Novel Regenerated CelluloseFiber Processes

COST-Action FP1205March 10, 2015

Herbert SixtaSchool of Chemical Technology

Aalto University

Fiber Market

263

5730

0,24

0,82

5,7

100

Lyocell Cotton0

2000

4000

6000

Water (m3/t)

x 17.5

x 3.4

x 21.8

Lyocell Cotton0,0

0,2

0,4

0,6

0,8

Hectares/t/a

Lyocell Cotton0

50

100

Environm. Impact

Fiber Year 2014Li Shen, Martin Patel (2007)

Synthetics Wool Cotton MMCF0369

1220

30

40

50

60

70

+9.1%/a

+0.0%/a

+0.9%/aAnn

ual a

mou

nt (M

io t)

Fibers

2000 2010 2013 2020e

+3.6%/a

Sustainability of MMCF

Spinning processes

1. Wet Spinning: three-component spinning with solvent, polymer and anti-solvent: CV, CMD, CUP

2. Dry-jet Wet or Air-Gap Spinning: three component spinning with solvent, polymer, antisolvent: CLY, liquid crystallinesolutions

3. Dry Spinning: two-component spinning with solvent andpolymer: CA, CTA

Wet-SpinningStretch bath

Stretch unit

Spinningpump Spin bath

take-up godet

Spinningpipe

spinneret

overflowFiltercartridge

Spin bathregeneration

Exhaust

2. CUPRO: Cu(NH3)2(OH)2

3. CARBAMATE

Cell O CO

NH2

CarbaCell®1.5 dtex

WO 03/09987313; DE 102008018745A1

4. BIOCELSOLNaOH/ZnO

10 μm2.1 dtexVehvilaeinen, M. Cellulose (2008)

6. OthersLiCl/DMAcPhosphoric acidOther solventsNFC/water

1. VISCOSE: NaOH / CS2

5. NaOH-Urea (thiourea)NaOH/urea=7:12

Xiong, B. et al. Cellulose (2014)Li, R. et al. I&EC (2010)

Viscose Process

Cotton

Regular Viscose

Modal®wet modulus ≥ 4.5 cN/tex/5%ε

0 5 10 15 200

10

20

30

40

CV

CMDCO

Tena

city

(cN

/tex)

Elongation (%)

SteepingPressingshredding

Ageing

Alc

alic

ellu

lose

Xanthation

Dissolving

Filtration

Dearation

Ripening

Visc

ose

prep

arat

ion

Spinning

StretchingSpin

ning

Aftertreatment

Drying

Baling

Cutting

Stap

lefib

erpr

od

NaOH recyclingDialysis, NF

CS2 recycling

H2SO4 productionfrom H2S

Na2SO4 productionfrom spinbath

Rec

yclin

g

By-

prod

ucts

Steeping (alkalization): conversion to cellulose-II lattice⟶Ageing (DP adjustment)

3 4 5 6 70,0

0,5

1,0

Pulp

dw/d

(logM

M)

Log MM3 4 5 6 7

0,0

0,5

1,0

Pulp

0 h

dw/d

(logM

M)

Log MM3 4 5 6 7

0,0

0,5

1,0

Pulp

0 h

1.5 h

dw/d

(logM

M)

Log MM3 4 5 6 7

0,0

0,5

1,0

Pulp

0 h

1.5 h4 h

dw/d

(logM

M)

Log MM3 4 5 6 7

0,0

0,5

1,0

Pulp

0 h

1.5 h4 h

dw/d

(logM

M)

