Cellulose (2019) 26:2913–2940

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REVIEW PAPER

A critical review of manufacturing processes used

in regenerated cellulosic fibres: viscose, cellulose acetate,
cuprammonium, LiCl/DMAc, ionic liquids, and NMMO
based lyocell
Anwar J. Sayyed . Niteen A. Deshmukh . Dipak V. Pinjari

Received: 27 September 2018 / Accepted: 5 February 2019 / Published online: 12 February 2019
Ó Springer Nature B.V. 2019

Abstract It is essential for textile manufacturing rayon fibres and it has great potential to fulfil the
industries to invent new resources, composites and environmental and customer requirements. The pre-
industrial technologies, which are environmentally sent review delivers a complete account of all the six
acceptable and can fulfill the consumer necessities. types of cellulose regeneration processes namely
Therefore, in the recent years, large number of viscose, cellulose acetate, cuprammonium, LiCl/
research is focused on optimizing and modifying the DMAc as well as lyocell processes based on ionic
fibre manufacturing processes. The recent advances in liquid or NMMO. Additionally, the review considers
technology have allowed modifying these processes latest developments with process technology, cellu-
through various techniques and novel raw materials/ lose swelling and dissolution phenomena, factors
additives to manufacture the fibres. Among the various affecting the lyocell process and future prospects of
fibre regeneration processes, the NMMO based lyocell the lyocell fibres.
process has numerous advantages over conventional

A. J. Sayyed
Institute of Chemical Technology (ICT),
Matunga, Mumbai 400019, India

A. J. Sayyed  N. A. Deshmukh
Pulp and Fibre Innovation Centre (PFIC) - A Unit of
Grasim Industries Ltd. Taloja, Navi Mumbai 410208,
India

D. V. Pinjari (&)
National Centre for Nanosciences and Nanotechnology,
University of Mumbai, Kalina Campus, Kalina, Santacruz
(E), Mumbai 400 098, India
e-mail: [email protected];
[email protected]

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Graphical abstract

Keywords Fibre regeneration process  Cellulose generation of natural fibres varies from year to year
dissolution  Lyocell  Viscose  Cuprammonium  which causes inflation according to variations in
LiCl/DMAc unpredictable demand.
On the other hand, fibres manufactured by humans
are termed as man-made or artificial fibres or synthetic
fibres. Man-made fibres may also be divided into the
Introduction two categories, i.e., regenerated cellulosic fibres and
synthetic fibres. Synthetic fibres such as polyamides
Natural fibres with their long history of serving (Nylon 6, Nylon 66), acrylics, polyesters, and
mankind are very important in a wide range of polypropylene are produced from synthetic high
applications (kozłowski and Mackiewicz-Talarczyk molecular weight polymers obtained from polymer-
2012). For thousands of years, the usage of fibre has ization of monomers. Although, synthetic fibres have
been limited to natural fibres only depending upon high production rate, low cost, are more durable and
their respective applications to meet basic require- multipurpose than natural fibres, they are majorly non-
ments such as clothing, storage, building material, and biodegradable and their production involves processes
for items of daily use like ropes and fishing nets. that pose severe threats to the environment and human
Textiles were based only on natural products until the health (Singh and Bhalla 2017). Further, due to their
early years of the twentieth century. Natural fibres, high stiffness, poor moisture absorbency, difficulties
according to their origin, can be classified into plant- in finishing and washing, the wearing comfort of
based fibres, animal fibres, and mineral fibres (Fig. 1) synthetic fibre based clothing is diminished (Vignes-
(Jabbar and Shaker 2016). Natural fibres such as waran et al. 2014).
cotton, silk etc., are generally more comfortable to To overcome the limitations of synthetic fibres and
wear and environment friendly. Therefore, the incorporate the benefits of natural (cotton) fibres,
demand for the natural fibres has increased which cellulose-based regenerated fibres have attracted
made them expensive (Ramamoorthy et al. 2015). attention (Chavan and Patra 2004). Cellulose is one
However, natural fibres have limited reserves and low of the most abundant, biodegradable, biocompatible
production rate to meet the growing consumer and renewable polymer resources available to man-
demands (Chavan and Patra 2004). Also, the kind. Recent advances in technology have allowed the

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complete cellulose dissolution (Cuissinat and Navard

2006). Therefore, while studying fibre regeneration, a
great deal of focus should be on cellulose swelling and
dissolution apart from the spinning process.
Therefore, this review summarizes different cellu-
lose-based fibre manufacturing processes in textile
industries. Further, critical study of swelling and
dissolution phenomenon of the most commonly used
processes (viscose, cellulose acetate, cuprammonium,
Fig. 1 Classification of textile fibres
LiCl/DMAc, Ionic liquid, and lyocell) in fibre man-
ufacturing has also been illustrated herewith.
use of natural raw materials to be processed into man-
made fibres. As a result, regenerated cellulosic fibres,
utilizes natural cellulose as the raw material and are Fibre regeneration processes
processed by either derivatizing cellulose or by direct
dissolution. Viscose and cellulose acetate are exam- Regenerated fibres are derived from cellulose which is
ples of derivatized regeneration process while lyocell obtained from cotton linter or wood, and bamboo. The
fibres obtained from direct dissolution in NMMO, systematic classification of different regeneration
represents non-derivatized process. processes is shown in Fig. 2. There are two core
Being natural in origin, regenerated fibres provide regeneration processes: i.e., derivatizing process and
the comfort of natural fibre (Gorji and Bagherzadeh direct dissolution (non-derivatizing) process. In the
2016), breathability, lustre, softness, drapability etc. derivatizing process, cellulose is modified before
Due to these inherent qualities, the demands of dissolution. On the other hand, in non-derivatizing
regenerated cellulose fibres have been increased in process cellulose is directly dissolved in solvent
the global market. The worldwide production of without modification to regenerate fibres. This is
dissolving grade cellulose pulp has increased since described in detail in subsequent sections.
the beginning of the twenty-first century with a total
output of 2.67 million tonnes (MT) in 2001 to 4.2 MT Derivatizing process
in 2011 (Shen et al. 2010) and 6.68 MT in 2014 (Liu
et al. 2016). The current estimate is that dissolving In the derivatizing process, derivatives and complexes
pulp demand will hit 7.6 MT in 2018 (Young 2017). of cellulose like methylol cellulose, cellulose nitrite,
This boost in the market can be attributed to increased cellulose acetate and xanthate (viscose) are formed.
consumption and production of regenerated textile During derivatization, the chemical structure of the
fibres. However, there are also some limitations with starting cellulose is modified by adding another
the regeneration process like cellulose dissolution, reagent to it which forms an intermediate compound
solvent selection, and process parameters. Among such as sodium or acetate derivatives. Further these
these, cellulose dissolution is a critical part of the intermediate compounds are processed and dissolved
regeneration process and governs the spinning process followed by regeneration of cellulose fibre. However,
and fibre quality. Cellulose is difficult to dissolve it has except cellulose acetate and viscose (xanthate) pro-
high intermolecular hydrogen bonds that act as a cess, very few derivatives have been spun into fibres
restricting point for dissolution (Cuissinat and Navard and commertialized. The global viscose staple fibre
2006). Hence, various dissolution and regeneration market accounted for 5594.08 kilos metric ton in 2017
processes are developed. The process of cellulose (Mordor Intelligence 2018) due to growth in the textile
dissolution essentially involves cellulose pre-treat- industry. Similarly, global cellulose acetate market
ment with a solvent that swells the cellulose chains was estimated to be 614.03 kilo tons in 2016 and will
resulting in relaxation of cellulose molecules. This reach to 820.04 thousand tons by 2024, due to
boosts solvent diffusion kinetics to the crystalline increasing consumption of cigarettes where it is used
regions that are tightly packed thereby facilitating as filters (Reportbuyer 2017). Therefore, the detailed

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Fig. 2 Classification of
cellulose regeneration
processes

discussion of the derivatizing process is restricted to parameters in either one or more steps, it is possible to
viscose and cellulose acetate. generate a wide variety of rayons. An outline of the
viscose process is shown in Fig. 3. Briefly, in this
Viscose process process, wood pulp which comprises of short fibres of
cellulose is converted into a spinnable solution using
Viscose fibre is the most versatile of all man-made various controlled and co-ordinated steps which is
fibres in textile and other applications. This is because then converted into longer filaments. These long
the viscose fibre can be engineered chemically and filaments are precisely cut into staple fibres by
structurally in many ways. maintaining the length, denier, cross-sectional shape,
The viscose process comprises of various steps, and other physical properties.
which must be carefully controlled to produce the The first step for cellulose regeneration is swelling
desired end quality product. By modifying the process and dissolution of pulp. It is known that during

