile properties

10 10
10
9.81 10
1500 9.81
10
9.81 10
1.5 10
15 0.015
Stress-strain curves of Regenerated
Cellulose Fibers
1200
CMD IONCELL
CV NMMO
Tenacitycond [MPa]
1000
Cupro BOCELL

800

600

400

200

0
0 5 10 15 20 25
Elongationcond [%]
Structural vs. Mechanical Properties

Mechanical properties such as fibre tenacity, FFc,

are determined by
- the DPn in relation to the size of
- the elementary crystallites DPnL
- the degree of lateral order, Xc, and
- the degree of orientation, fc and ftot.

Krssig has shown a linear relationship between

FFc and
valid for cellulose fibres including fortisan,
polynosic and HWM.

Hans Krssig: Cellulose (1993), p161

Effect of molecular an structural characteristics
on the conditioned tensile strength

Tenacity (cN/tex) 70
60
50
40
30
20
10
0
0 5 10 15

Hans Krssig: Cellulose (1993), p161

 Short-chain molecules, DP < 100
VISCOSE FIBRES
Maximum strength
550
Working Strength[cN/tex*%]

properties (tensile strength

times elongation) of regular
500 visose fibres dependend on
the amount of DP<100
fraction.
450

commercial dissolving pulps

0 3 6 9
DP < 100 weight fraction in pulp [wt%]
 Continuous chain model
- Chains are oriented parallel to the
symmetry axis and the orientation
angle of this axis with the fiber axis
shows a distribution

- Elastic tensile deformation is due to

the chain elongation and the shear
deformation.

- Chain modulus, eC, purely elastic,

shear deformation, g, is determined
by intermolecular H-bonding (time
dependent) and denotes the shear
CELL I CELL II between adjacent chains.

Chain modulus = Chain modulus = 1 1

140 GPa 90 GPa 2
orientation parameter
, , elastic, chain, shear moduli
tensile stress
 Ultimate strength of cellulose fibers
100 2,2
chain modulus
Dynamic modulus, GPa

max CELL II
2,0

Tensile stress (GPa)

80
1,8 DuPont
EHM
60 1,5
Fortisan Bocell
1,2 Fortisan
40 Hemp
0,9
IC-F
20 0,6 TC

CLY
0,3 CV CMD
0
0 1 2 3 4 5 0,0
Extension, % 0 20 40 60 80100
Young's modulus (GPa)
Dynamic modulus depends only on the Emax: ~ 60 GPa (IC-F: 35)
extension: E as a f ( for well-
oriented regenerated cellulose fibers: max: ~ 1.8 GPa (IC-F: 0.9)
second loading cycle.

Northolt, M.G. Lenzinger Berichte, (1985), 59, 71-79. De Vries. Appl. Sci. Res. A3, 111 (1952).
Fiber Cross-Sections, Cryo Fractures

CV

CMD

CLY 10 m
1 m 1 m

Magn. *1070 * 6000 *20 000

 Structure and Mechanical Properties
Fiber Mechanical properties Structural properties

C C Fw DPv Xc fC ftot
GPa % %

CV 0.38 20 0.50 430 28 0.62 0.41

CMD 0.51 13 0.57 650 29 0.66 0.47
CLY-NMMO 0.60 15 0.90 900 41 0.85 0.59
CLY-IL 0.85 10 0.92 900 0.96* 0.81*
Bocell 1.30 7 0.85 650 59

Fw ratio wet-to-dry strength

xc WAXS degree of crystallinity
fc crystalline orientation parameter (Hermans, 1946)
ftot total orientation parameter
* different method

1 0.91 *T. Rder, P. Zipper (2003), Lenzing AG
**H-P Fink (2014)
 Absorbed Water in Cellulose Fibers

CO Cotton absorbs only little water

CLY
Tencel shows uniform water absorption
over the whole fiber cross section

CMD Crystalline skin of Modal

contains less water than the
core

Visualization of water: Uneven

Solvent exchange procedure followed by water
isoprene polymerization and OsO4 staining in distribution in
aqueous solution: viscose
19
M. Abu-Rous et al. Cellulose, 13, 411-419 (2006) CV
 Water Vapour Sorption