Log MM

8 h

0 2 4 6 8

0

2

4 U = M

w /Mn -1

Time, h

ORO

O-Na+

O-Na+HO OH

OROO

OHO OH

C

S-Na+

S

CS

S-Na+

CS2

00:00 00:15 00:30 00:45 01:000

200

400

600

800

discharge

pres

sure

, mba

r

time, h:m

Xanthation

10 1000

1

2

3

4

frequ

ency

particle diameter, μm

Viscose Filtration

2 6 → 3Ripening

0 20 40 60 800,0

0,2

0,4

0,6

C-2+C-3

DSxanthogenate

Time, h

total

C-6

20°C

SPINNING

Xanthate decomposition

STRETCHING

AFTERTREATMENT

Cutter

WASHER DRYER

Skin plastic

Core not yetcoagulated

Cross section of Viscose Fiber

Cupro ProcessDissolution by complexing cellulose: Cuoxam completely dissolves cellulose bydeprotonating and coordinative binding the C2- and C3-OHs positions of the AHG.

cellulose-Intg

tg

cuoxam cellulose

n

cellulose-IIngt

gt

Regeneration bath:water, OH-

OO

H

HO

O

O H

O

OH

HO

OOH

O OO

H

OO

OH

HO

CuNN

OO

O HCu

NN

OO

OOH

HO

O

O H

O

OH

O

O H

OH

O

Cu(NH3)2

m Cu(NH3)2(OH)2

-2m H2O-m(n-2) NH3

Cupro Process

• Only producer is ASAHI Chemical Industries Co(NoBeoka, Japan) Bemberg™

• Bemberg™ cupro regenerated cellulose fiber from cotton linters.

• Made by Asahi Kasei Fibers since 1931, Bemberg™ is used in applications ranging from linings to outerwear, innerwear, sportswear, and beddings.

• Recovery of copper improved from 70% in 1930 to 99.9% in the 1980 (ion exchange resin)

Cuprofiber products

• Filament and staple fiber• Nonwovens• Hollow fiber membrane: UF, haemodialysis• Artificial kidney• Virus removal filter: mean pore diameter 15±2 nm

Cellulose-NaOH Spinning SolutionsBioCelsol NaOH/urea* CarbaCell®

DP-Pulp

Shredding Endoglucanase

DOPE, 3ºC7.8 wt% NaOH6 wt% Cellulose0.84 wt% ZnO

Wet Spinning5-15 wt% H2SO4coagulation bath

NaOHZnO

M. Vehviläinen, Cellulose 15, 671-680, 2008

Pulpin o-xylene

Azeotropic Distillation (vac)

Wet SpinningH2SO4/ Na2SO4

16%NaOH odp70% urea odp

-water-xylene

Xylene dist (N2)

NH3

DOPE carbamate in NaOH

NaOH

ureaLoth, F. et al. DE102 53 672 B3

SOLVENT7 NaOH+12 urea, wt%at -12.5ºC

DOPE, 5ºC5.2 wt% Cellulose

Wet Spinning(a) 10 % H2SO4/15%Na2SO4(b) 5 % H2SO4

ShreddedPULP

*8% NaOH+6.5% thiourea+8%urea

J. Cai et al. Adv. Mat, 19, 821-825, 2007Lina Zhang et al. J.Phys. Chem B, 2014, 118, 10250Lina Zhang et al. Cellulose, 2014, 21, 4019

Fiber Properties derived from NaOH

0 5 10 15 200,0

0,1

0,2

0,3

0,4

0,5

BioCelsol

Tena

city

(con

d), G

Pa

Elongation, %

NaOH / urea CarbaCell

Viscose

Stress-strain

CV

Cross-sections

10 mm

BioCelsol2.1 dtex

CarbaCell®1.5 dtex

NaOH/Urea3.5 dtex

Fibers spun from cellulose NaOH/Ureasolutions

Lina Zhang et al. Ind. Eng. Chem. Res. 2010, 49, 11380–11384

5.2 wt% of Cotton Linters dissolved in NaOH/urea/H2O= 7:12:81 by weight at -12.5°C

d. 15:10 H2SO4/Na2SO4e: 5 wt% H2SO4

ViscoseSample σb

cN/texεb%

NaOH/urea 18±1.7 19±1.6

Viscose 22-25 20-25Cupro 15-22 10-23

Fiber spun from LiCl/DMAcPulp from poplar

• Steam explosion: 230°C, 2-6 min, (i) water wash (ii) acetone extraction

• Orientation of chains is hinderedby the presence of lignin (54% vs. 72%*)