Fig. 3 Schematic of
viscose process

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Cellulose (2019) 26:2913–2940 2917

swelling and dissolution the interaction between can be used for spinning. The process parameters such
aqueous alkali solutions and cellulose is very critical. as spinning temperature, spinneret type, spinning
One of the leading opinions in the case of the swelling pressure, spin bath conditions etc., are important to
system is that NaOH molecules form hydrates with make regeneration of viscose fibres from the dope.
water molecules and hence they are able to break the Therefore, investigations on effect of parameters and
inter- and intra-molecular hydrogen bonds between process optimization have been continuously carried
cellulose molecules (Cai et al. 2008). Due to this out on the viscose process.
phenomenon, the morphological structure and prop- In recent years, some researchers have used differ-
erties of the native cellulose changes. Morphologically ent raw materials and additives to regenerate the fibres
the entering point of NaOH solvent is the amorphous from this process for advanced applications like high
regions between the fibrils. It swells the amorphous breaking strength and shrinkage reistance fabric from
sections first, and later, the alkali ions diffuse into the modal fibre, fire retardant fibres, thermal stabilizers
more crystalline sections of the cellulose resulting in and electrical insulation applications. Some scientists
formation of an intermediate known as ‘‘alkali cellu- also tried to modify this process through different
lose’’ or alkcell. This intermediate shows irreversible techniques like blending, grinding and shaping treat-
swelling and the phenomenon is known as ‘‘mercer- ment. All the recent techniques using viscose process
ization’’ (Kihlman 2012). Schematic representation of has been summarized in Table 1.
the mercerization process as described by Okano and From Table 1, it can be observed that much
Sarko (1985) is explained in Fig. 4. preference is given to process optimization as well
In the mercerization process, NaOH is sturdily as fibre properties. The modal regeneration process is
acting on the primary wall morphology of cellulose one of the innovative and advanced method for the
fibre. For example, native cellulose changes its viscose process. However, modal is more expensive
crystalline structure from cellulose I to cellulose II than viscose rayon and cotton. Also, 100% modal
(Okano and Sarko 1985; Egal et al. 2007). It means fibres require ironing thoroughly as they tend to pile
that mercerisation is not cellulose dissolution phe- due to long fibres. Therefore, considerable work still
nomenon but a change in the morphology and needs to be done on the process optimization of the
crystalline structure under swollen state during the modal method.
formation of various alkali cellulose complexes Although viscose based regenerated fibres have
(Budtova and Navard 2016). Thus, in viscose process, found numerous applications such as home textiles,
the NaOH solvent changes the crystalline structure of clothing and industrial textiles including coated fab-
cellulose and forms mercerized alkcell. rics, conveyor belts, and automobile tyres (Krässig
This is followed by xanthation process during et al. 2004), the process produce toxic chemical waste
which, the mercerized alkcell reacts with CS2 vapour during production causing environmental pollution.
to produce sodium cellulose xanthate. It is this One of the biggest issue with viscose manufacturing is
derivative which is soluble in dilute caustic soda and the generation of harmful effluent (Deo 2001). Carbon
when dissolved forms homogeneous viscose dope that disulphide, which is used in significant quantity in

Fig. 4 Schematic
representation of the
mercerization process

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Table 1 Recent developments in viscose process

Sr. Process/ Process condition Application References
no. technique

1 Wheat Mixed with alcohol at 30–70 °C for 2–4 h, centrifuging and Protein fibres Xu et al.
gluten separating, collecting supernatant, and evaporation to (2017)
powder obtain a protein solution
Preparation of viscose spinning liquid, using cotton pulp,
immersing in NaOH solution
Spinning: continuously blending plant protein solution and
viscose spinning liquid in the pre-spinning injector,
mixing via a dynamic mixer and a static mixer, spinning
to obtain the product
2 Grinding Grinding the wood pulp Cellulose nano-fibres Yamane
treatment The pulp was treated with saturated steam (1.55 MPa, et al.
200 °C) for 3–9 min (2015)
The pulp was immersed in dilute aqueous NaOH solution to
prepare cellulose/alkali slurry
Agitation, mixing gives to complete dissolution
3 Shaped Steeping at 30 °C to about 50 °C, Xanthation is carried out Casting cellulose film Cockroft
articles using about 30–40% carbon disulfide by wt. of cellulose and Fisher
present (2012)
Xanthation is carried out, at least partially, at about 20 °C
to about 30 °C, dissolution. Is carried out, at least
partially, at about 10 °C to about 25 °C
4 Fire Used medicinal cotton and dissolve into 16–20 NaOH, Fire-resistant fibres Wang et al.
retardant alkalizing at 35–45 °C for 1.5–3 h; then adding CS2 (2012)
Yellowing at 35–45 °C for 3–5 h
Dissolution was done with 4–5% sodium NaOH solution
and adding carboxylic multi-wall carbon nanotube
(0.1–1 wt% of the medicinal cotton) to obtain multi-wall
carbon nanotube-dispersed yellowing cellulose viscose
5 Modal High wet modulus (HWM) rayon is a modified high wet The tactility and soft fluidity of Hibbert
fibre strength viscose derived from beech wood that will modalTM has focussed it on the (2014)
perform much like cotton when laundered underwear and fashion market
Fibres can also be mercerized for increased strength and
luster

viscose manufacturing process, is a source of major high BOD, COD and total and dissolved solids
environmental problem. Sulphur introduced in this (Camper and Bott 2006). The viscose rayon manufac-
process gets dispersed as sulphur compounds (CS2, turing process is also energy-intensive (Hergert and
H2S, COS, SO2) in the exhaust gases, process baths, Daul 1977). Besides this, viscose rayon production has
solid wastes and product itself. About 15% of the high labour demand, and takes longer time for dope
CS2 used is converted into H2S in the form of viscose preparation (nearly 48 h) as the process is very
by product and sodium tri-thio-carbonate. Recovery of complex and number of steps are involved in
all the sulphur used in the process is not possible and converting pulp into rayon fibres (Chavan and Patra
only about 50% CS2 reclaim is achieved. Moreover, 2004). Therefore, it is imperative to either improve the
zinc sulphate, a viscose spin-bath component, is often viscose dissolution and regeneration process or devel-
made at the rayon plant by dissolving metallic zinc in oped an alternative, non-polluting route for fibre
sulphuric acid. This chemical is toxic to the aquatic regeneration.
life. Overall process effluents from viscose plant have

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Cellulose acetate process of cellulose and has three hydroxyl groups which can
react to form acetate esters. The most common form of
Cellulose acetate is the acetate ester of cellulose. It cellulose acetate fibre has an acetate group on
was produced first in commercial scale by Celanese in approximately two of every three hydroxyls. Mecha-
the year 1923 in the form of silk. The United States is nism of the cellulose acetate preparation is explained
the largest producer of cellulose acetate fibre. This in Fig. 6 (Alnokta 2009).
fibre is produced by reacting cellulose pulp with acetic Cellulose acetate filaments are spun into acetate
anhydride which is explained in detailed below. yarns and blended with other fibre materials to form
Through this chemical reaction, cellulose acetate fabrics, apparel linings, and knitwears. Porous and
flakes are produced, which in turn are dissolved in a hydrophilic attributes of cellulose acetate filament
solvent, filtered, to obtain the spinning cellulose dope make it the preferred material to be used in textile,
solution (Ertas and Uyar 2017). This cellulose dope apparel application and cigarette filters. It is also used
solution is extruded through the spinneret with diam- as partial substitutes for production of general con-
eters ranging from 30 to 50 lm. The yarns are sumer articles including clothing, lining, felts, uphol-
produced by evaporating the solvent in the subsequent stery, carpets, umbrellas, and various kinds of
step. This process for producing acetate fibre is known knitwear, for example, to reduce fibre/fabric shrink-
as the dry spinning method (Fig. 5). After the cellulose age, to improve wrinkle resistance, and to lower raw
dope has been extruded through the spinneret, it takes material costs. Therefore, the focus of current research
on a round shaped cross section. However, if the rate is on the improvement in final applications of cellulose
of evaporation of solvent is very high then this would acetate fibres. This is briefly explained in Table 2.
lead to the formation of a skin layer on the surface of The summarized data of Table 2 shows that current
the fibre. After that, evaporation of the solvent from research has been focused on the Cigarette filters, drug
the inside of the fibre causes the skin layer to cave in delivery, nanofibre and textile/apparel. Cigarette
toward the fibre cross-section, giving rise to the final filters dominated the cellulose acetate global market
multi-lobal cross-section. with a share of 80% in 2014. This application sector is
During dissolution mechanism, the cellulose is expected to play a major role in the consumption of
reacted with acetic acid and acetic anhydride in the cellulose acetate by the end of 2023. Textile and
presence of sulfuric acid. It is subjected to a controlled, apparel was the second-largest application segment of
partial hydrolysis to remove the sulfate and a sufficient the global cellulose acetate market in 2014. However,
number of acetate groups to give the product with cellulose acetate fibres have certain drawbacks such as
desired properties (Watabe et al. 2018). The anhy- poor fibre strength, poor abrasion resistance, and poor
droglucose unit is the fundamental repeating structure thermal retention. In addition to that acetate fabrics are