Absorption capacity of
1800 g H2O
equivalent beds at 100 % RH
1500

1200 Lyocell beds helps to make a

comfortable sleeping climate.
900

600
Water absorption takes place in
300 the capillaires between the
0 fibrils only
Lyocell Wool Cotton PES

20

*Total textile material = 4.24 kg. H. Firgo et al., Dornbirn 2003

Nanofibrillar Structure of Lyocell Fibers

Nanofibrils act as a
microscopic canal
system that facilitates
moisture absorption and
transportation

Courtesy to Lenzing AG
https://mediadb.lenzing.com/pindownload/pindownload.do;jsessionid=B7E0B3E7C2021492BA5EDB8AA91143EE
 Lyocell Fiber NanoMultifilament
- Nonswelling hydrophilic crystalline microfibrils
- Swelling amorphous regions and interfibril capillaries

1 m

Skin, app. 100 nm dry, can

Fibre, diameter swell widely in H2O
8 - 30 m

Macro-fibril (0,5 - 1m), made

up of micro-fibrils (10 - 100 nm)
Microfibrils (D & A),
H. Firgo et al., Dornbirn 2003 non swelling
22
Fibrillation of Lyocell Fibres
 Tendency of Fibrillation

Cross-
linking

Mechanically treated Lyocell LF

Lyocell
Triacrylamido-trihydrotriazin 2,4-Dichloro-6-hydroxy-1,3,5-triazin
(Lenzing, A100). (Lenzing, Lyocell LF).

24
 Cross-Linking

water cross-linker

ONa N Cl ONa N OCell

HO-Cell
N N N N

Cl Cl
 Crimp
The crimp of a fibre increases the covering power
(capacity to cohere) and is the prerequisite for the further
processing to yarn and fabric.

Viscose Stapel fibres receive a spontaneous crimp due

to the skin-core structure
Summary

Thickness = Titer (linear density): (d)tex

Tensile strength = Tenacity: cN/tex
Stress-strain curved provides info on
Break strength
Elongation to break
Youngs modulus
CLY has higher orientation than viscos
type fibers which affects properties

27
Yarn production
 Textile Chain
Yarn Spinning

Ring: 20 m/min
Weaving
Compact: 20 m/min
Knitting
OE: 150 m/min
Air jet: 450 m/min Dyeing

Cotton Lyocell
woven

knitted

Lenzing AG
Yarn spinning techniques

Hand spinning
Rotor spinning
Ring spinning

Rotor spinning
carding of fibers
Ring spinning steps
sliver fed to the drafting machine

preparing of roving

ring spinning

yarn plying
Ionic liquids Ioncell-F
Ionic liquid (IL)
conventional salt melt
(> 100 C)
100 C

is a salt in its liquid state

liquid that consists
exclusively of ions Ionic Liquid (IL)
fused salts with a (< 100 C)
melting point below 100 C

25 C

Subclass: Room Temperature

Ionic Liquid (RTIL)
(< 25 C)
Ionic liquids as alternative cellulose solvents ?
Cations Anions
R1 R1
R1 R2 R1 R2
N N N
N R
R4 2
R3
R2
Ammonium Pyrrolidinium Piperidinium Pyridinium

R3 R2 R2 R3
R4 N R3 N R3 N N N
R2 N R1 N R2
R5 N R4 N R4 N R4 N
R1 R1 R1
Imidazolium 1,2,3-Triazolium 1,2,4-Triazolium

R3 R1 R1 R2
R4 R1 N
N
R2 P R S R6 R3
R4 2
R3 R2 N N
R5 S R3
R1 R5 R4

Thiazolium Phosphonium Sulfonium Guanidinium

N N

N N
R1 R1
1,8-Diazabicyclo[5.4.0]undec-7-enium 1,5-Diazabicyclo[4.3.0]non-5-enium
DBU DBN
Dissolution of Cellulose in ILs

Et
N
+N
Me 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
+ intersheet H-bond
bonds HO 2