• The fibers from the fully bleachedsteam-exploded poplar pulp arecomparable to those of regularviscose

Focher, B. et al. J. Appl. Polym Sci. (1994), 50, 583-591

Dissolution• in DMAc/7%LiCl

Wet-spinning into water (20°)• Monfilament extruded• 100 μm spinneret; DR=1-3

Fiber properties• 22 wt% Lignin, cP=9.7%; Pv=250

– DR=1(3): σb=150 (190)MPa, ε=10%(4); E=11(13) GPa

• No Lignin;cP=7.5 %; Pv =220– DR=1(3): σb=220 (250) MPa,

ε=18%(8); E=12(17) GPa

*birefringence ratio to mercerized ramie

Fiber spun from orthophosphoric acid

• 7-9 wt% cellulose, DP 400-600, solution in H3PO4

• Dissolution in 3 h

• Pilot plant for wet spinningof fibers

• Flame-resistant fibers:– Tenacity = 22 - 28 cN/tex– Elongation = 10 - 25%– E-modulus = 9 -15 GPa

Cellulose

Activation, Dissolution, Deaeration

H3PO4

H2O Filtration Molding

Distillation

Drying

Fibre

IPA

GREENCEL

Round-shapedcross-section

Grinshpan,D. J.Eng.Thermophys. 84 (2011), 594-598Grinshpan, D. D et al. Vestsi Natsyyanal'nai Akademii NavukBelarusi, Seryya Khimichnykh Navuk (2014), (2), 115-118.

NFC-based fibers (1)

Wet-extrusion of the NFC hydrogels into ethanol.

Transparent fibers: infiltrating a resin (acrylic resin) matching the refractive index of NFC

Fiber propertiesModulus 22.5 GPa (15)Tensile 275 – 410 MPa (600)Elongation 4-6 % (15)

( ) Lyocell

Walther, A. et al. Advanced Materials, 23, (2011), 2924 - 2928 Iwamoto, S. et al. Biomacromolecules, (2011)

NFC-based fibers (2)• Hydrodynamically induced fibril alignment:• CNF dispersion ejected from a nozzle followed by coagulation• Electrostatic repulsion between particles reduced by an electrolyte

diffusing into the suspension; aligned structure frozen as a gel• After coagulation in an electrolyte bath, the filament is washed with

water and then dried after solvent exchange with acetone.

Håkansson, K.M.O. et al. Nature Communications, 5, 4018 (2014)

Cases Q1 Q2 Titer Tenacity E Modulus Elongationmm3s-1 mm3s-1 sheath bath dtex MPa GPa %

A 6,5 7,5 100 0 9,9 490 17,6 6,4B 6,5 7,5 100 100 5,7 445 18,0 8,6C 6,5 7,5 50 100 12,0 300 12,4 11,2D 6,5 4,5 100 100 16,9 295 12,8 11,1

NaCL (mM)

Dry-Wet Spinning

1. LYOCELL: NMMO.H2O or any otherdirect solvent.

N

O

O

+_

2. BOCELL (Superphosphoric acid, 74% P2O5): liquid crystalline solution, spun in acetone

3. DUPONT (CA dissolved in TFA): liquidcrystalline solution with HCOOH as co-solvent, spun into cold MeOH (-33°C), steam drawn, saponified with NaOCH3/MeOH under tension.

4. MICHELIN dissolved in formic and phosphoric acid): liquid crystalline solutionspun in acetone and saponified in an alkalinesolution.

Global production 2014: 0.22 Mio t (4 sites)Lyocell Process

Tencel®

CottonVisualization of water: isoprenepolymerization and OsO4 staining in aqueous solution*Cellulose, 13, 411-419 (2006)

http://www.lenzing.com/en/fibers/tencel/specifications.html

Film truderShear stress

ElongationalStress

Diffusioncontrolled

Andrzej Ziabicki, Fundamentals of fiber spinning, John Wiley & Sons Ltd, (ISBN: 0-471-98220-2).