Fig. 5 Schematic diagram

of the cellulose acetate fibre
production

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Fig. 6 Mechanism of the

cellulose acetate preparation

sensitive to discoloration due to air pollutants (Cohen route and N-methylmorpholine-oxide (NMMO) route.
et al. 2012). Similar to rayon, it is often used as a These are described in the subsequent sections.
substitute for silk, but acetate is much weaker than
either rayon or silk and is generally used for apparel Cuprammonium process
that will not be worn often (Kadolph 2009). Specif-
ically, special occasion clothing is made from acetate Cuprammonium process invented in 1890s, resulted in
fabric (Cohen et al. 2012). Therefore, for practical rayon formation which most closely resembles silk. It
applications cellulose acetate fibres are combined with is the second artificial silk process that has been
other fibres that have sufficient strength, such as commercialized by the Swiss chemist Matthias
polyester. Other disadvantages of acetate fibres Eduard Schweizer in 1857. Post which the fibre
include low durability and high tendency to gather process was invented by a French Chemist, Louis-
static electricity. To offset or remedy these deficien- Henri Despeissis, who worked on spinning fibres from
cies, acetates are often chemically modified or blended Schweizer’s solution in 1890. In this process, cellulose
with other fibres. is dissolved in an aqueous solution of cuprammonium
hydroxide, and the resulting solution is spun to form
Direct dissolution process fibres. The production steps of the cuprammonium
process are presented in Fig. 7 (Woodings 2001).
In the direct dissolution process, cellulose directly Initially, the sticky and viscous material of cellulose is
dissolves in an organic solvent without the formation removed in advance by washing, to accelerate disso-
of an intermediate compound. This is a fundamental lution. Then cellulose solution is filtered by asbestos
difference between the direct dissolution and deriva- and sand to eliminate the un-dissolved material. The
tizing process. The direct dissolution processes solution is extruded into a coagulation bath of dilute
include cuprammonium, LiCl/DMAc, and lyocell acid, alcohol and concentrated cresol solution for
process. Among these, the lyocell process can be cellulose precipitation. It results in the regenerated
carried out by two different routes, i.e., Ionic liquid cellulose filaments.

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Table 2 Recent developments in cellulose acetate process

Sr. Process condition/applications Developments References
no.

1. Premade 25 mm cellulose acetate filters from 1R6F cigarettes Additional charcoal in cigarette filters for Goel et al.
were cut perpendicular to their length into two pieces: mouth reduction of many toxicants from tobacco (2018)
end (10 mm) and tobacco end (15 mm) smoke
Create a central cavity like plug-space-plug configuration in
cigarette holder
The cavity was filled with 0–300 mg of pre-weighed activated
charcoal with the remaining space filled with glass beads
(500–750 lm)
The cigarettes were conditioned for testing by removing them
from cold storage and placing them in a constant humidity
chamber (60% relative humidity, 22 °C), for at least 24 h
before smoking
2. A weighed amount of cellulose acetate (CA) powder was Synthesis of cellulose acetate nanofibres for Mehrabi
dissolved in 3:1v/v acetone/dimethylformamide (DMF) to drug delivery et al.
obtain a CA solution at a concentration of 8 to16% w/v (2017)
Acetaminophen or morphine-loaded CA solutions were
prepared by dissolving CA powder and Acetaminophen (A) or
morphine in the weight ratio of 5:1, in an acetone/DMF
mixture
Under optimum condition, they were electrospun into sandwich
structured membranes with the coaxial method and cellulose
acetate as the surface layer and cellulose acetate/drugs as the
core
3. Filter segments of cigarettes were modified to contain a central Modification in cellulose acetate-cigarette Morabito
cavity containing charcoal granules between two plugs of filters for mainstream smoke carbonyl et al.
cellulose acetate filter reduction (2017)
Pre-weighed charcoal loadings were placed between these plugs
Due to the extent of carbonyl reduction observed for king-size
cigarettes
Observation of the mouth end of experimental cigarettes after
machine smoking did not suggest charcoal release in the
present study
5. Application of cellulose acetate fibre in filtering material Development of cellulose acetate fibre and Si et al.
Application in cigarette filter tip cellulose acetate nanofibre used as filtering (2015)
materials
Cellulose acetate fibre or mixture of cellulose acetate fibre and
other fibres was processed into spunlace nonwoven without
pollution in the production
Application of CA nanofibre in filtering material
Application in air filter material
Application in biomedical material

The dissolution mechanism of cellulose in cupram- solution of copper sulphate by using either sodium
monium solution is based on Schweizer’s reagent. hydroxide or ammonia to form the reagent.
This reagent is the chemical complex of tetra-amine- A complex between Cu2? and (C6H8O5)2- n ions are
diaquacopper dihydroxide, [Cu(NH3)4(H2O)2](OH)2]. formed which aids the dissolution of cellulose in
Copper(II) hydroxide is precipitated from an aqueous Schweizer’s reagent. The equilibrium complex for-
mation is shown in the below reaction (1)

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Fig. 7 Production steps of

cuprammonium process

nCu2þ þ ðC6 H10 O5 Þn þ 2nOH !½CuC6 H8 O5 n cuprammonium rayon as an input for the circular
economy is the use of wasteful auxiliary hazardous
þ 2nH2 O:
chemicals used in the manufacturing process. Such as,
ð1Þ sodium hydroxide and sulfuric acid are both corrosive
After this complex formation, cuprammonium and care should be taken during handling. Ammonia is
cellulose solution reacts with sulfuric acid solution corrosive and exposure in air causes burning of the
after extruding through the spinneret to decompose eyes, nose, throat and respiratory tract. It should be
cuprammonium complex to cellulose. The regenera- noted that these chemicals are used in manufacturing
tion phenomenon mentioned above results in higher and are not present in the end product. Due to these
tensile strength (TS) and lower tensile elongation (TE) health related, environmental issues and expensive
for cuprammonium rayon than viscose rayon. Due to cellulose dissolution process, cuprammonium process
which cuprammonium rayon finds its application in is becoming unpopular in recent years.
knitted and woven wearing apparel, upholstery, and
decorative fabrics. Recently, cuprammonium rayon LiCl/DMAc process
are commonly used in depolymerization of cellulosic
biomass, preparation of helical fibres and nonwoven With the aim of dissolving cellulose, the solvent used
sheet, which are summarized in Table 3. A review of in LiCl/DMAc process is N,N-dimethylacetamide
the literature concludes that a lot of effort has been (DMAc). DMAc dissolves cellulose derivatives such
taken to improve and modify the quality of cupram- as cellulose acetate or (hydroxypropyl) cellulose on its
monium regenerated fibres. Table 3 illustrates the own. DMAc has the power to dissolve cellulose only
research work focused on the various mode of process when it conjugates with lithium chloride (LiCl).
parameters, like pre-treatment, modification of spin- LiCl/DMAc was found to be the only functioning
ning parameters and on the nonwoven section. In the lithium salt-organic solvent combination for cellulose
non-woven area, sheet formation application is com- dissolution in 1980 by McCormick. This system is
paratively simple and economically acceptable. used as a non-degrading solvent to determine cellulose
Although, cuprammonium rayon is replacing the molecular weight (MW) distribution (Bikova and
natural silk and it is widely used in wearing apparels, Treimanis 2002). On the other side, Rayonier group
upholstery, and decorative fabrics section, the process (1981) tried to discover the possible route for higher
is expensive and pose the environmental concern of amounts of cellulose regenerated through this solvent
releasing copper in the waste stream. Its manufacture system. So, that LiCl/DMAc solvent system could be
is illegal in the United States (US) at present, due to the considered for commercialization. The current opti-
chemicals used in this process. The biggest issue with mized process can dissolve cellulose up to 16% with

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Table 3 Recent applications of cuprammonium regenerated fibres

Sr. Modification Process detail Results References
no.

