Preparation and

Characterization of
Cellulose Dopes in NMMO

Frank Meister, Birgit Kosan

Thuringian Institute for Textile and Plastics Research,
Breitscheidstraße 97, 07407 Rudolstadt, Germany
meister@titk.de

1
 Germany
Where TITK is localised ?

Thuringia District Saalfeld-

Rudolstadt

Rudolstadt

TITK, F. Meister 15.04.2015 2

 A brief history
1954 Prof. Dr. Böhringer constitutes the Institute for Textile Technology of man-made Fibres
(ITC) in fact and law independent from the man-made fibre mill Schwarza
1970 ITC looses its independence and becomes a part of the central textile research of the
man-made fibre mill (R&D activities on all fields of Textile Research; up to 480 employees
at the end of 1980’s)
1991 re-foundation of the TITK as a first private, non-profit R&D institute of Thuringia strong
linked to business interests of SME (55 employees)
1992 formation of the OMPG as a 100 % subsidiary of the TITK
1997 TITK/OMPG transferred together with Zimmer Corp. results of self-contained Lyocell
technology (ALCERU process) into pilot plant scale 300 t/y of textile staple fibres and 10
t/y textile filaments
2002 Competence centre for Polysaccharide Research Jena–Rudolstadt is founded.
2005 TITK becomes an “Associate Institute” at the Technical University of Ilmenau;
2006 1,000 t/a pilot plant for textile Lyocell staple fibres manufacturing is launched at Shanghai
by Chinese Partner and TITK
2009 TITK became a member European Centre of Excellence for Polysaccharide Research
(EPNOE), TITK is awarded with Thuringian R&D Price for Transfer of Lyocell fibres
2011 installation of centre of excellence for direct dissolution and dry-jet-wet technologies
named Hugo-Richard-Küttner Centre

2014 Smartpolymer Ltd. is launched as 100 % subsidiary of OMPG

TITK, F. Meister 15.04.2015 3

 - since 1991 the TITK has taken its textile expertise to become a
modern institute for materials research,
- whereby TITK's R&D activities are primarily focussed on studies
with natural and synthetic polymers.
The Research Departments: • Native Polymers and Chemical Research

• Textile and Materials Research

• Plastics Research
• Functional Polymers Systems

The fields of expertise:

• Synthesis of polymers and functional additives
• Characterisation, forming and functionalisation of polysaccharides, particularly
cellulose and proteins
• Technical textiles
• Fibre-reinforced composites
• Polymer nano composites
• Polymer electronics,
• Polymer photovoltaic,
• Roll to roll coating,
• Materials modified by photo-chromic, thermo-chromic, electro-chromic and
solvato-chromic additives

15.04.2015 4
 TITK Group
TITK OMPG
Thuringian Institute for Textile and East Thuringian Material Testing
Plastics Research Company for Textiles and Plastics
(100 % subsidiary of TITK)

Employees: 125 Employees: 31

Members: about 90

 Research and development projects  analytical services (chemical, physical)

on polymer materials, processing and  polymer and material testing
technologies (50 R&D projects each  exclusive R&D orders
year)  product commercialisation and technology
transfer

smartpolymer GmbH
(100 % subsidiary of OMPG)
Employees: 30
 product commercialisation and technology transfer

TITK, F. Meister 15.04.2015 5

 Cell SolutionTM clima Cell SolutionTM skin care

Cell SolutionTM filaments

Cell SolutionTM bioactive

Smartpolymer GmbH
Cell SolutionTM ceramic

Cell SolutionTM protection

Cell SolutionTM hygienic

TITK, F. Meister 15.04.2015 6

 Outline
1. Pulp characterisation and impact of pulp impurities
1.1. General view
1.2. Effects of pulp impurities