Faero

Dry-Wet Spinning Temperature profile in air-gap

. ∙0 50 100 150

0

20

40

60

80

100

Tem

pera

ture

,°C

Distance from spinneret (mm)

Spinneret diameter:40-400μm

Mortimer, S.A. Peguy, A.A. Cell Chem Technol., 30, 117-132 (1996)

0 50 100 150 200 2500

2

4

6

8

10

12

V/V

0

Distance from spinneret (mm)

DR=10.0a =0.0313

200 μm orifice

Filament velocities

Total orientation parallel to dimensionless velocity

Strain hardening and shear thinning

spinneret face

bath-surfacebath-exit

undried fibre

dried fibre

50

100

150

200

0,00

0,01

0,02

0,03

0,04Δn

Dia

met

er, μ

m

Orientation of the fiber

BOCELL Fiber

0 10 20 30 400

30

60

90

120isotropic

Tc (ºC)

Cellulose (%w/w)

anis

otro

py s

tarts

anisotropic

Presolvent74% P2O5

H3PO4

H6P4O13

KneaderPulp

filter

acetone

airg

ap

SpinneretD

isso

lutio

n, 1

7.1%

cel

lulo

se, 5

0->7

4ºC

H. Boerstoel, PhD Thesis, University of Groningen, 1998

liquid crystallinesolution, at c>8w%

Clearing Temperature

σb = 1.3 - 1.7 GPaEi = 45 GPaεb = 6.5 %

BoCell Viscose

X-ray diffraction patterns

High Crystallinity and Orientation

Solvent: superphosphoric acid

DUPONT process

• Air-gap spinning of anisotropic cellulose solution

• Optimum spinnability obtained at– 30-42% cellulose triacetate (DS≥2.7) in TFA:H20 = 1.5-2.5;

alternatively, water can be replaced by CH2Cl2 or formic acid.

• Solution air-gap spun into cold methanol (-26 to-35°C) at draw ratios 2-8. Solution temperature must be keptbelow 40°C to preserve the liquid crystalline state. – Tenacities: 54-104 cN/tex– Elongations: 7-11%– E-modulus: 14-15 GPa

O`Brian, John, John Philip, EP 0103398

DUPONT processHeat treatment of cellulose triacetate fibres: tension of 1-10% under superheated steam treatment (110 - 260°C):

– Cellulose triacetate: • Tenacity: 118-128 cN/tex; • Elongation: 5-6%; • E-modulus: 30-37 Gpa

– Regenerated cellulose after saponifcation undertension (hung with lead shot weights) at roomtemperature (NaOMe in MeOH)• Tenacity: 128-164 cN/tex• Elongation: 6-8%• E-modulus: 41-46 GPa

O`Brian, John, John Philip, EP 0103398

MICHELIN process• Cellulose is dissolved in a mixture of formic and phosphoric acid.

In-situ derivatization (formate) occurs.

• Excess of formic acid and phosphoric acid serve as a solvent

• Solution is liquid crystalline: spun through an air-gap and cellulose is coagulated in acetone.

• Cellulose formate is then saponified by using an alkaline solution.

P.Villaine, C. Janin, WO 85/05115 (Michelin)

100 200 300 400 500 6000

20

40

60

80

100

Tena

city

(cN

/tex)

DP0 10 20 30

0

50

100

150

200

250

300

Vis

cosi

ty (P

a.s)

Cellulose (%)

C*

Dry-Spinning

recovery

Steam drawn

Saponification in alkaline solution

Aftertreatment, drying

2.5 acetate in acetone

Fortisan® Fiber

FORTISAN®: Cellulose acetate(thermoplastic properties) is stretched under steam and pressure in the first step.