1. Efficiently enhance cellulosic oxygen A solution prepared by mixing copper Improve Cao and
sensitivity through cellulose pre- hydroxide and ammonia with a particular depolymerization of Zhao
treatment method catalyst cellulosic biomass (2015)
Which enhanced cellulose oxygen
sensitivity
Fenton reactions were carried out at RT and
add the H2O2 within 1.5 h
After Fenton reaction, recovered the
sulphuric acid by ammonia stripping under
nitrogen
2. Modification of spinning parameters The cellulose solution was inhaled into a Plant tendrils with a Jia et al.
such as spinning height, flow rate syringe with 2.28 mm dia helical structure (2014)
and moving speed of the coagulating The CuO helical fibre was obtained by prepared from a
bath calcination at 500 °C for 10 h cellulose solution
The flow rate of the cellulose solution was
7–10 mL/min
3. A nonwoven sheet is formed without Reduced hot water solubility of the Nonwoven sheet for Nomura
using a binder and surface treated for nonwoven sheet up to 0.1 wt% glass-like sheet (2004)
dust prevention The inserting paper is formed from only materials
regenerated cellulose
As results, a significant effect was observed
on suppressing dirt on the glass surface.
Sheet presses by a flat roller, it becomes
super calender
Super calendered sheet obtained thought 14
stage, 13 nips, a linear pressure of 1960 N/
cm, 80 °C and 60 m/min

Fig. 8 LiCl/DMAc process

steps

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minimum time (4–6 h) and temperature (85 °C). The LiCl/DMAc process is that, it does not lead to any
steps of the process are shown in Fig. 8, in which thermal runaway reaction unlike the NMMO process
cellulose activation, solvent preparation, and slurry where there is a probability of runaway reaction at
preparation are essential steps for complete dissolu- high temperature. Additionally, in the LiCl/DMAc
tion of cellulose. Subsequently, precipitation, regen- process, no additive or specialized equipment’s are
eration and solvent recovery steps are involved in fibre needed, and the process is also claimed to be
manufacturing. recyclable with a high recovery rate (Duchemin
Before dissolution, the cellulose polymer chains 2008). Due to the ease of processing of LiCl/DMAc
must be activated and opened into a relaxed confor- process and other advantages discussed above, many
mation thereby enhancing the solvent diffusion kinet- researchers prefer to use this process for advanced
ics to the crystalline regions that are packed tightly. research in pulp processing from various sources. For
Moreover, the activation step does not affect cellulose example, this process has been used to study solubility
crystallinity. The time required to unfold the chains is of wood-cellulose and native wheat straw material,
around 4–6 h. It has been shown that such unfolding membrane preparation and hydrogel film preparation.
can be achieved most effectively by swelling in a polar These are summarized in Table 4.
medium such as water followed by N,N-dimethylac- It can be understood from Table 4 that extensive
etamide at room temperature (Ramos et al. 2011). research has been done on various cellulose sources,
Literature has reported many dissolution mechanisms which is mostly from nature wastes, for example,
for different mixed inorganic/organic systems. sugar cane bagasse is one of the high research focused
As a part of the dissolution mechanism, the Cl- ion raw material for the regeneration processes. However,
(due to its basicity) interacts with cellulose which is the drawback of LiCl/DMAc is that cellulose has to be
followed by an exchange of DMAc in the lithium co- ‘‘activated’’ prior to being dissolved in the solvent
ordination sphere by cellulose hydroxyl groups. Fig- (Huber et al. 2012), which unfortunately makes it
ure 9 (Medronho and Lindman 2014) depicts that Cl- expensive and time-consuming. This ‘‘activation pro-
ions get accumulated along the cellulose chain which cess’’ usually involves a solvent exchange of the
results in an anionically charged polymer, and the cellulose or distillation of the DMAc/LiCl/cellulose
macro cation (Li–DMAc) acts as the counterion. (Olsson and Westm 2013). Moreover, the solubility of
Polymer molecules are then forced apart due to charge cellulose increases with bigger LiCl proportions. Also,
repulsion known as a polyelectrolyte effect. Addition- DMAc in combination with LiCl is also highly toxic,
ally, due to the high osmotic pressure, there is a corrosive and volatile, leading to a higher degree of
continuous influx of solvent which further disrupts the health and safety related issues; hence it has not been
cellulose binding forces until the polymer is solvated commercialized so far (Duchemin 2008; Olsson and
(Medronho and Lindman 2014). The advantage of the Westm 2013).

Fig. 9 Mechanism of the

cellulose dissolution in the
LiCl/DMAc solvent system

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Cellulose (2019) 26:2913–2940 2925

Table 4 Current research on LiCl/DMAc process

Sr. Process detail Results References
no.

1. Dissolve native wheat straw materials thought LiCl/ Efficient enzymatic hydrolysis can be achieved using Qi et al.
DMAc regeneration process the LiCl/DMAc system (2017)
2. Dissolution of sugar cane bagasse in LiCl/DMAC Biocompatible cellulose hydrogel film regenerated Nakasone
solution et al. (2016)
3. Dissolution of bacterial cellulose by phase Hemodialysis regenerated cellulose membrane (RBC) Yang et al.
inversion method in LiCl/DMAC solution (2014)
4. LiCl/DMAC solvent system was used to dissolve Modified cellulose (wood source) can be used for the Jing et al.
cellulose from a wood source synthesis of new functional materials (2007)

Lyocell process bis(trifluoro-methylsulfonyl)imide and 1-allyl-3-

methylimidazolium chloride ([Amim]Cl) (Sun
Lyocell is a relatively new type of regenerated 2010). It is known that ionic liquids have been
cellulosic fibre that is produced by a direct solution investigated either to dissolve or to create
spinning process based on the ability of the solvent to appropriate media for the functionalization of
dissolve cellulose (Rosenau et al. 2001; Sayyed et al. cellulose. For cellulose solubility, it has been
2018a). The name lyocell, given in 1989 for solvent- realized that the imidazolium type ionic liquids show
spun fibres (Borbély 2008), owes its genesis to the the best performance (Swatloski et al. 2002). These
Greek word lyein (meaning dissolve) from which ILs demonstrate good dissolution characteristics, and
comes ‘‘lyo’’ and to ‘‘cell’’ from cellulose. This name it is possible to prepare cellulose dopes in
was recognized as the generic name by BISFA concentration ranges that exhibit good spinnability.
(International Bureau for the Standardization of It is possible by using a dry–wet spinning process to
Rayon and Synthetic Fibres, Brussels) and the Federal achieve cellulose fibres with good physical properties.
Trade Commission (USA) (Rojas 2016). There are The IL process for the production of regenerated
many other organic polar solvents, like DMSO, DMF, cellulose fibres is illustrated in Fig. 10 (Cao et al.
DMAC, NDMA, HMPA, etc. which are used for 2009).
cellulose dissolution (Chavan and Patra 2004). But, Many ionic liquids have been reported in the
only two solvent systems have higher cellulose literature that can efficiently dissolve cellulose
dissolving capacity than these organic polar solvents (Derecskei and Derecskei-Kovacs 2006; Kosan et al.
i.e., ionic liquids and N-methylmorpholine-N-oxide 2008; Cao et al. 2009). Figure 11 shows a possible
(NMMO). The ionic liquid process comes under dissolution mechanism of cellulose in ionic liquids
lyocell technology, because cellulose solutions were (Cao et al. 2009). [Amim]Cl dissociates into individ-
spun according to the NMMO-based lyocell tech- ual Cl- and Amim? ions followed by association of
nique, that is, in a dry-jet wet spinning process where free Cl- ions with cellulose hydroxyl proton and
the liquid filament first passes through an air gap complexation of free cations with cellulose hydroxyl
before immersion in the coagulation bath where the oxygen. It disrupts hydrogen bonding in cellulose and
regenerated cellulosic fibres are formed (Vagt 2010; leads to the dissolution of cellulose. However, the role
Shirin et al. 2015). It is discussed in detail in the of individual ionic species is not clearly understood
following sections. (i.e., chloride, bromide, phosphate, sulfonate, imide,
and acetate) in the dissolution of cellulose (Medronho
Ionic liquid-based lyocell process Ionic liquids (ILs) and Lindman 2014).
are usually composed of imidazolium, pyridinium, or Apart from this, due to their high thermal and
organic ammonium cations and anions such as chemical stability, non-flammable nature and solubil-
chloride, bromide, or more complex structures such ity with many other solvent systems, ionic liquids
as hexafluorophosphate, trifluoromethyl sulfonate, remain effective for cellulose dissolution. Due to these