2. Dope characterisation
2.1. Dope inhomogeneities
2.2. Rheological measurements of dope characteristics

3. Fibres spinning

4. Conclusions

TITK, F. Meister 15.04.2015 7

 Fibres and spinning procedures

Fibres are materials, what: - possess a huge length to thickness ratio

- molecules are preferentially oriented into MD

Fibres

natural man-made

animal, like silks,

modified natural
wools or hairs synthetics,
like PP, PA, PET,
vegetable, like PAN, PVC, PU
cotton or bast fibres inorganic,
like carbon,
mineral, like glass, metal,
basalt organic, like cellulose CV,
asbestos
CLY, CUP, CA, CAB, CC

TITK, F. Meister 15.04.2015 8

 Varieties of fibres spinning processes

 spinnability - is the capability to form mechanical stable liquid filaments

Melt spinning Solution spinning

polymer pellets polymer powder

h0 = 80 - 20,000 Pa s solvent
molten mass spinning dope
200 - 2,000 mm hole diameter,
h0 = 20 - 20,000 Pas
50 - 6,000 m/min take-up speed
melt spinning dry spinning wet spinning dry-wet spinning
10 – 60,000 spinning holes 40 - 250 mm
hole diameter,
cooling, cooling, drafting,
80 - 120 m/min
consolidating, consolidating take-up speed, coagulating
drafting, 2,000 up to
crimping drafting, 200,000 washing,
crimping spinning holes crimping

fibres, filaments fibres, filaments

TITK, F. Meister 15.04.2015 9
 What is the Lyocell Process cycle ?

N-methylmorpholine-
Dissolving Pulp N-oxide solution
(enzymatically activated)

Pre-dope
© holz.bayern.de
preparation

Biodegradation
Dissolving
Textile use recycled solvent
and process water
Textile
Spinning
processing After-treatment
washing, bleaching,
finishing, drying

Shaped bodies,
like fibres, filaments, MB-non-woven, films
TITK, F. Meister 15.04.2015 10
 Analytical methods for pulp characterisation at TITK
 Determination of ash content, Fe, Cu, Mn, Cr, Ni, Na, K, Mg and Ca
= important for process safety in the case of NMMO and the
contamination of spinning bathes because of solvent recovery

 Determination of Cuoxam-DP by capillary viscometry

= average degree of polymerisation for estimation of usable
cellulose concentration for dissolution tests, evaluation of
cellulose degradation at dissolution and shaping processes

 Molecular weight distribution (MWD) by size exclusion

chromatography (SEC)
= MWD of the pulp influences the solution properties, the spinning
behaviour and attainable fibre properties

 Content of carbonyl and carboxyl groups

= influenced by pulp cooking processes and MWD of the pulp

 a-cellulose content
= important for solution properties and attainable fibre properties

TITK, F. Meister 15.04.2015 11

 Main solvent degradation effects in the system cellulose /
N-methylmorpholine-N-oxide (NMMO)
Thermal degradation
NMMO _
O
labile oxidant O +N 2/3 O N + 1/3 O N H + 1/3 CO2 + 1/3 H2O

Cellulose
end groups Hydrogen bond system Oxidation of cellulose, deoxygenation of NMMO
sugar acids between cellulose and NMMO O
radicals OH OH
OH
OH O N
OH Cell-O O Cell-O OH
O
Cell-O
RO
HO
O
OO
HO
OR
HO OH HO OH + O N
HO O-Cell
OH OH OH O
Impurities O
OH
O
N
O

H
especially iron O H
OH
CH3 O O
O
H N
or copper ions H OH
Polonovski type reaction
Cell-ON O H O OH
O HO
CH3 HO O-Cell
O
O
RO HO
OR O
OH
O
AA B
Properties of OH O N O N O N CH2 + O-Acyl + H-B
OH
additives O-Acyl
-
pH value, OH

proton AA = acylating agent O NH

donating B = Base O N CH2OH
groups like + HCHO
carboxyl, or temperature
amino, and Radical reaction
pore size,
pressure
particle size ,
O N
O
+ Fe(II)
2 H+
O
.
N + Fe(III)
-H2O
porosity