Liu, H.; Sale, K.L.; Simmons, B.A.; Singh, S. Phys. Chem. B 2011, 115, 1025110258.
 IL-spinning in literature
Spin- Nozzle
IL Conc 0 Temp diameter
DP DR Titer Tenacity Elongation Ref.
wt-
Pa.s at C C m dtex cN/tex %
%
[amim]Cl 12.5 75 100 1180 10.5 1.3 32.2 8.4 Laus et al.
[amim]Cl 10 100 100 815 8.6 1.6 26.8 10.8 Laus et al.
[amim]Cl 10 80 100 920 10.5 1.3 36.8 11.2 Laus et al.
[bmim]Cl 11 100 100 920 10.5 1.3 33.1 11.5 Laus et al.
[bmim]Cl 11 105 100 580 13.7 1.0 37.9 11.3 Laus et al.
[bmim]Cl 11 170 n.s. Laus et al.
[bmim]Cl 11 100 100 920 15.2 0.9 51.2 8.5 Bentivoglio
[amim]Cl 11 70 100 920 6.2 2.2 41.6 12.2 Bentivoglio
[bmim]Cl 10.4 70 790 2.9 1.7 38.6 13.2 Michels, Kosan.
[bmim]Cl 10.4 100 569 6 1.7 43.8 15.3 Michels, Kosan.
[bmim]Cl 10.4 130 569 10.9 1.6 44.7 12 Michels, Kosan.
[bmim]Cl 13.6 47 540 85 116 100 569 10.6 1.5 53.4 13.1 Kosan et al.
[emim]Cl 15.8 24 900 85 99 90 514 7.9 1.8 53.1 12.9 Kosan et al.
[bmim]OAc 13.2 9 690 85 90 90 493 7.3 1.7 44.1 15.5 Kosan et al.
[bmim]OAc 18.9 63 630 85 98 90 486 10.7 1.6 48.6 12.6 Kosan et al.
[emim]OAc 19.6 30 560 85 99 90 479 10.3 1.8 45.6 11.2 Kosan et al.
[bmim]Cl 12.1 17 550 85 100 515 7.8 1.8 56.8 9.6 Kosan et al.
[bmim]Cl 11 ~4500 90 90 145 790 20.7 6.8 Cai et al.
[bmim]Cl 8 ~1350 85 85 145 686 2.4 26.4 8 Cai et al.
[bmim]Cl 8 ~1350 85 85 145 722 3.5 29.3 7 Cai et al.
[emim]OAc 8 85 145 722 3.5 32.0 7.8 Cai et al.
[emim]OAc 10 18 000 20 20 90 1120 2.3 4.1 24.6 3.8 Ingildeev et al.
[emim]OAc 6 33 90 90 40 592 0.5 1.6 22.2 8 Ingildeev et al.
[emim]dep 10 18 000 60 60 90 592 1.9 4.9 26.4 6 Ingildeev et al.
[bmim]Cl 5 50 90 90 150 592 5.0 2.22 35.1 6.6 Jiang et al.
[bmim]Cl 5 50 90 90 150 514 5.0 2.22 38.8 6.5 Jiang et al.
[bmim]Cl 5 50 90 90 150 514 5.0 2.22 42.1 6.2 Jiang et al.
[emim]OAc 6 90 32 514 1.0 0.5 17.6 6.5 Hermanutz et al.
Thermal stability
Possible degradation reaction upon long-term heating

Meine et al. J. Green Chem. 2010, 12, 1711-1714.

 Limitations of [emim][OAc]
[EMIM][OAc], one of the best cellulose solvents:
Limited thermal stability (~ 0.01%/h at 100 - 110C)
Reaction of imidazolium cation with the REG

Formation of carboxylic acids, HCOOH, as a result of pulp

degradation
Accumulation of inorganic salts from the pulp in the IL

Ebner, G. et al. Tetrahedron Letters (2008), 49(51), 7322)

 Novel cellulose solvent:
1,5-diazabicyclo[4.3.0]non-5-enium acetate

1
[emim]OAc
Dynamic Viscosity [Pas]

[DBNH]OAc

0.1

0.01
0 20 40 60 80 100
Temperature [C]
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