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2926 Cellulose (2019) 26:2913–2940

Fig. 10 ILs based cellulose

regeneration process

Fig. 11 Mechanism of
cellulose dissolution in Ionic
Liquids (AmimCl)

qualities, ionic liquids are a topic of growing interest On the other hand, imidazolium-based ionic liquid
in new cellulose processing and material technologies. solvents containing chloride anion probably limits
Table 5 summarizes the latest developments in ionic their practical application in processing and cellulose
liquid processing such as a super base-based ionic derivatization. This ionic liquid also requires high
liquid. The research for non-imidazolium-based sol- temperatures for cellulose dissolution, which possibly
vents, investigated at Aalto University and Helsinki results in thermal decomposition of ionic liquid and
University were emerging as a new cellulose spinning produces some organohalogenides (Gorman-Lewis
solvent consisting of a superbase/acid ion pair, which and Fein 2004). Additionally, the corrosive nature of
is relatively suitable for spinning stability, in which imidazolium chloride ionic liquid is also thought of as
1,5-diazabicyclo[4.3.0]non-5-enium acetate, [DBNH] a potential limitation to the future industrial applica-
[OAc], turned out to be the suitable superbase-based tion (Cao et al. 2009). Hence, there is a great scope to
ILs for air gap spinning (Lindman et al. 2015; Sixta improve the existing ionic liquid solvent system in
2015). However, further research and optimization is terms of halogen-free, non-toxic and low viscous
required to make this solvent more sustainable for solvent.
industrial application. For example, recovery or recy- On the other hand, the processing difficulties
cling system of super base-based ILs can be optimized related to cellulose dissolution, spinning of high
to avoid significant hydrolysis; otherwise, it may have viscosity cellulose dope and solvent recovery, needs
a more inhibitory effect on cellulose dissolution to be overcome for large-scale production. These
(Parviainen et al. 2015). issues directly impact the cost of production of ILs

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Cellulose (2019) 26:2913–2940 2927

Table 5 New developments in Ionic liquid process

Sr. Process detail Results References
no.

1. Captures all the possible phenomena governing the Developed a phenomenological model for Ghasemi
dissolution of semicrystalline polymers dissolution of semi-crystalline polymers et al.
Like, solvent penetration, the transformation from crystalline (2017a)
to amorphous domains, specimen swelling, and polymer
chain untangling
The model is validated for the case of cellulose fibre swelling
and dissolution in an ionic liquid
The diffusion coefficient of disentangled (dissolved)
cellulose chains (Dp) was calculated
2. The homogeneous spinning solution was prepared from Provide complimentary information on the Wanasekara
cylinder shaped cellulose at 80 °C microstructure of the fibres et al.
Fibres regenerated at 80 °C in water coagulation bath via an (2016)
air gap
The extrusion velocity was 5.7 m/min
Investigation of molecular deformation of the fibres with an
imaging microscope equipped with a thermoelectrically
cooled CCD detector
3. The bamboo pulp/ionic spinning solution obtained from Bamboo cellulose pulp exhibits better solubility Zhang et al.
bamboo pulp and ionic liquid at 80 °C in ([EMIM] Cl) salt than ([BMIM]DEP) ionic (2016)
Over here, bamboo pulp is activated with NaOH solution liquids
Rotational rheometer was used to measure the rheological
properties
4. Cellulose pulp ground by Wiley mill to produce Cellulose fibres produced from a particular Parviainen
homogeneous cotton-like material ionic liquid system et al.
Synthesis of the [DBNH][OAc] at 100 °C (2015)
Wood pulp was added in the synthesis of Ionic liquid for
dissolution; it required approximately 1 h
Regeneration of fibres from the homogeneous cellulose
solution
5. [DBNH][OAc] was first liquefied at 70 °C using a water bath Developed novel regenerated cellulose fibre Sixta (2015)
and then mixed with air-dried pulp to a final consistency of process
13 wt%
High-strength regenerated cellulose fibre by super base-
based ionic liquid
The mixture was stirred at 80 °C, and 10 rpm under reduced
pressure (50 mbar) and complete dissolution were
observed in less than 90 min
The solution was then filtered using a hydraulic press
filtration device (1–2 MPa, metal filter fleece, 5–6 lm
absolute fineness
The solution was shaped to the dimensions of the spinning
cylinder and solidified within 1–3 days after preparation

based fibres and hence the ILs regeneration process is improvement and optimization is needed to make this
costly as compared to other regeneration processes. process commercially successful.
Due to these limitations ionic liquid-based lyocell
process is still not commercialized and substantial

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2928 Cellulose (2019) 26:2913–2940

NMMO (N-methylmorpholine-N-oxide) based lyocell effluent produced is non-hazardous. The fibre manu-
process Aqueous NMMO solution based lyocell facturing process is shown in Fig. 12.
process was launched in 1980s on an industrial scale As described above, the lyocell fibres are produced
and this technology has been used currently in large- through cellulose solution after complete dissolution
scale production of cellulose fibres (Gavillon and of cellulose and regenerated in aqueous NMMO
Budtova 2007; Sayyed et al. 2018b). Under lyocell solvent. However, cellulose swelling phenomenon is
process, many efforts have been made to dissolve an essential pre-condition or process step for cellulose
cellulose directly in different solvents, and literature dissolution. During swelling, the solvent molecules
reports some successful results of the same (Fink et al. (NMMO and water) penetrate into the inter-crystalline
2001; Rosenau et al. 2001; Kim et al. 2004; Cao et al. and the intra-crystalline region of the cellulose
2009; Zhang et al. 2009; Le Moigne et al. 2010; Mäki- structure and swell the pulp fibres to a certain extent
Arvela et al. 2010; Agbor et al. 2011; Sen et al. 2013; (Sayyed et al. 2018b). Further, in the dissolution
Karimi and Taherzadeh 2016). Among these, the process, it is expected to thoroughly destroy the whole
aqueous NMMO solvent turned out to be the best crystalline structure of cellulose for formation of a
solvent system for cellulose dissolution. This route homogeneous solution (Medronho and Lindman
was developed to replace other polluting processes, 2014). In lyocell, swelling and dissolution mechanism
especially viscose process. Different companies have is based on the tertiary aliphatic amine N-oxide
come up with their brand names for the fibres hydrates system. NMMO has an active N–O moiety
produced from this technology such as Tencel with strongly dipolar character. Due to this, the
(Lenzing), Alceru (TITK Rudolstadt), Newell (Akzo oxygen groups form one or two hydrogen bonds with
Nobel), Acelon (Greencell) and Excel (Grasim). anhydrous glucopyranose unit (AGU) of cellulose. It
In the lyocell process, cellulosic fibres are obtained is known theoretically that three cellulosic H-bonds
from wood pulp after regeneration. Firstly, the wood- can be attacked simultaneously (Pinkert et al. 2010). It
pulp is dissolved in NMMO solvent which results in leads to the cleavage of intermolecular hydrogen
homogenous cellulose solution. Subsequently, this bonds of cellulose chains and facilitates the strong
solution is extruded (spun) through spinnerets in the complex formation between the cellulosic hydroxyls
form of filaments followed by solvent removal in a (–OH) and the NO group of NMMO. The process and
spin bath. The recovery of this solvent is more than interactions between the cellulose hydroxyl groups
99%, which helps in the minimization of the effluent. and NMMO are demonstrated in Fig. 13 (Pinkert et al.
The NMMO solvent itself is non-toxic and all the 2010).