In the second stage, thestretched yarn is saponified witha solution of caustic soda

Celanese Corporation (1955) introducedFortisan-36: Tc= 72 cN/texCaroll-Porczynski, C.S. Natural trade press, London (1961)

Moncrieff, R.W. Silk and Rayon Rec., 27, 1012 (1953)

Fortisan fiber• 1955, the Celanese Corporation of America introduced a

super-strong type of Fortisan, Fortisan-36.– Dry tenacity 72 cN/tex at 6.2% elongation 65-70% wet tenacity.

• Application– Reinforcement for belts

Flexible fuel hosePower transmission beltsBalloon fabric

Caroll-Porczynski, C.S. Natural polymer man-made fibers. Natural trade press, London (1961)

Stress-strain curves

Regular wet-spun fibers show low-to-moderate tenacitiesAir-gap spun fiber reveal good tensile propertiesDry spun, steam drawn and saponified fibers show excellenttenacities (≥0.8 GPa) and elastic modulus (≥30 GPa)

0 5 10 15 200

300

600

900Te

naci

ty (M

Pa)

Elongation (%)

CUP CV CMD Biocelsol Lyocell Fortisan

Why Alternatives to NMMO?• Transition metal ions• Tends to autoxidation reactions• Acids (Polonowski reaction)• Formaldeyhde release• Carbonium-iminium ions: autocatalytic decomposition

HO

HOOH

O

O

n-propyl gallateStabilizer

• Radical scavenger• Formaldehyde trap

Rosenau, T. et al. Cellulose, 2002, 9, 283Rosenau, T. et al. Progress in Polymer Science, 2001, 26(9), 1763-1837.

Ionic liquids as alternative cellulose solvents ?

N

NR3

R1

R4NR1 R2 N

R1 R2 NR1

R1

NR4 R3

R2

R1

PR4 R3

R2

R2

Ammonium

ImidazoliumPyridiniumPyrrolidinium Piperidinium

Phosphonium

R5R2

N N

NR6

R5

R3

R4

R1 R2

Guanidinium

Cations Anions

IL-spinning in literatureIL Conc η0

Spin-Temp

Nozzlediameter DP DR Titer Tenacity Elongation Ref.

wt-% Pa.s at °C °C µm 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.

Cellulose (In)stability

Effect of Cation

Pulp ABIM-Cl AAIM-Cl BMIM-Cl AMIM-Cl0

50

100

150

200 100°C, 3% cellulose

Polydispersity

MW

, km

ol/g

1

2

3

4

Bentivoglio, G. et al. Lenz. Ber., 86 (2006), 154-161

Effect of Anion

AMIM-Cl AMIM-Dimpo BMIM-Cl BMIM-Dimpo0

50

100

150

100°C, 3% cellulose

MW

, kg/

mol

Bentivoglio, G. et al. Lenz. Ber., 86 (2006), 154-161

Limitations of [emim][OAc]

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

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

• Formation of carboxylic acids, HCOOH, as a result of pulpdegradation

• Accumulation of inorganic salts from the pulp in the IL

Novel cellulose solvent:

0 20 40 60 80 1000.01

0.1

1

[emim]OAc

Dyn

amic

Vis

cosi

ty [P

a·s]

Temperature [°C]0 20 40 60 80 100

0.01

0.1

1

[emim]OAc [DBNH]OAc

Dyn

amic

Vis

cosi

ty [P

a·s]

Temperature [°C]

1,5-diazabicyclo[4.3.0]non-5-enium acetate

Rheological characterization

70 75 80 85 90 95 1000123

15000

30000

450006000075000 13 wt% EPHK

ω [s

-1]

[η] 0* , P

a.s

Temperature, C

at c

ross

-ove

r

IONCELLNMMOxH2O

0,01 0,1 1 10 1001E+02

1E+03

1E+04

G''

Dyn

amic

mod

uli,

Pa

Angular frequency, 1/s

G'13 wt% Euca-PHK

1E+02

1E+03

1E+04

Com

plex

vis

cosi

ty, P

as [η]0*

Dope from novel cellulose solvent1 shows stablespinning conditions at much lower temperaturethan dope from NMMO.