References: Lukanoff, B., Philip, B., Schleicher, H.: Acta Polymerica 35, (1984), 339-343
Taeger, E., Franz, H., Mertel, H.: Formeln, Fasern, Fertigware 4, (1985), 14-22
Buijtenhuijs, F.A., Abbas, M., Witteveen, A.J.; Papier 12, (1986), 615-619
Rosenau, T., Potthast, A., Sixta, H., Kosma, P. Prog. Polym. Sci. 26, (2001), 1763-1837
TITK, F. Meister 15.04.2015 12
 Dope preparation tests in laboratory scale
3
by preparation of about 250 g cellulose solution it will be possible to test most
suitable dissolution conditions, to characterise solution properties and to realise a
first laboratory spinning test

modified laboratory kneading system,

Haake Rheocord 900

TITK, F. Meister 15.04.2015 13

 Protocol for cellulose dope characterisation
4
 Refractive index: determination of water contents in solvents and in
cellulose dopes with known cellulose content,
important for the completion of the water
removing in the case of NMMO monohydrate
 Solids content: precipitation, washing, drying and weighing of the
cellulose from a definite dope sample
 DP and MWD: determination of the cellulose DP in cuoxam
solution and molecular weight distribution of
precipitated cellulose from dopes or fibres
Helos Particle Analyser

 Microscopy: monitoring of fibre residuals in cellulose dopes by

polarising microscope
 Particle analysis: particle content in dopes, particle size distribution
between 0.5 and 175 μm by laser diffraction
 Rheometry: zero shear viscosity, storage and lost moduli,
master curves and mean relaxation time of Haake Rheostress RS 100

cellulose dopes

TITK, F. Meister 15.04.2015 14

 Polarising microscopy
5

 visualisation of discrete particles with diameters greater than 10 μm

(not perfect dissolved fibre residuals, pulp or solvent impurities)

incomplete dissolving state a few fibre residuals of 10 to dope without visible particles
30 μm

TITK, F. Meister 15.04.2015 15

 Particle analysis by laser diffraction
 detection of particle sizes between 0.5 and 175 μm; particle content is based
on basic calibration using spherical particles
 verification of gel particles with minor differences in the refraction index by
means of Fraunhofer diffraction
 measurements only possible at low particle contents
 Helium-Neon laser working with wave length at 632 nm
 temperature controlled measuring cell
100 120

density q 3*(x) / %
80 100
Q 3(x) / %

80
60
60
40
40
20 20

0 0
0.5 1 5 10 50 100
particle size / µm

TITK, F. Meister 15.04.2015 16

 Rheological evaluation of polymer solutions
7
1. Determination of zero shear viscosity h0 by means of creep and creep recovery
 is one of the most important rheological parameter in polymer industry
 it permits to give relative information for change of molecular weight
 may be determined (a) by rotation test at controlled shear stress (90
Pa) or (b) frequency sweep (oscillation test) from h*, if angular velocity
w0
2. Characterisation of the viscoelastic flow behaviour and stress relaxation
 oscillation tests (frequency sweeps between 0.046 and 14.7 Hz) at
different temperatures for calculation of master curves (storage and loss
moduli as well as the complex viscosity depending on frequency
respectively angular rate, referring to a reference temperature, i.e. 85 or
95 °C)
 determination of the cross over between storage and loss modulus and
the plateau moduli (plateau value of the storage modulus)
 calculation of the weighted relaxation spectra (relaxation time lm,
information on the molecular mass distribution of the polymers which
are involved in the solution state by rheological methods
TITK, F. Meister 15.04.2015 17
 Rheometric evaluation of polymer dopes is realised by 2 different
experimental approaches:
1. Creep (and creep recovery trial) - shear stress steps
 determination of the linear viscoelastic behaviour of meltable or of
dissolved polymers above two shear stress steps (1) t = 0  t0
between t0 and t2 and (2) t0  t = 0 between t2 and t4
 calculation of zero shear viscosity h0 and molecular weight M (h0 
M3.4); at begin of the trial a constant shear stress t0 is impressed until
the end of reading
 h0 = t0 / tan b = t0 / [g3 / (t2 – t1)] = t0 / g0
g
t
t0 g3

ge

g2

g1 gv
t0 t2 t4 t
t0 t1 t2 t3 t4 t
TITK, F. Meister 15.04.2015 18
 2. Relaxation trial - deformation steps
- by dynamic-mechanical measurements (deformation steps) complex material
characteristics like  complex viscosity 𝜼∗ (𝝎)
 storage modulus G’(w) and
 loss modulus G”(w)
are detected at exactly allowed shearing amplitudes (amplitude sweep) or
frequencies (frequency sweep) and temperatures (commonly 85 °C)