Fig. 12 NMMO based

lyocell process

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Cellulose (2019) 26:2913–2940 2929

Fig. 13 NMMO—cellulose dissolution mechanism

Due to this strong interaction between the cellulose NMMO/cellulose/water. It causes detrimental effects,
and NMMO solvent, homogeneous cellulose solution such as degradation of cellulose, temporary or perma-
can be obtained, which changes the physical properties nent discoloration of the resulting fibres, decreased
and volumes of cellulose structure significantly. These product performance, pronounced decomposition of
changes are required for a cellulose polymer to be NMMO, increased consumption of thermal stabilizer
spinnable. During spinning, a polymer solution is (Rosenau et al. 2001). Furthermore, this fibre gener-
stretched in the air gap and regenerated in aqueous ates fibrillation during the wet state, which causes the
NMMO spin bath. It results in outstanding mechanical formation of longer crystalline and smaller amorphous
fibre properties compared to cotton or viscose rayon. regions in the fibre structure. This fibrillar structure is
Due to these unique properties of lyocell fibre, it responsible for the high fibre tenacity but low lateral
presents a perfect synthesis option between natural cohesion. Even though formation of fibrillation char-
and synthetic fibres (Fink et al. 2001). Thus, in the acteristic has been shown as an advantage in few
current years, large numbers of research are focused applications such as peach skin appearance, it has been
on NMMO based lyocell process to use in various proved to be disadvantageous for some other applica-
fields. Table 6 summarizes this research on the tions, such as the launderability of the product and
combination of new product obtained from lyocell difficulty to control the uniformity of color uptake
processes like Lyohemp, which is made from hemp during dyeing (Periyasamy and Khanum 2015). Due to
cellulose, new developments in antibacterial textiles this reason, in the initial year lyocell fibre was used
fibres and characterization methods. mainly in non-woven product applications (Woodings
As per above explanation, it can be concluded that 2003).
NMMO based lyocell process will be treated as the Moreover, in recent years new processing tech-
next-generation fibre research process for more sus- nologies and optimization in after treatment processes
tainable industrial development. Nevertheless, e.g. crosslinking (Zhang et al. 2006), crease-mark
NMMO lyocell process also has some disadvantages, reducing (Goswami et al. 2009), singeing before or
such as the occurrence of oxidative side reactions, after dyeing and enzymatic treatment (to prevent
thermal instability, or rather high temperatures fibrillation) resulted in considerable improvements in
required for the dissolution process (Mohd et al. the lyocell fibres. Therefore, lyocell fibres have now
2017) and uncontrolled fibrillation (Rosenau et al. been part of various kinds of applications for example
2001). As a result of this, several side reactions and textile products such as jeans, knits (Watkins 1999),
considerable by products are formed in the nonwovens (Macfarlane 1997), reinforcement

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2930 Cellulose (2019) 26:2913–2940

Table 6 New developments of NMMO based lyocell process

Sr. Process condition Developments References
no.

1. Mechanical pre-processed hemp fibre tow was Produced lyocell fibres from organically grown Paulitz et al. (2017)
treated by NaOH at 160 °C for 1 h hemp as LyohempTM cloth
A mixture of NaOH and surface-active additives
was applied as cooking liquor
Adjustment of cellulose pulp DP at 450 up to 700
using H2O2 subsequently and NaOCl
The pulp was dissolved at 100 °C, under a vacuum
and continuous mixer
Dry–wet spinning was used for dope extruding
through the holes of spinnerets
2. 10 g of chitosan added to 150 mL of 50 wt% Applications in antibacterial textiles fibres Li et al. (2016)
NaOH solution with mixing. Then it is stored at
- 18 °C for 48 h for alkalizing. After melting, it
was mixed with 20 mL isopropyl alcohol and
stirred for homogenization
Then 6 g chloroethanol is added under continuous
stirring at 80 °C for 12 h
After filtration and washing twice with alcohol, the
intermediate compound hydroxyethyl chitosan
(EHC) was yielded by vacuum-drying the solid
product
10 g EHC spread in 90 g of NMMO/H2O and
stirred at 90 °C for 12 h
Prepared EHC/cellulose polyblends dissolved in
50 wt% aqueous NMMO
3. Two separate series of simulations were Investigated effect of water content Rabideau and
conducted: NMMO/cellulose solution through Ismail (2015)
One at 1 wt% cellulose with a single unrestrained thermodynamics, structure, moreover, hydrogen
cellulose strand and bonding
Second at 15 wt% with 16 strands fixed in either a
crystalline or dissociated stat
The system is gradually heated to 373 K, at a rate
of 1 K/ps in the NPT ensemble at a pressure of
1 bar using a Nosé–Hoover thermostat and
barostat with coupling constants of 100 and
1000 fs, respectively
Using the 1 wt% simulations, we analyse the
hydrogen bonding between NMMO, water, and
cellulose. It was done using a set of geometric
criteria
4. The degree of polymerization in cuoxam solution Characterized the micro moreover, the Meister and Kosan
(DPCuoxam) was determined by capillary macroscopic structure of pulps and spinning (2015)
viscometry at 23 °C dopes, DP
Spinning dopes made by pre-dispersed wet pulp
(30% solid content) in aqueous NMMO (60%) at
100 °C
Obtained cellulose solutions are evaluated by
Refractive index

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Cellulose (2019) 26:2913–2940 2931

Table 6 continued
Sr. Process condition Developments References
no.
Undissolved particles by a polarizing microscope
Particle sizes and PSD by laser light diffraction
Dope rheology by oscillation rheometer
5. Cellulose dope contain 6–16 wt% cellulose, and Invention on lyocell fibre geometry, manufacturing (Jeong et al. 2017)
84–94 wt% NMMO techniques of various cross-sectional shapes and
Spinning carried out at temperature of 80–130 °C specific surface area
Outline the large number of spinneret holes
setting, so that large number of unit holes are
formed
Produced lyocell fibre comprising a monofilament
having a modified cross section and including
three protrusions
The number of holes that are included in the unit
hole are three
6. The lyocell fibre used organic salt in an amount Invention relates to the use of a lyocell fibre in wet (Opietnik et al.
from 0.1 to 50 wt%, preferably from 1 to or moist wipes for hygiene products, especially 2018)
10 wt%, especially preferred from 2 to 7 wt%, for disinfecting and sanitizing wipes for home,
based on the weight of the dry fibre food service, medical and other market areas
The quaternary ammonium salt employed for
making the wet or moist wipe is preferably a
quaternary ammonium chloride
Quaternary ammonium salt may be selected from
the group consisting of n-
alkylbenzyldimethylammoniumchloride (BAC
or ABDAC), di-n-alkyldim ethyl
ammoniumchloride (DDAC), n-
alkyldimethylethyl benzylammonium chloride
(ADEBAC), n-alkyltrimethylammonium
chloride, octyldecyldimethyl ammonium
chloride, and mixtures thereof

materials for composites (Seavey et al. 2001) and As observed from the above table, it can be said that
special papers such as cigar filters (Alwis and Taylor viscose, cellulose acetate, cuprammonium, and LiCl/
2001). After viscose process, lyocell is the only DMAc process are well developed but have environ-
commercialized process in textile industries. mental issues such as high toxicity, corrosiveness and
volatile nature of LiCl, leading to a higher degree of
health and safety related issues. Viscose process
Summary of regenerating processes releases a large amount of chemical discharge and
cuprammonium process has toxic effluents. Cellulose
It is imperative that new materials, composites, and acetate fabric causes air pollution during discoloration
manufacturing technologies are being continuously (Cohen et al. 2012). On the other hand, ionic liquid and
developed in the field of textiles which will allow the NMMO based lyocell process are eco-friendly.
industry to produce textiles that are environmentally Amongst the two, the ionic liquid process requires
improved and that meet the customer requirements. substantial improvement in identifying powerful halo-
Hence, it is necessary to find the potential growth in gen-free cellulose solvents with low melting point and
the regeneration process to fulfill the above require- low viscosity for commercialization.
ments. Hence, the derivatization and direct dissolution Hence, NMMO based lyocell process is by far one
processes are compared in terms of regenerated fibres of the most environment friendly and non-hazardous
property in Table 7. cellulose regeneration process. Also, as compared to

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2932 Cellulose (2019) 26:2913–2940

Table 7 Physical properties of different cellulose regenerated fibres

Evaluation Unit Derivatization process Direct dissolution process
terms
Viscose Cellulose Cuprammonium LiCl/DMAc Ionic liquid NMMO
acetate