1PCT/FI2014/050238, Application 04/04/2014

IONCELL-F

Dope at RT

Good spinnability

60

70ºC

Parameters affecting Spinnability

• Pulp source

• Molecular weight distribution

• Residual water content in the dope

• Polymer concentration

• Geometry of spinneret

• Extrusion velocity

• Coagulation bath temperature

• Draw ratio

37

Effect of pulp source on fiber properties

Pulp Dope Titer DR σc εc σw εc EWood 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

3 4 5 6 70,0

0,5

1,0

dw/d

(logM

M)

log MM

Euca-PHK: DP<100 = 3.2 wt% Birch-PHK: DP<100 = 4.6 wt% Spruce-AS: DP< 100 = 4.4 wt% Pine-K: DP< 100 = 4.9 wt%

0 5 10 150,00

0,02

0,04

0,06

Bire

fring

ence

Draw ratio [ ]

Euca-PHK Birch-PHK Spruce-AS Pine-K

Molecular Weight Distribution

• 6 blends to adjust high and low molar mass fractions• 3 commercial dissolving pulps

Green fraction: good spinnabilityYellow fraction: medium spinnabilityRed fraction: not spinnable

Molecular Weight Distribution

3 4 5 6 7

Blend 1Spr-S 1521x0.22Spr-S 218x0.78

3 4 5 6 7

Blend 5Spr-S 1521x0.09CL 318x0.91

3 4 5 6 7

Blend 2Spr-S 577x0.75Spr-S 174x0.25

3 4 5 6 7

Blend 3CL729x0.02CL415x0.98

3 4 5 6 7

Blend 4CL 420

3 4 5 6 7

Blend 6CL 524x0.69

Spr-S 192x0.31

3 4 5 6 7Log (Mw)

Euca-PHK

DP<100

3 4 5 6 7Log (Mw)

Spruce-S

3 4 5 6 7

DP>2000

Log (Mw)

Beech-S

Source: Anne Michud (2015)

Molecular Weight Distribution

2 3 4 5 6 7 830

35

40

45

50Te

naci

ty, c

N/te

x

DP<100, wt%

Source: Anne Michud (2015)

Effect water in the dope

5 wt% 8 wt% 11.4 wt%

0 5 10 15 200

10

20

30

40

50

60

Tena

city

(cN

/tex)

con

dDraw ratio

0 wt% water 2 wt% water 5 wt% water

0 1 2 3 4 5104

2x104

3x104

4x104

Zero

she

ar v

isco

sity

, Pa.

s

Water content, %0

1

2

3

ω at 80C

ω at 70Cη0 at 80C

ω a

t CO

P, s

-1

η0 at 70C

• 5 wt% water in [DBNH][OAc] allows complete dissolution of 13 wt% birch-PHK

• The presence of water in an amount of 1-5 wt% decreasesthe viscosity and increases the viscose properties of the dope

IONCELL-F Performance

0 5 10 15 200

200

400

600

800

1000

Lyocell

Draw ratio (DR)

Tens

ile s

treng

th (M

Pa)

*

* in the conditioned state

13 wt% EPHK

Regular viscose

Modal

3 4 5 6 70,0

0,5

1,0

dw/d

(logM

M)

log(MM)

PULP DOPE FIBER

Very little degradation, which could be furtherreduced by reduced dissolution temperature

kDa PULP DOPE FIBERMw 240.4 216.0 207.5Mn 72.2 76.8 77.5PDI 3.3 2.8 2.8

Draw Ratio Cellulose Concentration

Polymer Stability

0 5 10 15 200

200

400

600

800

1000

Draw ratio (DR)

10 wt% 13 wt% 15 wt% 17 wt%

Tens

ile s

treng

th (M

Pa)

** in the conditioned state

Effect of (residual) lignin

Recycledcard board

Ash = 0.1 %Lignin = 3 %Hemi = 16.6 %[η] = 500 mL/g

Pretreat-

ment

0 5 10 15 20 25 30 350,0

0,2

0,4

0,6

0,8

1,0

B3B4

B5

P2B2

CLY

Stre

ss (G

Pa)