TITK, F. Meister 15.04.2015 19

 100,000 10,000
WLF = Williams, Landel, Ferry plateau modulus
31,700 Pa
h* 
Storage / Loss Modulus [Pa]

Complex Viscosity [Pas]

Dope 1: 10,000 1,000

11.8 % cotton linters in NMMO

 G’’
Cuoxam-DP pulp: 584 cross over
2.9 rad/s // 4,255 Pa
DPL: 570 1,000 100

h0 (85°C): 8,211 Pas

 G’

 h0 could also be calculated

100 10
0,01 0,1 1 10 100 1,000
from the plateau value of w [rad/s]
the complex viscosity storage modulus loss modulus complex viscosity

TITK, F. Meister 15.04.2015 20

 Master curve of spruce pulp in NMMO
(reference temperature: 85°C)
100000 10000

Dope 2: Plateau Modulus

27200 Pa
12.1 % spruce pulp dissolved in
NMMO
Storage / Loss Modulus [Pa] h* 

Complex Viscosity [Pas]

10000 1000

DP pulp: 615  G’
DPL: 564
h0 (85°C): 12,760 Pas  G’’
1000 Cross over 100
1.3 rad/s // 2390 Pa

100 10
0,01 0,1 1 10 100 1000
w [rad/s]

12.1 % SP - Storage modulus 12.1 % SP - Loss Modulus 12.1 % SP - Complex Viscosity

TITK, F. Meister 15.04.2015 21

 Shear stress relaxation

 relaxation is a specific material function and controls time-dependent deformation and

back-deformation of polymer fractions of defined molecular weight and molecule
structure
 such specific functions aren’t directly detectable, but could be calculated by means
of linear viscoelastic (LVE) theory - generalised Maxwell model
 relaxation = f(h*(w), G(t)) (1), because validity of Boltzmann super positioning principle
at LVE region t(t) = 𝒊 𝝉𝒊 𝒕 = 𝜸𝟎 ⋅ 𝒊 𝑮𝒊 ⋅exp (-t / li) (2)
t(t) = tmax , if t = 0, t(l) = 0.368 ⋅tmax , if t = l and t(t) = tmax  1/e = 0, if t =  (3)
3000

11.8% CL in NMMO
12.1% SP in NMMO
2500

H(l)l ...
2000

- represents the collectivity of similar

H(l) * l [Pas]

1500
molecules of a polymer
- indicates the frequency of
1000 occurrence of macro molecules
exhibiting a low or a high relaxation
500 time l

0
0,001 0,01 0,1 1 10 100 1000

Relaxation time l [s]

TITK, F. Meister 15.04.2015 22
 Rheometric parameter and its structural relevance

Rheological dopes data: 11.8% CL (584) 12.1% SP (615)

in NMMO in NMMO
0 𝜂
𝑈𝜂 = 𝜂+# - 1, : rheological poly- zero shear viscosity (85°C) Pas 8,211 12,760
dispersity angular rate w at cross over rad/s 2.9 1.3
storage modulus G' at cross over Pa 4,255 2,390
plateau modulus Pa 31,700 27,200
h  : complex viscosity at cross over rheological polydispersity Uh 3.0 3.7
relaxation time lm at H(l)m s 2.4 11.6

wco Mw (as lower wco as higher Mw, if PDI (Uh) is more or less identic )

Gco‘ PDI (as lower Gco‘ as higher PDI (broader MWD), if DP=const.)

lm important value for spinning safety (viscoelastic dope behaviour)