Dry g/den 2.0–2.6 1.2–1.4 1.7–2.7 1.9–3.7 3.5–4.1 4.5–5.0

tenacity
Wet g/den 1.0–1.5 0.65–0.75 1.6–1.7 0.6–2.6 2.3–3.1 3.9–4.0
tenacity
Dry % 17–25 25–35 12–13 06–12 7–8 11–16
elongation
Wet % 21–30 35–45 26–27 8–18 09–12 16–18
elongation
Density gm/ 1.53 1.32 1.54 1.5 1.5 1.5
cm3
Moisture % 11–13 3.5–6.5 11–2.5 10–12 10–12 10–13
content
Refs. Hauru et al. Cook (1984) Hearle and Dawsey and Kosan et al. Hearle and
(2017) and and Pocien Woodings Mccormick (2008) and Woodings
Zhang et al. et al. (2001) (1990) and Hong Jiang et al. (2001) and
(2018) (2004) et al. (1998) (2012) Hauru et al.
(2017)

above explained regenerated cellulose fibres, NMMO Cellulose regeneration processes as discussed in the
based lyocell fibres have good fibre strength and other above section suggests that NMMO based lyocell
physical properties (Chavan and Patra 2004) as shown process is one of the recent technologies for textile
in Table 7. Therefore, lyocell fibres have numerous industries and it has great potential to fulfill the
advantages over conventional rayon fibres (Borbély environmental and customer requirements. However,
2008). The salient features of lyocell process are there are only few reports that have systematically
mentioned below: studied the effect of raw material, process parameters
on dope, overall process and fibre quality. One of the
1. Compared to the commonly used regenerated
most important factors affecting the lyocell process is
fibre, lyocell fibre involves less steps and chem-
the swelling and dissolution of cellulose in NMMO
icals for its manufacturing.
solution and lot of work is being done to understand
2. Solvent and water can be recycled in the lyocell
and improve the latter. The following section evalu-
process.
ates the mechanisms of cellulose swelling and disso-
3. Fibre production method is potentially more cost
lution in NMMO solution.
effective and faster than above regenerated
rayons.
4. Lyocell fibres has the unique characteristics of
Studies of cellulose swelling and dissolution
being soft and silky, lustrous and bulky touch.
in NMMO based lyocell process
5. A rich look stands out as the hallmark of its
aesthetics and very comfortable to wear (Chavan
Lyocell process has provided a versatile platform for
and Patra 2004; Gorji and Bagherzadeh 2016).
the extensive use of cellulose resources and has
6. Lyocell fabrics is more comfortable than other
allowed for the preparation of new cellulose-based
rayon’s, because, it has natural breathability and
materials with special properties. In this section, the
good moisture absorption (Firgo et al. 2006).
research progress in the field of swelling and disso-
7. Furthermore, lyocell fabric has good wicking
lution of cellulose with aqueous NMMO is reviewed.
abilities which keeps the skin dry and provides
The factors affecting the lyocell process are also
comfort (Gorji and Bagherzadeh 2016).
discussed.

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Cellulose (2019) 26:2913–2940 2933

Cellulose swelling in aqueous NMMO ballooning phenomenon occurs without disrupting

the primary layer of fibre. Whereas, heterogeneous
The swelling of cellulose in NMMO solvent has been swelling occurs between 76 and 81% NMMO con-
the subject of numerous investigations. Most research centration. Here in heterogeneous swelling the pri-
work is aimed at understanding swelling phenomena mary layer of fibre membrane (cell wall) bursts
and developing measurement techniques to determine (Fig. 14, mode 4) (Cuissinat and Navard 2006).
extent of swelling. In the same year (2006), another study of enzymatic
Generally, cellulose swelling is an essential pre- swelling by Navard and Cuissinat found peel off the
condition for cellulose dissolution. Therefore, it is primary wall of natural cellulose and because of this,
important to understand the swelling behaviour of the swelling phenomenon with ballooning disap-
cellulose in NMMO/water system. During swelling, peared. The primary wall of fibre gets destroyed due
the solvent molecules penetrate and expand the to enzymatic treatment and get easily broken, resulting
cellulose structure to a certain extent and significantly in reduced ballooning phenomenon during swelling
alter the biopolymer chain (Medronho and Lindman (Navard and Cuissinat 2006).
2014). However, certain mechanisms that are involved Le Moigne et al. also tested the effect of enzyme
at structural levels during the swelling and dissolution treatment on swelling mechanisms of cellulose fibres,
steps are still not well understood and controlled. For in the concentration range of 76–81% NMMO. Their
that reason, the complex phenomenon of swelling and study also showed that instead of swelling by
dissolution of cellulose fibres (such as the ballooning ballooning, fibres get fragmented and subsequently
or helical phenomenon) were discussed continuously. dissolution take place (Le Moigne et al. 2010).
Recent literature and studies have shown that the It should be noted that other than solvent concen-
swelling behavior of cellulose fibres are intensely tration, temperatures, cellulose type, swelling pre-
dependent on the solvent quality, temperature, cellu- treatment can impact on swelling and dissolution. For
lose origin, and additives or enzymes (Chanzy 1982; example, the ultrasound treatment through acoustic
Cuissinat and Navard 2006; Moigne and Navard cavitation improves the penetration of solvent in the
2010). Chanzy (1982) reported that the nature of cellulose chain (Sayyed et al. 2018a).
cellulose-NMMO interaction is based on water level Cuissinat et al. studied the swelling mechanism of
present in the NMMO solvent system and explained wood and cotton fibre in different solvent systems
the fibres swelling behavior depends on the origin of such as aqueous NMMO, aqueous NaOH, and ionic
the fibre-water level of the solvent and temperature liquids and compared different swelling modes. They
range. Based on this study, Cuissinat and Navard observed similar swelling mechanism for all the
(2006) had identified following five different regions systems (Cuissinat et al. 2008). In 2011, Spinu et al.
of swelling for wood and cotton fibres based on tested the swelling capacity of never-dried and dried
function of the concentration of the solvent: wood pulps (hardwood and softwood) and cotton
linters pulp. They found that the swelling capacity
1. no swelling and no dissolution,
depends on the origin of the fibres, type of aqueous
2. homogeneous swelling and no dissolution,
solvent and moisture percentage of fibres (Spinu et al.
3. large swelling by ballooning and partial
2011). Moigne and Navard (2010) also stated that fibre
dissolution,
morphology, wood type, pulping process and moisture
4. large swelling by ballooning, and then dissolution
percent of fibres affect swelling mechanism.
of the whole fibre,
More recently, the focus of swelling study has been
5. fast dissolution by disintegration into rod-like
shifted toward the development of mathematical
fragments (Cuissinat and Navard 2006).
model. Attempts have been made to develop a model
The attempted ways to explain these different describing swelling behavior, solvent penetration, and
regions of swelling and dissolution modes is graphi- change in structural morphology. Ghasemi et al.
cally given in Fig. 14. (2017b, c) developed the phenomenological model
It has also been reported that the cellulose fibres for swelling and dissolution in an ionic liquid solvent.
exhibit a homogeneous swelling between 70 and 75% Peng et al. (2017) developed the solvent diffusion
NMMO concentration. In homogeneous swelling, model of fibre swelling and investigated the difference

123
2934 Cellulose (2019) 26:2913–2940

Mode 2: Homogeneous swelling and no

Mode 1: No swelling and no dissolution
dissolution

Mode 3: Ballooning and partial

Mode 4: Balloon busting and then
dissolution
dissolution

Mode 5: Fibre disintegration into rod-like fragments

Fig. 14 Schematic drawing of different modes of a swollen fibre

between the swelling behavior of different cellulose (wood type and pulping process), temperature,
fibres. They found that, if the concentration of NMMO concentration on extent of swelling. In
NMMO/water solvent system is varying, the rate of addition to that the structural changes occurring in
swelling also changes. It means that, with decreasing pulp can also be captured with the help of sophisti-
NMMO concentration in solution, concentration dif- cated techniques such as scanning electron micro-
ference of solution inside and outside layer of fibres scope and XRD. The structural changes happening in
reduces. Due to this, its rate of swelling also reduces terms of gain or loss in individual fibre dimensions and
(Peng et al. 2017). Lot of quality work has been done loss or gain in amorphous and crystalline phase can be
till date to understand swelling phenomena, role of quantified with the help of these techniques. The
various influencing parameters and their interrela- knowledge generated through this will help in further
tions. However still, there is considerable scope for a optimizing downstream dissolution process condi-
consolidated study to understand effect of pulp type tions. In addition to this various possible pre-treatment