Young's modulus (GPa)

CVCMD

P1

Ioncell-F(best)B... recycled board

P.... recycled paper

3 4 5 6 70,0

0,5

1,0

dW/d

Log(

MM

)

Log (MM)

Recycled board Fiber

Recycled card board, B2

Pulp / Lignin Blends

0 5 10 15 200

10

20

30

40

50

Tena

city

cond

[cN

/tex]

Elongationcond [%]

Viscose 0 wt% lignin 10 wt% Kraft 15 wt% Kraft 20 wt% Kraft 10 wt% Organosolv 15 wt% Organosolv 20 wt% Organosolv 30 wt% Organosolv

0,3 0,4 0,5 0,6 0,70

20

40

60

Cellulose

10 wt% Organosolv Lignin

C-C

car

bon

in to

tal C

, %

O/C atomic ratio

Milled wood Lignin

30 wt% Kraft Lignin

Lignin dyed textiles

Board

15 wt% Lignin

In each batch: white Ioncell, cardboard Ioncell, Lignin containing Ioncell Reactive dyes:

Batch dyeing process in 60 °C (Linitest , test dyeing machine)

Mechanical vs. structural properties

0 10 20 30 40 500

200

400

600

800

1000 10 wt% 13 wt% 15 wt% 17 wt%

Tens

ile s

treng

th, σ

F (M

Pa)

Elastic modulus, E (GPa)0 5 10 15

0,4

0,6

0,8

200

400

600

800

1000σF

σ F(M

Pa)

Draw ratio [-]

15

20

25

30

35

40

You

ngs

Mod

ulus

, E (G

Pa)

E

0 5 10 150,4

0,6

0,8

200

400

600

800

1000σF

amorphous orientation

Orie

ntat

ion,

f

Draw ratio [-]

crystalline orientation

15

20

25

30

35

40

CrIE

0 5 10 150,4

0,6

0,8

200

400

600

800

1000σF

σ F(M

Pa)

Draw ratio [-]

15

20

25

30

35

40

CrI

Cry

stal

linity

, CrI

(%)

E

400 600 800 10000,0

0,2

0,4

0,6

0,8

1,0

1,2

wet

-to-d

ry te

naci

ty

Tensile strength* (MPa)

10 wt% 13 wt% 15 wt% 17 wt%

*conditioned state200 400 600 800 1000

0

5

10

15

20

25

10 wt% 13 wt% 15 wt% 17 wt%E

long

atio

n at

bre

ak*

(%)

Tensile strength* (MPa)*conditioned stateSixta, H. et al. NPPRJ, 30(1), 2015, 43-57

Comparison of Fibers

Viscose Modal NMMO (Tencel®)

IONCELL13 wt% 15 wt%

Titre [dtex] 1.4 1.3 1.3 1.2 1.4Tenacity cond. [cN/dtex] 23.9 33.1 40.2 50.5 57.6Elongation cond. [%] 20.1 13.5 13.0 8.5 9.5Tenacity wet [cN/dtex] 12.5 18.4 37.5 46.4 56.7Elongation wet [%] 22.0 14.1 18.4 9.6 10.7

Röder et al. Lenzinger Berichte, 2009, 87, 98-105;Gindl et al. Polymer, 2008, 49, 792-799.

0 5 10 15 20 250

200

400

600

800

1000

CuproViscose, CV

NMMO

Tena

city

cond

[MP

a]

Elongationcond [%]

IONCELL-F

Modal, CMD

0 10 20 30 400,0

0,2

0,4

0,6

0,8

1,0

CV CMDNMMO

Tirecord

σ, GPa

Young's modulus [GPa]

IONCELL-F

Fabrics and garments from IONCELL-F

designed by Tuula Pöyhönen

SCARFNov. 2013

DRESSMar. 2014

MEN’S ACCESSORIESAug. 2014

knitted knitted woven

AALTO University, Biorefinery Research GroupFebruary, 2015

Thank you for your attention!