(as higher lm as higher safety of use of a longer air gap)

h0 Mw (as higher h0 as higher Mw, h0  Mw3.4)

Haake Mars II rheometer

References (German language, only):
Schrempf, Ch.; Schild, G.; Rüf, H.: „Pulp-NMMO-Dopes and their Flow Behaviour“ Das Papier 12/1995, 748-757
Michels, Ch. et al.: About Determination of Molecular Mass Distribution in Cellulose from Rheometric Data,
Das Papier 1/1998, 3-8
TITK, F. Meister 15.04.2015 23
 Final examination: Laboratory spinning tests
13
 dry-wet spinning tests for preparation staple fibres using available
laboratory spinning equipment
 testing of suitable spinning parameters (temperature, air gap length,
take-up velocity, conditioned air gap clima, …)
 detection of textile-physical values of the prepared fibres using
defined ambient atmosphere (fineness, elongation, tenacity, loop
tenacity, fibrillation behaviour, modulus)

TITK, F. Meister 15.04.2015 24

 Continuous dry-wet spinning testing plant at TITK

dope
preparation
fibre
staples dry-jet-wet
cutter spinning bar

fibre after-
filament
treatment
washing
and fibre
finishing

filament
dryer

fibres dryer
and
bobbin
baling press
winding-up

TITK, F. Meister 15.04.2015 25

 Conclusion

- air-gap spinning of cellulose is among solution spinning and needs a lot

of additional knowledge toward polymer properties in dissolved state
- analytical protocol of pulp and dope characterisation is a very suitable
instrument to guarantee save and optimal solvation and spinning
procedures
- rheological properties of polymer solutions are influenced by:
 properties of the polymer (DP, MWD, a-cellulose content)
 chemical -physical behaviour of the solvent (NMMO, different ILs)
 polymer concentration
 dissolving state
- dope characteristics are important criteria for
 most secure air-gap spinning procedure
 adjustment of intended fibre properties (fineness, tenacity,
elongation, …)
- all the properties of pulp and cellulose dopes have always to be adapted
for the shaping process, shaped product and intended application
TITK, F. Meister 15.04.2015 26
 Thank you very much for your kind attention !
Comments or any questions ?
Acknowledgement
Research activities presented
were financial supported by the
Federal Ministry of Economy
and Energy and the Thu-
ringian Ministry of Economy,
Labour and Development.
We also wish to express our
thanks to company partners for
cooperation and support and
textile research institutes
(STFI, HIT, TITV) for
processing and application
studies complementing the
TITK‘s R&D-activities. Contact:
Thuringian Institute for Textile and Plastics Research
Chemical Research Department
Breitscheidstraße 97, 07407 Rudolstadt
Phone: +49(0)3672 37 92 00 Fax: +49(0)3672 37 93 79
E-mail: kosan@titk.de, meister@titki.de http://www.titk.de
TITK, F. Meister 15.04.2015 27
 Agenda 04/08/2015 at TITK

14.15 Arrival of participants at TITK, walk to IUK

14.20 – 14.50 Presentation „Preparation and Characterization of Cellulose Dopes in NMMO“,

Dr. Meister

14.55 – 16.20 Activity centres for explanation and demonstration in following topics
1. Characterisation of cellulose dopes in NMMO
Dr Meister
2. Dry-jet-wet (air-gap) sping of cellulose dopes at laboratory scale
Mrs Dr Kosan
3. Demonstration electrospinning
Mrs Dr Römhild
Three groups (about 10 persons) are guided by TITK staff.
Group 1 begins at Station 1 and ends up at Station 3, Dr. Schaller
Group 2 begins at Station 2 and ends up at Station 1, Dr. Schulze
Group 3 begins at Station 3 and ends up at Station 2, Hr. Schmuck

about 16.20 every group immediately adjourns to the bus

16.25 Trip to the smartpolymer pilot plant at Prof.-Hermann-Klare-Straße 23

16.30 Round tour through the pilot plant, Dr. Meister

17.00 End of the course at TITK, return to Jena, Dr. Koschella

TITK, F. Meister 15.04.2015 28