123
Cellulose (2019) 26:2913–2940 2935

techniques such as ultrasonication etc. can also be concentration and also used for determination of
considered to augment extent of swelling. A simple complex material characteristics (Meister and Kosan
mathematical model can also be developed based on 2015). Zhang et al. developed rheology-based analysis
this study. method for prediction of MW scale and MWD of
cellulose and investigated the effect of different
Cellulose dissolution in aqueous NMMO cellulose concentration on predicting results. How-
ever, when the cellulose concentration was high (i.e.,
Cellulose dissolution in aqueous NMMO solvent is the 13–16%), there was no significant effect observed on
topic of various investigations by a growing number of predicting results (Zhang et al. 2009). Collier et al.
researchers (Moigne and Navard 2010; Spinu et al. (2000) characterized the rheological behavior of
2011; Meister and Kosan 2015; Li et al. 2016; Peng different cellulose sources of NMMO based lyocell
et al. 2017). During the cellulose dissolution, NMMO solutions and identified that the viscous and elastic
solvent destroys the crystalline structure of cellulose behavior of lyocell solution was affected by cellulose
and results in a clear homogeneous solution where the concentration and molecular weight. Chae et al.
polymer chains are molecularly isolated. measured the three different modes of rheological
The structures of the cellulose upon dissolution properties of 11 and 13 wt% solutions of cellulose.
have been investigated intensively but are still not Also, investigated the difference between the slit
comprehensively understood. For that reason, various (capillary) rheometer and parallel plate (oscillatory)
scientific methods have been employed to characterize rheometer (Chae et al. 2002).
the same, such as thermal analysis, rheology, laser The elongation rheology of lyocell solution governs
diffraction and other unconventional techniques (Fujii high spinnability during the dry jet spinning process.
et al. 2001). In which, characterization of the rheo- Recently, several experimental measurements of the
logical property has received a lot of attention in elongational viscosity of lyocell have been reported.
recent years. The rheological investigation is an Nagarkar et al. (2006) measured the elongation
essential analysis tool, to determine the optimum viscosity of lyocell solution and proposed that by the
spinning conditions of cellulose solution before spin- use of semi-hyperbolic die and viscoelastic simula-
ning operation. Therefore, it is also essential to tions it is possible to determine the elongation
analyze both, oscillatory and elongational shear rhe- viscosity of lyocell solution. Petrovan et al. (2000)
ology because shearing rheology contributes in under- investigated the shear and elongational rheology of
standing the processing of solutions whereas lyocell solution at different temperatures. In another
elongational behavior influences fibre properties, study, the same group of authors Petrovan et al. (2001)
especially orientation and fibrillation (Chae et al. performed the elongational and shear rheology by
2002). using different degrees of polymerization (DP) of
In these regards, Li et al. investigated the rheolog- cellulose solution and characterize the dynamic
ical behavior of cellulose co-solution by both steady viscosity and effect of lyocell solution on elongational
and dynamic state rheology and determine the viscosity. However, the study of the extensional flow
spinnability of the cellulose co-solution. They demon- behavior of cellulose/NMMO solutions is very lim-
strated that in steady state the addition of ethylamine ited. It could be because experimental measurements
hydroxyethyl chitosan preserves the power-law flow of elongation viscosity present greater difficulties than
of cellulose in the aqueous NMMO solution (Li et al. the measurement of shear viscosity due to the effects
2016). Frank Meister and Birgit Kosan characterized of free surface (Schweizer 2000), de-cohesion
the chemical and physical approaches of lyocell (Spiegelberg and McKinley 1996), inertia, end effect
solution through rheological analysis, like zero shear (Spiegelberg et al. 1996), and cohesive failure (Petrie
viscosity, storage, and loss modulus and relaxation 1995).
time spectrum. They used the fundamental rheological Many articles have been published till date, dealing
data for investigation of the chemical structure of pulp with the cellulose solution characterization. However,
and suitability of pulp in cellulose solution. Zero shear the effect of pulp type and pulping process on rheology
viscosity was used to determine the effect of pulp of cellulose solution (shear and elongation viscosity)
degree of polymerization (DP) on different polymer can be extensively studied. In addition to that, above

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mention swelling study, including understanding the compared to the past 5 years, suggesting rapid pace of
effect of pulp and pulping process parameters on change. Due to developing technologies that have led
structural properties of pulp can be extended to to the evolution of improved fibre quality and devel-
understand the impact of all these parameters on opment of recyclable fibres, the lyocell fibre products
downstream cellulose solution (dope) preparation demand has escalated. As a result, the lyocell fibre
process and quality. market is set to grow from its current market value of
more than $850 million to over $1.5 billion by 2024; as
reported in the latest study by Global Market Insights,
Scope and future prospects of lyocell fibre Inc.
Further, favourable government regulations regard-
As compared to other processes, the lyocell process is ing the adoption of sustainable fibres for the textile
modern and advanced method of creating regenerated industry will drive lyocell fibre market by 2024. The
natural fibres from cellulose without polluting environ- growing online retail trading will further aid the growth
ment. The process recycles[ 99% of all the solvent used of this segment over the coming years. Companies
and is far more energy efficient than any other methods quickly adapting to this changing landscape are
of regeneration. However, there is a lot of scope for emerging as the top performers and earning attractive
further research to improve lyocell process and enhance revenues through sustainable transition, innovation,
its fibre properties. Therefore, more focused research on efficient pricing and sales execution strategies.
fibre quality (fibrillation issue), decrease in production Increases in both domestic and export-oriented
cost, increase in production rate and making the process revenues are observed for key players in the global
more sustainable and eco-friendly by lowering water Lyocell Fibre market. However, challenges such as
consumption should be done. increasing buyer bargaining power, emphasis on high-
Inspite of the above-mentioned research scope quality products at low costs are forcing significant
lyocell fibres have made its mark in the apparel and changes in the Lyocell Fibre supply chain.
fashion textile sector during its initial period of
commercialization. There has been a huge change in
the current industry scenario with lyocell fibres being Conclusions
sought after by the industrial and technical sectors
apart from apparel sector as they are also commonly It is essential for textile manufacturing to improve
used in the manufacture of various non-woven prod- industrial technologies to produce high-quality textile
ucts such as filters, wipes, and hygiene. Further, the fibres without much environmental impact. The
staple lyocell fibres are highly suitable for manufac- NMMO based lyocell process is one of the recent
turing thick fabric products such as carpets, blankets, technologies for textile industries, and it has great
coats, and rugs etc. The increasing demand for these potential to fulfill the environmental and customer
commodities from the colder countries will lead to requirements. The properties of lyocell fibres are
industry growth. appropriate for many textile applications.
Furthermore, the recent advances in the lyocell Pulp swelling, and dissolution steps play a critical
research such as functional lyocell fibres having anti- role in lyocell manufacturing process. It is clear from
bacterial property, flame retardant property, thermally this review that the solvent concentration strongly
stable fibres, super absorbent fibres, blend fibres and influences the swelling and dissolution of cellulose,
nano-structured fibres projects to better prospects of temperatures range, types of the pulp, forms of the
lyocell in the coming years. pulp (sheet, pulp fibre or powder) and source of the
According to a new market report published by pulp. Therefore, considerable attention is required
Credence Research ‘‘Global Lyocell Fibre Market towards the (1) swelling enhancement by other
Growth, Future Prospects and Competitive Analysis, possible treatment, (2) focused study on the swelling
2017–2025,’’ the Lyocell Fibre market is expected to mechanism and structural changes during slurry stage
expand at a CAGR (compound annual growth rate) of (3) simplified kinetic model for calculating the rate of
8.9% from 2017 to 2025. Hence, more growth swelling and (4) focused study on dissolution and
opportunities will turn up between 2018 and 2025 as rheological properties pivoted on raw material types.

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Acknowledgments The authors are grateful to Pulp and Fibre Dawsey TR, Mccormick CL (1990) The lithium chloride/
Innovation Centre (PFIC)—A Unit of Grasim Industries Ltd. dimethylacetamide solvent for cellulose: a literature
Aditya Birla Group Company for funding the Ph.D. program. review. J Macromol Sci C Polym Rev 30:405–440
We also would like to thank Institute of Chemical Technology Deo HT (2001) Ecofriendly textile production. Indian J Fibre
(ICT) for academic support. Text Res 26:61–73
Derecskei B, Derecskei-Kovacs A (2006) Molecular dynamic
studies of the compatibility of some cellulose derivatives
with selected ionic liquids. Mol Simul 32:109–115
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