Final dope has to be filtrated and degassed

43
 Rheological characterization
13 wt% Euca-PHK 75000 13 wt% EPHK

[]0*, Pa.s
'
60000 NMMOxH2O
G
[]0* IONCELL

Complex viscosity, Pas

45000
Dynamic moduli, Pa

1E+04 1E+04
30000
''
G
15000
1E+03 1E+03
3

s-1
at cross-over
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 solvent1 shows stable

spinning conditions at much lower temperature
than dope from NMMO.
1PCT/FI2014/050238, Application 04/04/2014
 Fiber spinning units
KS42 KS80
Total volume 500 ml 2000 ml
Extrusion rate 0.4 4.0 ml/min 1.277 12.77 ml/min
Filament number 16 60 150 200
Fiber output per ca. 50 g ca. 150 200 g
day
Studying of Primarily for demo
different products
substrates
 Standard spinning conditions
Molar Mass Distribution Dope rheology
Substrate Viscosity DP<100 DP>2000 PDI 0* COP GCOP
(mL/g) wt% wt% (Pas) (1/s) (Pa)
Birch PHK 476 4,7 24,2 4,1 75C 35 382 0,725 4360
Fiber 447 4,3 20,5 3,2 80C 27 148 0,991 4435

Birch PHK pulp G'

Complex viscosity (Pas)

1,0 Fiber *
0

Dynamic moduli (Pa)

4
10
dm/d(Log MM)

G''
103 G''
0,5

102 75C
G' 80C

0,0 101
3 4 5 6 7 0,01 0,1 1 10 100
Log (Molar Mass) Angular Frequency [1/s]
 Mechanical vs. structural properties
1000 40 1000
F

Youngs Modulus, E (GPa)

IONCELL-F

Tenacitycond [MPa]
800
F(MPa)

Crystallinity, CrI (%)

CrI 35 800
600
E
400 NMMO
30 600
crystalline orientation Modal, CMD
200
400 Viscose, CV
Orientation, f

25
amorphous orientation Cupro
0,8

20 200
0,6
0
0,4 15 0 5 10 15 20 25
0 5 10 15
Draw ratio [-] Elongationcond [%]
2,0 MAX
Spinning of anisotropic solutions
Tensile stress (GPa)

DuPont
1,5
Bocell
to exploit the full strength potential
Fortisan Carbamate/
of cellulose II:
0,9 NMMO
Tirecord
IONCELL Emax: ~ 60 GPa (IC-F: 35)
0,6
CLY
max: ~ 2.1 GPa (IC-F: 0.9)
0,3 CV
CMD

Northolt, M.G. Lenzinger Berichte, (1985), 59, 71-79.

0,0
0 10 20 30 40 60 80 100 De Vries. Appl. Sci. Res. A3, 111 (1952).
Young's modulus (GPa) Sixta, H. et al. NPPRJ, 30(1), 2015, 43-57
 Demonstration runs
SCARF: 11/13 Marimekko Mens
DRESS: 3/14 accessories
9/14

Knitted fabric Knitted fabric Woven fabric

designed by Tuula Pyhnen
 Effect of hemicellulose content
Pulp Dope Titer DR c c w c E
Wood Process Hemi wt% pulp dtex cN/tex % cN/tex % GPa

Euca PHK 2.6 13 1.2 17.7 50.5 8.5 46.4 11.5 26.5
Birch PHK 5.6 13 1.6 12.4 52.6 10.1 46.0 11.4 19.7
Spruce AS 3.3 13 1.6 12.4 48.5 10.0 45.7 11.8 21.7
Pine K 15.1 13 1.7 10.6 48.4 11.0 41.3 11.2 25.1
Euca-PHK: DP<100 = 3.2 wt%
Birch-PHK: DP<100 = 4.6 wt%
Spruce-AS: DP< 100 = 4.4 wt% 0,06
1,0 Pine-K: DP< 100 = 4.9 wt%
dw/d(logMM)

Birefringence
0,04

0,5
0,02
Euca-PHK
Birch-PHK
Spruce-AS
Pine-K
0,0 0,00
3 4 5 6 7 0 5 10 15
log MM Draw ratio [ ]
 Waste paper and
cardboard as raw material
 Waste material as cellulose source

Fine paper

73% fully bleached chemical pulp 77% cellulose

27 % ash 21% hemicellulose
2% lignin

Cardboard
mixture of mechanical, semi-chemical 64% cellulose
and chemical pulps 21% hemicellulose
27 % ash 17% lignin

Ma et al. Green Chem. 2015, online, DOI: 10.1039/C5GC01679G 51

 Waste material as cellulose source

Fine paper

Cardboard

Ma et al. Green Chem. 2015, online, DOI: 10.1039/C5GC01679G 52

Waste material as cellulose source

Intrinsic Hemi-
Cellulose Lignin
viscosity cellulose
[ml/g] % % %
fine paper 76.6 20.8 2.4
P1 11.5% 470 75.5 24.1 0.4
P2 13% 428 88.1 11.3 0.6
cardboard 57.6 20.8 16.6
B1 13% 447 63.8 20.9 15.3
B2 11.5% 500 80.2 16.6 2.9
B3 13% 470 88.3 9.8 1.9
B4 13% 353 89.6 9.7 0.8
B5 13% 436 82.4 16.7 0.9

Ma et al. Green Chem. 2015, online, DOI: 10.1039/C5GC01679G 53

Fibers spun from paper and cardboard

900 60 conditioned 17.8 15.9

Tenacity (tensile strength)

wet
750 50 15.9 19.8
16.8
600 40 14.1 Tencel

cN tex-1
MPa
450 30
Viscose
300 20 3.5

150 10

0 0
P1 P2 B1 B2 B3 B4 B5

Ma et al. Green Chem. 2015, online, DOI: 10.1039/C5GC01679G 54

 Fabrics from lignin containing yarns

The yarns were knitted. The natural color of the

fibers were used to create patterns.
Further, the fibers showed good dyeability, allowing
for the production of colorful garments without any
bleaching step.

awarded with

55
Waste textiles as raw
material

56
Raw material
Focus on cellulosic part = cotton
Initial studies on hospital bed sheets

2000
Cellulose DP

1500

1000

500 Challenge:
Cotton in textile waste shows wide
0
spectrum of intrinsic viscosity
1

3
h

depending on history of textile

tc

tc

tc
Ba

Ba

Ba

Chemical and ultrastructural changes in cotton cellulose induced by laundering

and textile use 57
Palme et al. Cellulose 2014, 21, 4681-4691.
 Adjustment of cellulose DP

1600
1400
1200
Cellulose DP

1000
800
600 Acidic or enzymatic
400 degradation to
200 different DP levels
0

58
 Final fiber properties
1000
Conditioned

Tensile strength (MPa)

900 CoW
60 wet
Enocell ref CoW /SW
Tenacity (cN/tex)

800
50 CoW
700 CoW/SW
40
600
30
500 Lyocell
20
400 Viscose
10
300
0
10 20 30
PH
K tile pu
lp
pu
lp
ml
/g
s tex le + r. 2 Young's Modulus (GPa)
yptu a ste e xti de
g
e 45
l w t + ti l
ca gr. ste tile ex
Eu e a tex
te t
c id
d
g r. w as te w as
a de w

59
 Effect of (residual) lignin
Pulp / Lignin Blends

100
80
50 0%L
60

Weight wt%
10% KL
Tenacitycond [cN/tex]

10% OL 40
40
20% KL
20% OL 20
30 30% OL 15 0% lignin
50% OL 10 15 wt% kraft
20 wt% kraft
Viscose 5 Kraft lignin
20
0
0 200 400 600 800
10
Temperature [C]

0
0 5 10 15 20
Elongationcond [%]
 Effect of residual lignin

Kraft coking Acidic viscosity Dissolution

different intensity adjustment +spinning

50 20
T dry

Lignin content (%)

T wet
Tenacity (cN/tex)

40
15
30
10
20
5
10

0 0
200 400 600 800 1000 1200
H-factor (h)
Master thesis Jonas Stubb
 Recycling of ionic liquid

Fundamental studies (VLE) on [DBNH][OAc]-

water mixtures to evaluate process parameter

Challenges
Hydrolytic stability of IL at T > 80C

Strong IL-H2O interactions

Accumulation of impurities
Ostonen, A. et al. European Symposium on Applied Thermodynamics (2015)
Ahamad, W. et al. 10th European Congress on Chemical Engineering (2105)
Parviainen et al. RCS Adv., 2015, 5, 69728-69737
Summary

[DBNH]OAc potential alternative to NMMO

Good solubility for other biopolymers allows for
processing of bio composite material
even from cheap sources such as waste material are
suitable as starting material
Fibers show properties similar to Tencel

63